A New Era for Microbial Corrosion Mitigation Using Nanotechnology: Biocorrosion and Nanotechnology [1st ed.] 9783030495312, 9783030495329

This book focuses on corrosion and microbial corrosion, providing solutions for these problems based on nanotechnology a

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A New Era for Microbial Corrosion Mitigation Using Nanotechnology: Biocorrosion and Nanotechnology [1st ed.]
 9783030495312, 9783030495329

Table of contents :
Front Matter ....Pages i-xviii
Basic Corrosion Fundamentals, Aspects and Currently Applied Strategies for Corrosion Mitigation (Basma A. Omran, Mohamed Omar Abdel-Salam)....Pages 1-45
The Catastrophic Battle of Biofouling in Oil and Gas Facilities: Impacts, History, Involved Microorganisms, Biocides and Polymer Coatings to Combat Biofouling (Basma A. Omran, Mohamed Omar Abdel-Salam)....Pages 47-99
Emphasis on the Devastating Impacts of Microbial Biofilms in Oil and Gas Facilities (Basma A. Omran, Mohamed Omar Abdel-Salam)....Pages 101-123
Corrosion and Biofouling Mitigation Using Nanotechnology (Basma A. Omran, Mohamed Omar Abdel-Salam)....Pages 125-157
Biologically Fabricated Nanomaterials for Mitigation of Biofouling in Oil and Gas Industries (Basma A. Omran, Mohamed Omar Abdel-Salam)....Pages 159-195
Back Matter ....Pages 197-201

Citation preview

Advances in Material Research and Technology

Basma A. Omran Mohamed Omar Abdel-Salam

A New Era for Microbial Corrosion Mitigation Using Nanotechnology Biocorrosion and Nanotechnology

Advances in Material Research and Technology Series Editor Shadia Jamil Ikhmayies, Physics Department, Isra University, Amman, Jordan

This Series covers the advances and developments in a wide range of materials such as energy materials, optoelectronic materials, minerals, composites, alloys and compounds, polymers, green materials, semiconductors, polymers, glasses, nanomaterials, magnetic materials, superconducting materials, high temperature materials, environmental materials, Piezoelectric Materials, ceramics, and fibers.

More information about this series at http://www.springer.com/series/16426

Basma A. Omran Mohamed Omar Abdel-Salam •

A New Era for Microbial Corrosion Mitigation Using Nanotechnology Biocorrosion and Nanotechnology

123

Basma A. Omran Petroleum Biotechnology Laboratory Processes Design and Development Department Egyptian Petroleum Research Institute Nasr City, Cairo, Egypt

Mohamed Omar Abdel-Salam Analysis and Evaluation Department Nanotechnology Research Center Egyptian Petroleum Research Institute Nasr City, Cairo, Egypt

ISSN 2662-4761 ISSN 2662-477X (electronic) Advances in Material Research and Technology ISBN 978-3-030-49531-2 ISBN 978-3-030-49532-9 (eBook) https://doi.org/10.1007/978-3-030-49532-9 © Springer Nature Switzerland AG 2020 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

Some things are worth waiting for….. I keep asking myself what it takes to be superior. I realized that desire, dedication, determination, focusing on my goal shall be the keys. I dedicate this work to the person who meant and continues to mean the world to me, My Mother. This is for you, Mom. Thanks for always being there for me in each step of the way. I lovingly dedicate this book to my husband, Mohamed Omar, my little boy, Mazen and to my new baby, Yassin. Thanks for your love, patience and endless support when I needed you. You kept pushing me to accomplish this work, I love you dears. This book is dedicated to my sister; Lamis and brother; Mohamed. I love both of you to the moon and back. Finally, this work is dedicated to the soul of my beloved father who is always in my heart. May Allah rest your soul in peace….To Allah we belong and to Allah we do return.

I love all of you and I am doing my best to deserve your love. Basma Ahmed Ali Omran

Preface

Petroleum, gas and oil industries in both developed and developing countries suffer a lot from the devastating consequences of corrosion and biofouling. Both problems arose since long time ago. The lethal deposition of microorganisms (bacteria and fungi) and macroorganisms (mussels, barnacles, mollusks, algae and invertebrates) along with other constituents results in impairment in the performance of industrial equipment and operations as well as decrease in the efficiency of service life machines. Besides the contamination of the produced products, loss of products, deleterious consequences which may be catastrophic to the working personnel and to the surrounding environment. Furthermore, presence of microbial consortium such as bacteria (aerobic and anaerobic), cyanobacteria, fungi and algae adhered to a metal via microbially produced extracellular polymeric matrix results in biofilm formation. Biofilms cause severe problems in a number of disciplines including healthcare industry, water treatment, freshwater systems, marine, medical implants and oil and gas industries. Mitigation of both corrosion and biofouling still represents a major challenge that faces researchers and engineers. Different mitigation strategies have been employed including; paints and coatings, employment of corrosion inhibitors and biocides. Chlorine, tributyltin, diuron, tetrakishydroxymethyl phosphonium sulfonate, benzyl trimethyl ammonium chloride, formaldehyde, glutaraldehyde, etc. are among the employed corrosion inhibitors and biocides. However, they are extremely toxic to the aquatic fauna and to the non-target benthic organisms. The consequences of using chemical based biocides are so intense. Hence, exploring anti-biofouling properties of natural sources and employment of nanoparticles (NPs) as alternatives is the need of the hour. This book has been written for readers, researchers and engineers who are interested in getting the latest information and published data concerning corrosion and

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biofouling. The book emphasizes the problems, the current and the new trends employed in combating corrosion and biofouling. Moreover, detailed data concerning the employment of nanotechnology and nanobiotechnology in treating and minimizing the severe effects of both problems are covered in this book. Nasr City, Cairo, Egypt

Dr. Basma A. Omran Researcher in Microbiology Dr. Mohamed Omar Abdel-Salam Researcher in Environmental Chemical Engineering

Contents

1 Basic Corrosion Fundamentals, Aspects and Currently Applied Strategies for Corrosion Mitigation . . . . . . . . . . . . . . . . . . . . . . . 1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2 Corrosion: Problem Definition . . . . . . . . . . . . . . . . . . . . . . . 1.3 Developments in Corrosion Science . . . . . . . . . . . . . . . . . . . 1.4 Impact of Corrosion on Economy and Life . . . . . . . . . . . . . 1.5 Forms of Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.5.1 Sweet Corrosion or CO2 Corrosion . . . . . . . . . . . . . 1.5.2 Sour Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.5.3 Uniform or General Corrosion . . . . . . . . . . . . . . . . 1.5.4 Localized Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 1.5.5 Pitting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 1.5.6 Crevice Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 1.5.7 Galvanic Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 1.5.8 Erosion Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 1.5.9 Oxygen Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 1.5.10 Selective Leaching or Dealloying . . . . . . . . . . . . . . 1.5.11 Microbial Corrosion . . . . . . . . . . . . . . . . . . . . . . . . 1.6 Engineering Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.6.1 Carbon Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.6.2 Mild Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.6.3 Ferrous and Steel Alloys . . . . . . . . . . . . . . . . . . . . 1.6.4 Non-ferrous Metals . . . . . . . . . . . . . . . . . . . . . . . . 1.7 Corrosion Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.7.1 Metal Sample Preparation . . . . . . . . . . . . . . . . . . . . 1.7.2 Corrosion Test Medium . . . . . . . . . . . . . . . . . . . . . 1.7.3 Gravimetric and Electrochemical Measurements . . . . 1.8 Corrosion Mitigation Strategies . . . . . . . . . . . . . . . . . . . . . . 1.8.1 Paints and Coatings . . . . . . . . . . . . . . . . . . . . . . . .

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1.8.2 Corrosion Inhibitors . . . . . 1.8.3 Cathodic Protection . . . . . 1.8.4 Use of Corrosion Resistant 1.9 Conclusions . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . .

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2 The Catastrophic Battle of Biofouling in Oil and Gas Facilities: Impacts, History, Involved Microorganisms, Biocides and Polymer Coatings to Combat Biofouling . . . . . . . . . . . . . . . . . . . 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Definition and Impacts of Biofouling . . . . . . . . . . . . . . . . . . 2.2.1 Medical Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2 Marine Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3 Industrial Sector . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 Microbial Biofouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.1 History of Research on Microbial Corrosion . . . . . . 2.3.2 Mechanism and Microorganisms Involved in Biotic/Aerobic Microbial Corrosion . . . . . . . . . . . 2.3.3 Mechanism and Microorganisms Involved in Abiotic/Anaerobic Microbial Corrosion . . . . . . . . 2.4 Macrobial Biofouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5 Factors Affecting Biofouling Process . . . . . . . . . . . . . . . . . . 2.6 Metals Susceptible to Biofouling . . . . . . . . . . . . . . . . . . . . . 2.6.1 Copper and Its Alloys . . . . . . . . . . . . . . . . . . . . . . 2.6.2 Carbon Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.3 Stainless Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.4 Aluminium-Based and Nickel-Based Alloys . . . . . . . 2.6.5 Titanium-Based Alloys . . . . . . . . . . . . . . . . . . . . . . 2.7 Analytical Techniques and Tools Used for the Assessment of Microbial Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7.1 Microbiological Assays . . . . . . . . . . . . . . . . . . . . . 2.7.2 Electrochemical Assays . . . . . . . . . . . . . . . . . . . . . 2.7.3 Surface Analysis Assays . . . . . . . . . . . . . . . . . . . . . 2.7.4 Molecular Microbiological Assays . . . . . . . . . . . . . . 2.7.5 Other Spectroscopic Assays . . . . . . . . . . . . . . . . . . 2.8 Use of Biocides to Combat Biofouling . . . . . . . . . . . . . . . . . 2.8.1 Oxidizing Biocides . . . . . . . . . . . . . . . . . . . . . . . . . 2.8.2 Non-oxidizing Biocides . . . . . . . . . . . . . . . . . . . . . 2.9 Recent Research Towards Green Biocides . . . . . . . . . . . . . . 2.9.1 Extracts of Plant Biomaterials as Biocides . . . . . . . . 2.9.2 Micro- and Macro-Algae and Seaweeds . . . . . . . . . . 2.9.3 Inhibition of Quorum Sensing to Combat Biofouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.9.4 Biofouling Inhibition by Microorganisms . . . . . . . . .

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2.10 Use of Polymer Coatings to Combat Biocorrosion . . . . . . . . . . . 2.11 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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3 Emphasis on the Devastating Impacts of Microbial Biofilms in Oil and Gas Facilities . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2 Biofilm Definition and Composition . . . . . . . . . . . . . . . . 3.3 Developmental Stages of Biofilms . . . . . . . . . . . . . . . . . 3.4 Estimated Economical Costs Due to Biofilm Formation in Oil and Gas Industries . . . . . . . . . . . . . . . . . . . . . . . 3.5 Techniques Employed for Biofilm Characterization . . . . . 3.5.1 Confocal Laser Scanning Microscopy (CLSM) . 3.5.2 Scanning Electron Microscopy (SEM) . . . . . . . . 3.5.3 Cryo-Electron Microscopy (EM) . . . . . . . . . . . . 3.5.4 Scanning Transmission X-Ray, Atomic Force, Soft X-Ray and Digital Time-Lapse Microscopy 3.5.5 Fourier Transform Infrared, Nuclear Magnetic Resonance and Raman Spectroscopy . . . . . . . . . 3.6 Characterization of EPS . . . . . . . . . . . . . . . . . . . . . . . . 3.7 Multiple Roles of Biofilms in Microbial Corrosion . . . . . 3.8 Prevention of Biofilm Formation . . . . . . . . . . . . . . . . . . 3.8.1 Incorporation of Antimicrobial Nanomaterials . . 3.8.2 Polymer Coatings . . . . . . . . . . . . . . . . . . . . . . . 3.8.3 Naturally Occurring Antibacterial Surfaces and Their Biomimetic Counterparts . . . . . . . . . . 3.8.4 Anti-adhesive Surfaces . . . . . . . . . . . . . . . . . . . 3.9 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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4 Corrosion and Biofouling Mitigation Using Nanotechnology . 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2 Metal Nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.1 Zero Valent Iron Nanoparticles (ZVI) NPs . . . . . 4.2.2 Gold Nanoparticles (AuNPs) . . . . . . . . . . . . . . . 4.2.3 Silver Nanoparticles (AgNPs) . . . . . . . . . . . . . . 4.2.4 Cobalt Nanoparticles (CoNPs) . . . . . . . . . . . . . . 4.2.5 Copper Nanoparticles (CuNPs) . . . . . . . . . . . . . 4.3 Carbon Based Nanomaterials (NMs) . . . . . . . . . . . . . . . 4.3.1 Fullerenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3.2 Carbon Nanotubes (CNTs) . . . . . . . . . . . . . . . . 4.4 Metal Oxide Nanoparticles . . . . . . . . . . . . . . . . . . . . . . 4.4.1 Cobalt Oxide NPs . . . . . . . . . . . . . . . . . . . . . . 4.4.2 Iron Oxide Nanoparticles (IO) NPs . . . . . . . . . .

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4.4.3 Zinc Oxide Nanoparticles (ZnO NPs) . . . . . . . . . . . 4.4.4 Titanium Oxide NPs (TiO2 NPs) . . . . . . . . . . . . . . . 4.4.5 Cerium Oxide Nanoparticles (CeO2) NPs . . . . . . . . 4.5 Nanoparticle Synthesis Approaches . . . . . . . . . . . . . . . . . . . 4.5.1 Top-Down Approach . . . . . . . . . . . . . . . . . . . . . . . 4.5.2 Bottom-Up Approach . . . . . . . . . . . . . . . . . . . . . . . 4.6 Applications of Nanotechnology Science in Gas and Oil Industries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.6.1 Application of Nanotechnology in Drilling and Hydraulic Fracturing of Fluids . . . . . . . . . . . . . 4.6.2 Formulation of Nano-Emulsions for Cement Spacers via Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . 4.6.3 Application of Nanotechnology in Operations’ Logging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.6.4 Control of Formation Fines During Production via Nanotechnology . . . . . . . . . . . . . . . . . . . . . . . . 4.6.5 Hydrocarbon Detection Using Nanotechnology . . . . 4.6.6 Enhanced Oil Recovery Applications . . . . . . . . . . . . 4.6.7 Application of Nanotechnology in Corrosion and Biofouling Inhibition . . . . . . . . . . . . . . . . . . . . 4.7 Conclusions and Challenges Facing Nanotechnology in Oil and Gas Industries . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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5 Biologically Fabricated Nanomaterials for Mitigation of Biofouling in Oil and Gas Industries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2 Definition of Nanobiotechnology . . . . . . . . . . . . . . . . . . . . . . 5.3 Biological Entities Employed for Generation of NPs . . . . . . . . 5.3.1 Use of Microorganisms for Production of Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3.2 Biological Synthesis of NPs Using Algae . . . . . . . . . 5.3.3 Use of Plant Extracts for Nanoparticle Synthesis (Phytonanotechnology) . . . . . . . . . . . . . . . . . . . . . . . 5.3.4 Use of Agro-Industrial Wastes for Nanoparticle Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4 Critical Parameters Affecting the Biological Synthesis of NPs . 5.5 Employment of Biologically Synthesized Nanoparticles as Biocides and Corrosion Inhibitors . . . . . . . . . . . . . . . . . . . 5.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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Glossary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197

Abbreviations

2D 2-MCP 3D ADBAC AERS AFM AgNO3 AgNPs Ag-PNC AHL AI-2 ALD AMPS AP APB APS APTES ARTP ASM ASTM ATCC ATP ATR-FTIR AuNPs AZC BHI bio-Ag0 BKC BNPB CA

Two Dimensional 2-Mercaptopyridine Three Dimensional Alkyldimethylbenzylammonium Chloride Alkaloids Extract of Retama Seeds Atomic Force Microscope Silver Nitrate Silver Nanoparticles Silver Polymer Nanocomposite N-Acyl Homoserine Lactone Autoinducer 2 Atomic Layer Deposition 2-acrylamido- 2-methylpropane sulfonic acid Attack Phase Acid Producing Bacteria Adenosine 5’-phosphosulfate 3-Aminopropyltriethoxysilane Atom Radical Transfer Polymerization American Society of Metals American Society for Testing and Materials American Type Culture Collection Adenosine Triphosphate Attenuated Total Reflection-Fourier Transform Infrared Gold Nanoparticles Apcomin zinc chrome Brain Heart Infusion Biogenic Silver Nanoparticles Benzalkonium Chloride 1,4-Bis (4-Nitrophenoxy) Benzene Contact Angle Measurements

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CASTAN CDs CDT CeO2 NPs CITCE CLSM CMC CNTs CoNPs CPVC CR CRAs CS CSTET CTAC CuNPs CZNC-10 DBNPA DC DCOIT DDMP DGGE DI DLC DLS DMO DMSP DNA Dsr DWCNTs EC Ect EDTA EDX EEPG EIS EJTLE ELIZA EM EOCP EOR EPA EPM

Abbreviations

Cashew Nut Testa Tannin Carbon dots Cathodic Depolarization Theory Cerium Oxide Nanoparticles Comite International de Thermodynamique et Cin Etique Electrochimique Confocal Laser Scanning Microscope Critical Micelle Concentration Carbon Nanotubes Cobalt Nanoparticles Critical Pigment Volume Concentration Corrosion Rate Corrosion Resistant Alloys Carbon Steel Cryo-Scanning Transmission Tomography 1-(3-Chloroallyl)-3, 5, 7-Triaza-1-Azoniaadamantane Chloride Copper Nanoparticles Chitosan-ZnO NPs at 10% Initial ZnO Loading 2, 2-Dibromo-3-Nitrilopropionamide Direct Current 4, 5-dichloro-2-octyl-4-isothiazolin-3-one 5-dihydroxy-6-methyl-4H-pyran-4-one Denaturing Gradient Gel Electrophoresis Deionized Water Diamond Like Coating Dynamic Light Scattering 4, 4-Dimethyloxazolidine Dimethylsulphopropionate Deoxyribonucleic Acid Dissimilatory Sulfite Reductase Double-Walled Carbon Nanotubes European Commission Electron Cryotomography Ethylenediamine Tetraacetic Acid Energy Dispersive X-Ray Spectra Ethanol Extract of Piper guinensis Electrochemical Impedance Spectroscopy Eriobotrya japonica thunb leaf extract Enzyme Linked Immunosorbent Assay Cryo-Electron Microscopy Open Circuit Potential Enhanced Oil Recovery Environmental Protection Agencies Extracellular Polymeric Matrix

Abbreviations

EPNG EPR EPS ESEM eV Fcc Fe-EPS FESEM FIB FIB-SEM FISH FTIR GAE GAIN GC-MS GMZnO-Si GNP GO GO-Ag GP GSOB GUPCO HCCs HIC HIV HMF hNRB HPF HPLC HPLC-MS HPLC-Q-TOF-MS HRTEM ICCP Icorr ICP-MS ICPs IE% IEP IOB ISE ISO Kan-AuNPs

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El Paso Natural Gas Electron Paramagnetic Resonance Extracellular Polymeric Substances Environmental Scanning Electron Microscopy Electron Volt Face Centered Cubic Iron-Extracellular Polymeric Substance Field Emission Scanning Electron Microscope Focused Ion Beam Focus Ion Beam Scanning Electron Microscopy Fluorescent in situ Hybridization Fourier Transform Infrared Spectroscopy Garlic Extract Global Agricultural Information Network Gas-Chromatography Mass Spectroscopy Zinc Oxide-Silica Nanohybrid Based Sustainable Geopolymer Gross National Product Graphene Oxide GO Sheets Decorated with AgNPs Growth Phase Green Sulfur-Oxidizing Bacteria Gulf of Suez Petroleum Company Hydrophilic Carbon Clusters Hydrogen Induced Cracking Human Immune Deficiency Virus 5-hydroxymethylfurfural Heterotrophic Nitrate Reducing Bacteria High Pressure Freezing High Performance Liquid Chromatography High Performance Liquid Chromatography-Mass Spectroscopy High-Pressure Liquid Chromatography Coupled with Quadrupole Time-Offlight Mass Spectrometry High Resolution Transmission Electron Microscope Impressed Current Cathodic Protection Corrosion Current Density Inductively Coupled Plasma Mass Spectrometry Inherently Conducting Polymers Inhibition Efficiency Percentage Isoelectric Point Iron Oxidizing Bacteria International Society of Electrochemistry International Standardization Organization Kanamycin-Capped AuNPs

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KPS LC-MS LEO LPR MAPLE MAR MB MBA MBC MBEC MBF MBIC MBO MBT MCFF MCRs MF MgO NPs MIC MIT MMMs MMTS MMTSO MOB MPC-b-MPS MPN MPT mpy MRI MRSA MRSE MS MSSA MWCNTs NIAC Ni-P NIPAm NMR NMs NNI NPs NRB NSP-GO

Abbreviations

Potassium Persulfate Liquid Chromatography-Mass Spectrometry Lemon Grass Essential Oil Linear Polarization Resistance Morus Alba Pendula Leaves Extract Microautoradiograghy Methylene Blue N, N-methylenebisacrylamide Minimum Bactericidal Concentration Minimum Biofilm Eradication Concentration Marine Biofilming Bacteria Minimum Biofilm Inhibitory Concentration 3, 30-methylenebis (5-methyloxazolidine) 2-mercaptobenzothiazole Mycelial Cell-Free Filtrate Multicomponent Reactions Melamine Formaldehyde Magnesium Oxide Nanoparticles Minimum Inhibitory Concentration Massachusetts Institute of Technology Molecular Microbiological Methods S-methyl methanethiosulphinate Methyl Methane Thiosulphinate Manganese Oxidizing Bacteria 2-methacryloyloxy ethyl phosphorylcholine-b-3-(trimethoxysilyl) propyl ethacrylate Most Probable Number 2-Amino-4-(4-Methoxyphenyl)-Thiazole Mils Per Year Magnetic Resonance Imaging Methicillin Resistant Staphylococcus aureus Methicillin Resistant S. epidermidis Mass Spectrometry Methicillin Sensitive S. aureus Multi-Walled Carbon Nanotubes Nano Iron Oxide Impregnated Alkyd Coating Nickel-Phosphorous N-isopropylacrylamide Nuclear Magnetic Resonance Nanomaterials National Nanotechnology Initiative Nanoparticles Nitrate Reducing Bacteria Nitrogen, Sulfur and Phosphorous with Graphene Oxide Nanostructure

Abbreviations

OBM OCB OCP OFAT OOMW-NPh OOMW-Ph PAA PANI PANI/G PBS PBT PCB PCR PDI PDMS PDVF PEG PEMA PES PNZ ppb ppm PPy Psi PSOB PTFE PVA PVC PZC qPCR QPE QS QSI QUATS R&D Rct REACH RO ROS Rp SACP SAEV SASS SCC

xvii

Oil Based Mud Oxidized Carbon Black Open Circuit Potential One-Factor-at a-Time Technique Olive Oil Mill Wastewaters Non Phenolic Olive Oil Mill Wastewaters Phenolic Peracetic Acid Polyaniline Polyaniline-Graphene Nanocomposite Phosphate Buffer Saline Polythiophene Polychlorinated Biphenyl Polymerase Chain Reaction Polydispersed Index Polydimethylsiloxane Polyvinylidene Fluoride Polyethylene Glycol Poly Ethyl Methacrylate Polyethersulfone Polyaniline-Zinc Oxide Hybrid Nanocomposite Part Per Billion Part Per Million Polypyrrole Pounds Per Square Inch Purple Sulfur-Oxidizing Bacteria Polytetrafluoroethylene Polyvinyl Alcohol Polyvinylchloride Point of Zero Charge Quantitative Polymerase Chain Reaction Quince Pulp Extract Quorum sensing Quorum Sensing Inhibition Quaternary Ammonium Compounds Research and Development Charge Transfer Resistance Registration, Evaluation, Authorization, and Restriction of Chemicals Reverse Osmosis Reactive Oxygen Species Polarization Resistance Sacrificial Anode Cathodic Protection Saudi Aramco Energy Ventures Super Austenitic Stainless Steel Stress Corrosion Cracking

xviii

SEM SEM-EDX SERS SKP SOB SO-NRB SPA SPR SRB SS STXM SWCNTs SXT TBT TEM TEOS TEPES TGA TGBAPB THNM THPS TMV TOAg-NPs ToF-SIMS TPP UF USA USDA UV UV/Vis VFAs VOC VRSA XPS XRD ZnO NPs ZnO NRs ZOI ZVI

Abbreviations

Scanning Electron Microscope Scanning Electron Microscopy-Energy Dispersive X-Ray Surface Enhanced Raman Spectroscopy Scanning Kelvin Probe Sulfur-Oxidizing Bacteria Sulfide-Oxidizing, Nitrate Reducing Bacteria Single Particle Analysis Surface Plasmon Resonance Sulphate Reducing Bacteria Stainless Steel Scanning Transmission X-Ray Microscopy Single-Walled Carbon Nanotubes Soft X-Ray Tomography Tributyltin Transmission Electron Microscope Tetraethoxysilane Triethoxypentylsilane Thermogravimetric Analysis Tetraglycidyl 1, 4-Bis (4-Amine-Phenoxy) Benzene Tris (Hydroxymethyl) Nitromethane Tetrakis Hydroxymethyl Phosphonium Sulfate Tobacco Mosaic Virus The derived AgNPs from T. ornata Time of Flight-Secondary Ions Mass Spectrometry Tripolyphosphate Ultrafiltration United States of America United States Department of Agriculture Ultra Violet Ultraviolet/Visible Spectrophotometry Volatile Fatty Acids Volatile Organic Compounds Vancomycin Resistant Staphylococcus aureus X-Ray Photoelectron Spectroscopy X-Ray Diffraction Zinc Oxide Nanoparticles Zinc Oxide Nano-Rods Zone of Inhibition Zero Valent Iron Nanoparticles

Chapter 1

Basic Corrosion Fundamentals, Aspects and Currently Applied Strategies for Corrosion Mitigation

Abstract Metallic materials represent the most widely used type of materials mainly in mechanical engineering, construction and industrial disciplines. Despite, the importance of alloys and metals, their utilization is constrained due to the devastating problem of corrosion. The destructive damage in the properties of metals is referred to as corrosion. Such damage may take place by either chemical (dry corrosion) or electrochemical (wet corrosion) reactions with the environment surrounding the metal. Corrosion causes catastrophic impairment to metals and alloys. Corrosion damage appears in many forms including; uniform corrosion attack, crevice corrosion, galvanic corrosion, pitting, erosion corrosion, inter-granular corrosion, stress corrosion cracking and selective leaching (dealloying). This results in severe economic consequences represented in repairing and replacing the corroded substrates, loss of products, release of toxic products to the environment in addition to severe health effects. This chapter emphasizes corrosion concept, historical incidence of corrosion, different types of corrosion, materials susceptible to corrosion and the impact of corrosion prevalence. Furthermore, a spot upon the usual tests that are carried out to detect corrosion is also introduced. Besides, this chapter focuses on the current and new preventative strategies that are employed to inhibit corrosion such as paints, cathodic protection, coatings as well as corrosion inhibitors. Keywords Corrosion · Economic impact · Forms of corrosion · Corrosion tests · Prevention and control · Coatings · Corrosion inhibitors · Green inhibitors

1.1 Introduction Since the early use of metals, damage caused by corrosion has accompanied humanity since many thousands of years ago. It is a common phenomenon around the globe. Corrosion is an invasive process and it is usually existed at important sites of a system operation. Both developing and developed countries suffer from the consequences of corrosion which in turn results in loss in the gross national product (GNP). One of the most famous misunderstandings concerning corrosion is the confusion between corrosion and rusting. In fact, all forms of rusting are corrosion but not all types of © Springer Nature Switzerland AG 2020 B. A. Omran and M. O. Abdel-Salam, A New Era for Microbial Corrosion Mitigation Using Nanotechnology, Advances in Material Research and Technology, https://doi.org/10.1007/978-3-030-49532-9_1

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corrosion are rusting. Indeed, if ferrous alloys (for instance steels) experience corrosion, it can be an example of rusting. Conversely, aluminum and copper corrode but they do not get rusted. Another important confusion is that non-metals such as composites, concrete, polymers and glass do not corrode. Precisely, non-metals are only exposed to deterioration and degradation as both processes are physical processes in which no ion exchange takes place. Generally, materials’ degradation takes place through three well known routes including; fracture, corrosion and wear. Fracture is linked to mechanical operations that break bonds; corrosion is usually related to chemical processes that cause breaking in chemical bonds, while wear is related to motions that cause bondage break. However, they are all interconnected processses as chemical environments speed up fractures and wear and vice versa (Rummel and Matzkanin 1997). Humans have been trying since a long ago to understand and monitor metallic corrosion. Metals become unstable when existed in aquatic as well as gaseous environments for instance sulfur-containing gases, acid vapors, ammonia gas and formaldehyde gas. Corrosion process is electrochemical in nature and very similar to that of batteries (Dai et al. 2017). When metal atoms are exposed to an aqueous environment, they release electrons, and then the metals become positively charged ions to establish a complete electrical circuit. Although there are numerous routes for combating corrosion damage, the best control methodology relies on the early diagnosis and prevention of the problem (Melchers 2019). However, in many cases such control methods are somehow difficult to be applied as for example in oil and gas industries as the defected systems may exist at remote sites and at giant depths. Sometimes, even at successful business, companies’ major corrosion failures cannot be endured, especially failures which affect humans, working personal, mortalities; unpredicted shutdowns and severe environmental contamination. Corrosion also leads to failures in plant infrastructure as well as equipment which are usually expensive to fix. Furthermore, contamination and/or loss of products takes place which in turn leads to environmental pollution. These are just few reasons that clarify why great efforts are dedicated to corrosion monitoring at both the design and operational stages. Henceforth, decisions concerning the maintenance of an operating system and its components are governed by the accurate assessment of the circumstances that led to the occurrence of corrosion. By getting such information, wise decisions can be taken into action regarding the expenses, the required steps to repair and further to avoid such severe consequences of corrosion.

1.2 Corrosion: Problem Definition In 1964, the American Electrochemical Society defined corrosion as the “destruction of a metal by chemical or electrochemical reactions with its environment” (Robertson and Chilingar 2017). Most corrosion reactions are electrochemical processes (Maab and Peibker 2011). The word “corrosion” is derived from a Latin word “rodere” that means gnawing and the Latin word corrodere which means “gnawing into pieces”

1.2 Corrosion: Problem Definition

3

(Sastri 2011). Corrosion occurs in our daily life in several forms, for instance pipes, automobiles, shovels, pots and pans. Corrosion is a costly materials science problem. Metallic corrosion has been a problem since common metals were first put into use. In natural circumstances, most metals tend to return to their chemically oxidized stable form in which they often exist in nature during the corrosion process. The destruction of metals by corrosion takes place by either direct chemical attack at high temperatures in dry environments or by electrochemical processes at decreased temperatures in a moist environment (Robertson and Chilingar 2017). Furthermore, corrosion occurs due to re-oxidation of metals to more stable forms in which they were originally existed in nature such as oxides, sulfides, carbonates or sulfates. Corrosion is usually associated with electric current flow via an electrolyte between two different points on metal surface because of the difference in either potential or voltage. The electrolyte medium may be moist soil, water or a moisture film on metal surface. For a corrosion process to proceed, four basic components are required for the electrochemical cell to begin working. These four components are: • • • •

Electrolyte medium which is required for the passage of ionic current, Anode where an oxidation reaction (corrosion) takes place, Cathode where a reduction reaction occurs, External passage for the released electrons.

The most characteristic feature of most corrosion processes is that oxidizing and reductive reactions take place at separate locations on the metal. This occurs because metals are conductive. Hence, this allows electrons to flow through the metal from the anodic to cathodic sites. Anodic sites tend to be existed at specific locations in the metal while the cathodic sites appear in almost any part within the metal. It is important to mention that presence of water is vital for the transportation of ions to and from the metal, even in the form of a thin film of moisture. Corrosion often begins via a two-step process. First, metal ions dissolve in the moisture film and the resultant electrons migrate to another location; where electrons are utilized by a depolarizer. The most common depolarizer is oxygen. Afterwards, the generated hydroxide ions react with the Fe2+ and form the mixture of hydrous iron oxides which appears as rust (Eqs. 1.1–1.4) (Fig. 1.1). The anodic reaction appears as: Fig. 1.1 A schematic representation for the occurrence of metal corrosion

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Fe(s) → Fe2+ + 2e−

(1.1)

While the cathodic reaction may involve one of the following steps; (a) reduction of oxygen gas or reduction of protons or metal ion reduction, where M is a metal. O2 + 2H2 O + 4e_ → 4OH− H+ + e− →

1 H2 (g) 2

M2 + 2e− → M(s)

(1.2) (1.3) (1.4)

1.3 Developments in Corrosion Science During the period of Gupta Dynasty from 320 to 480 CE, production of iron in India reached high levels of production, as confirmed by the Dhar Pillar which contains approximately 7000 kg of iron (Sastri 2011). The presence of such pillar indicated that iron production from oxide ore was a common process, and people who worked in establishing this iron pillar were aware of the reverse oxidation reaction of iron into iron oxide. Furthermore, the Greeks used copper nails coated with lead to construct lead covered decks for ships (Sastri 2011). Romans also managed to protect iron by tar and bitumen. In 1675, two important publications introduced by Robert Boyle (1627–1691) contributed to the development of corrosion science and they were “Of the Mechanical Origin of Corrosiveness” and “Of the Mechanical Origin of Corrodibility” (Hackerman 1993). Late at the nineteenth century, the discovery of galvanic cells (Lynes 1951) and Davy’s theory that clarified the relation between electricity and chemical alterations resulted in understanding some of the basic corrosion principles (Davy 1800). Some of the most leading organizations in corrosion science are: American Society for Testing Materials (ASTM), American Society of Metals (ASM), Corrosion Division of the Electrochemical Society, National Association of Corrosion Engineers, Comite international de thermodynamique et cin etique electrochimique (CITCE), International Society of Electrochemistry (ISE), International Corrosion Council, The Corrosion Group of the Society of Chemical Industry, Belgium Centre for Corrosion Study, Commission of Electrochemistry, National Corrosion Centre (Australia), Australian Corrosion Association, Chinese Society of Corrosion and Protection and National Association of Corrosion Engineers (Canada). Some of the industrial companies which established their own research laboratories such as U.S. Steel, DuPont, International Nickel Company and Aluminum Company of America.

1.4 Impact of Corrosion on Economy and Life

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1.4 Impact of Corrosion on Economy and Life Metal corrosion is a major challenge from which the world economy has suffered a lot. Economics of corrosion are related to capital costs which may include replacement of buildings and equipment and the need for extra tools. Also, control costs include the need for repair and maintenance. Moreover, design costs may be required for carrying out special operations and getting new materials for construction. Associated costs may involve product loss, technical support and insurance (Sastri 2011). It is important to guarantee safety for the labors and the working industrial personnel, as accidents sometimes occur, regardless the high precautions. So, corrosion damage is not only expensive but also poses risks to human life and safety. For instance, corrosion in ships’ iron hills leads to extreme threats to the working crew. Additionally, accidents may take place in chemical industries which deal with corrosive chemicals that result in the release of hydrogen cyanide and cyclohexene. Deadly airline accidents, gas pipelines bursting, bridge breakdown and failure of steam pipes in nuclear power plants all lead to losses of life. Corrosion can also impact the environment (Sastri 2011). Moreover, several lethal consequences on environment concerning water and air pollution are generated from corrosion-related failures in oil and gas pipelines and tanks. Corrosion related accidents lead to destruction of aquatic flora or fauna. According to Hou et al. (2017), the annual global corrosion cost roughly reaches USD $2.5 trillion. Furthermore, this cost is predicted to increase since the world is witnessing outstanding technological progress. Metal corrosion caused serious catastrophic incidences throughout history. Popoola et al. (2013) reported that on 28 April 1988, a 19-year old manufactured Boeing 737 aircraft, operated by Aloha, lost a big portion of the upper fuselage close to the front of the plane as a result of corrosion damage. Unbelievably, the pilot succeeded in landing the plane on the island of Maui, Hawaii, nevertheless one flight attendant died and a number of passengers suffered from serious injuries. Umoren et al. (2019) reported that on November 22, 2013, a corroded underground Sinopec pipeline “the Donghuang II oil pipeline” exploded in Qingdao, eastern China and resulted in the death of 62 people and the injury of another 136 people. The explosion did not only cause disastrous loss in human life but also cost the company a high economic loss of 750 million yuan (USD $124.9 million). Also, on August 19, 2000, an explosion took place in 30-inch natural gas pipeline possessed by El Paso Natural Gas (EPNG) and resulted in release of gases that kept burning for 55 min. These gases exposed the life of many children and infants to danger as well as damage to three vehicles and twelve facilities. As stated by the National Transportation Safety Board, the explosion was as a result of a significant reduction in the pipe wall thickness which was attributed to severe internal corrosion. Similarly, the Statue of Liberty which was installed on 28 October 1866, on Bedloe’s Island, in New York harbor had undergone severe galvanic corrosion. In April 1992, a huge explosion took place in sewer because of corrosion damage and resulted in the death of more than 200 people in Guadalajara, Mexico. One thousand and six hundred buildings were damaged and 1,500 people were injured. The damage costs

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were valued to reach 75 million USD $. Thus, corrosion is given great attention and adequate measures and precautions should be taken into account to control it as human lives are in danger because of such devastating problem.

1.5 Forms of Corrosion Corrosion occurs in versatile forms of appearance. Fontana and Greene (1967) sorted corrosion into eight forms namely; uniform or general attack, galvanic or two-metal corrosion, crevice corrosion, pitting, intergranular corrosion, selective leaching or parting, erosion corrosion, and stress corrosion. General corrosion is the most common form of corrosion that chiefly occurs because of chemical or electrochemical reactions. Galvanic corrosion occurs between two different metals when exposed to a corrosive environment. Localized corrosion is a type of corrosion which occurs within crevices and other protected areas on metal surface when exposed to aggressive environment. Pitting corrosion occurs as holes or pits on the metal surface. Intergranular corrosion is a kind of corrosion where the margins of metal crystallites are more susceptible to corrosion than their insides. Selective leaching is the displacing of one element from a solid alloy by corrosion reactions. For instance, the selective removal of zinc in brass alloys. Erosion corrosion is the speeding up in the rate of metal dissolution owing to the relative movement between a corrosive system and the metal surface. Eventually, stress-corrosion cracking is the form of corrosion that is caused by the simultaneous presence of tensile stress and a specific corrosive medium.

1.5.1 Sweet Corrosion or CO2 Corrosion Sweet corrosion is usually recognized by simple metal dissolution followed by pitting. Sweet corrosion is a popular type of corrosion in the oil fields and it is defined as “the deterioration of metal because of a contact with carbon dioxide, fatty acids, or other similar corrosive agents except for hydrogen sulfide (H2 S)” (Eduok and Szpunar 2020). Since a long time, CO2 corrosion has been a major problem in oil and gas industries as well as transportation facilities. CO2 is one of the main corroding agents in the oil and gas production systems. It is important to mention that dry CO2 gas is not corrosive by itself at ambient temperatures within oil and gas production systems (Jian et al. 2018). It only becomes corrosive when dissolved in an aqueous phase through which it can endorse an electrochemical reaction between the contacting aqueous phase and the steel. CO2 reacts with water, forming carbonic acid (H2 CO3 ) and therefore makes the fluid acidic. CO2 corrosion is influenced by several factors such as temperature, pH values, composition of the aqueous stream, presence of non-aqueous phases, flow condition, and metal characteristics (Popoola et al. 2013). Till now, it is the most prevalent form of attack facing the oil and gas

1.5 Forms of Corrosion

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production industries. Sweet corrosion always takes place in gas-condensate wells. Condensate wells produce water with pH less than 7 at the well head and usually as low as 4 at the bottom of some wells. This is due to presence of high CO2 contents which reaches up to 3%, high total pressure ranging from 1,000 to 8,000 lb per square inch (psi) at the wellhead beside the presence of organic acids, such as acetic acid (CH3 COOH) (Robertson and Chilingar 2017). Several mechanisms have been evolved for understanding CO2 corrosion processes but generally all of them include either carbonic acid or bicarbonate ion formed upon the dissolution of CO2 in water (Eqs. 1.5–1.9). De Waard and Lotz (1994) postulated the best known mechanism which was as the follow: H2 CO3 → H + HCO3

(1.5)

2H → H2

(1.6)

Fe(s) → Fe2+ + 2e− (Steel reaction)

(1.7)

CO2 + H2 O + Fe → FeCO3 + H2

(1.8)

1.5.2 Sour Corrosion Sour corrosion is referred to metal deterioration due to reactions with hydrogen sulfide (H2 S) as well as moisture (Robertson and Chilingar 2017). Even though, H2 S is not normally corrosive by itself, it becomes severely corrosive in presence of water. Reaction of sour corrosion can be expressed according to the following equation (Chilingar and Beeso 1969): H2 S + Fe + H2 O → FeS X + 2H + H2 O

(1.9)

Different forms of corrosion usually take place because of the presence of H2 S with moisture including; blistering, embrittlement and stress corrosion cracking (SCC). H2 S prevents the union of hydrogen atoms and accordingly, hydrogen atoms become free and penetrate into the metal where they can cause blistering problems. Embrittlement occurs due to hydrogen-induced and hydrogen embrittlement cracking which lead to steel failure. Tubes and pipelines are vulnerable to such effect. SSC cracking failure takes place in presence of low concentrations of H2 S and it increases with decreases in pH (Treseder and Badrack 1997). It has been observed that wells yielding hydrocarbon liquids along with H2 S are less susceptible to many forms of corrosion such as SSC and pitting. For instance, it has been reported that some Canadian condensate wells yielded fluids with 40 mol% H2 S and 10% CO2 for about 30 years

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without suffering from any sever corrosion problems. This was attributed to the formation of a protective FeS film which was further wetted by the oil/liquid hydrocarbon (Treseder and Badrack 1997). SCC is characterized by the formation of cracks on metal surface due to the dual action of corrosive media, tensile stress and the presence of a kind of a metal that is susceptible to that type of corrosion (Panahi et al. 2018). Usually, the greater the tensile stress, the lesser is the time taken for equipment damage. SCC takes place in two main forms including; intergranular in which cracks develop along the grain boundaries or trans-granular in which cracks pass through the grain of the material. SCC may not be accompanied by general corrosion of the metal. In the past few years, certain types of metals and environments were susceptible to SCC (Uhlig and Revie 2008) which led to enormous environmental damage (Ahmad 2006; Parkins 2011). Thus, predicting the incidence of SCC becomes more complicated.

1.5.3 Uniform or General Corrosion Uniform corrosion can also be referred to as “general corrosion”. Uniform or general corrosion is mainly based on visual assessment of corrosion damage. Moreover, it usually takes place as regular loss from metal surface. It is worth noting that general attack occurs when the corrosion elements i.e. anodic and cathodic sites keep changing places from site to site along the metal surface. Contrary, when the anodic and cathodic sites are fixed in one place along the metal surface, this is usually referred to as non-uniform or localized corrosion. Uniform attack is very popular worldwide. Measuring the effect of uniform corrosion can be estimated via either surface thinning of the metal or via mass loss. Corrosion rate is expressed in units of millimeter per year (mm/year) or milliinch per year or mils per year (mpy).

1.5.4 Localized Corrosion The type of corrosion that takes place at separate sites on a metal surface is referred to as “localized corrosion”. Both pitting and crevice types of corrosion can be categorized under the category of localized type of corrosion.

1.5.5 Pitting Corrosion Pitting corrosion is a type of corrosion that results from the localized attacks and metals’ penetration. Formation of small holes or pits or cavities in the metal is referred to as “pitting corrosion”. It is considered as one of the most damaging and harsh forms of corrosion. Pitting corrosion causes equipment failure because of perforation and

1.5 Forms of Corrosion

9

is usually associated with a small percentage of weight loss of the whole structure. Generally, areas where a brass valve is existed in steel or galvanized pipelines become vulnerable to pitting corrosion. The joint between the two areas is frequently pitted and may result in a leak (Sastri 2011). It occurs in industries, farms and homes. Pit shape and depth vary extensively on metal surface. Sometimes it is hard to detect and control pitting corrosion as it may occur as very small holes that can be completely covered with corrosion products. It also develops very rapidly leading to failure in machineries and industrial equipment. The main occurrence behind the incidence of pitting phenomena is the development of a stable corrosion cell on the surface of a passive metal because of the collapse or damage in the protective oxide layer. Among the main factors which initiate pitting corrosion is the presence of chlorides. In addition, other types of corrosion such as erosion, cavitation or impingement might lead to appearance of pits. The variation in the number and depth of pits make it difficult to measure in laboratory tests (Sastri 2011). Usually, pitting corrosion requires several months to a year to appear but it sometimes occurs suddenly. Pits grow and develop downwards from horizontal surfaces in a gravitational direction. Reduction of oxygen results in metal dissolving and consequently pit formation. Some metals and alloys displayed resistance against pitting corrosion and they follow the order of Titanium > Hastealloy C > Hastealloy F > Type 316 stainless steel > Type 304 stainless steel as reported by Sastri (2011). Formation of pits in iron takes place in presence of water and air. Iron becomes oxidized by reaction with water and turns into Fe2+ , which is then released. The pit starts to form at this point. Owing to iron release, two electrons are liberated and pass through the iron till reaching the cathodic area where they combine with the depolarized oxygen (O2 ) and produce hydroxyl ions (OH– ). Afterwards, Fe2+ reacts with the hydroxyl ions to produce hydrous iron oxide (Fe(OH)2 ) which is known as rust (Makhlouf et al. 2018). The incidence of mechanical damage, such as a scratch or dent to the protective oxide film results in occurrence of pitting corrosion. Passive films can be degraded by water molecules. Additionally, dissolved oxygen concentration causes reduction to the stability of the protective film. Furthermore, high-chloride concentration media, for instance seawater, the passive film integrity is reduced, causing corrosion. There are several forms of pits that may take place such as uniform, wide, shallow, narrow, or deep, however, all types perforate the metal wall thickness (Makhlouf et al. 2018). The different shapes of pitting corrosion can be studied via the science of metallography (Fig. 1.2). Pit shape, size and depth can be measured by cross-sectioning of the tested sample.

1.5.6 Crevice Corrosion Crevice corrosion is also referred to as “gasket or deposit corrosion”. Crevice corrosion is considered as a type of localized corrosion. It results from the presence of differential aeration cells. It takes place in gaps and crevices formed either between metals or between a metal and a non-metal material (Makhlouf and Botello 2018).

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Fig. 1.2 Different shapes of pitting corrosion; a wide and shallow, elliptical, narrow and deep; b subsurface, undercutting; c horizontal and vertical grain attacks

Frequently, the gap contains electrolytes that are motionless and the oxygen concentration becomes extremely less than its concentration outside the gap. Consequently, the metal surface in the gap represents the anode and the adjacent outer metal surface plays the cathodic role. When crevice rusting begins, it develops rapidly. Different parts in the construction materials are subjected to crevice corrosion among which are gaskets, lap joints, flanges, bolt holes, rolled pipe ends, threaded joints, rivet heads, seams, etc. The susceptibility of a metal to be attacked by crevice corrosion depends on metallographic structure and alloy composition. It is worth mentioning that both active and passive metals can be subjected to crevice attack for instance stainless steel and the attack may be extremely damaging. Different environmental parameters affect that type of corrosion including; oxygen and chloride concentrations, temperature and pH. Indeed, corrosion is more intense in chloride environments. Some preventive actions can be performed to combat crevice corrosion and they are (a) using welded butt joints to replace bolted or riveted joints; (b) continuous welding to close crevices in lap joints; (c) designing vessels that permit complete drainage without stagnancy; (e) getting rid of solid deposits; (f) use of non-absorbent gaskets for instance Teflon; and (g) equipment flushing with inhibitors (Sastri 2011). Additionally, certain procedures can be done to inhibit crevice corrosion such as cathodic protection, use of alloys resistant to crevice corrosion, keeping the circulation fast enough to renovate the solution and to increase the oxygen supply to sufficient quantities.

1.5 Forms of Corrosion

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1.5.7 Galvanic Corrosion Galvanic corrosion is a type of corrosion which takes place when two different metals are in contact with each other in an electrolyte (Al-Mazeedi et al. 2019). It is sometimes referred to as “bimetallic corrosion”. Consequently, galvanic corrosion is a result of the presence of a galvanic cell and it takes place because of the potential difference between the coupled metals in an environment. The larger the potential difference between the two coupled metals, the greater the cathode surface compared with that of the anode, the more severe the anodic corrosion will be. The electromotive force is usually initiated by the difference in potential between that of anode (lower potential) and that of cathode (higher potential). Certain defensive measures can be applied to prevent galvanic corrosion among which; (a) choosing metals that are somehow near to each other in galvanic series; (b) maintaining surface area ratio of anode/cathode to the smallest level as possible; (c) assuring the presence of insulation between the two unlike metals; (d) use of coatings; (e) employment of corrosion inhibitors to lower the corrosivity of the medium; (f) keeping away threaded joints between different metals; (g) allowing the application of an appropriate design so that replacing anodic portions becomes easy; and (h) use of a third metal that would act as anodic for both metals (Sastri 2011).

1.5.8 Erosion Corrosion Erosion corrosion mechanism depends on increasing corrosion rate via the continuous removal of the passive layer of corrosion products from the pipe walls (Makhlouf et al. 2018). The passive layer is made up of a thin film of corrosion products that truely aid in stabilizing the corrosion reaction and slowing it down. The erosion corrosion usually occurs where there is high turbulence flow regime with significantly high corrosion rate and is dependent on fluid flow rate and on both the density and morphology of solids existed in the fluid.

1.5.9 Oxygen Corrosion Drilling pipe usually includes oxygen that is dissolved in drilling fluids. Oxygen ingress takes place in the well fluids through leaking pump seals, casing, and process vents and open hatches. Oxygen speeds up the anodic dissolution of metal as it serves as a depolarizer and electron acceptor in cathodic reactions. The high velocity flow of drilling fluids continues to supply oxygen to the metal and it becomes damaging at concentrations as low as 5 part per billion (ppb). The presence of oxygen maximizes the corrosive effects of hydrogen sulfide as well as carbon dioxide. The inhibition of corrosion promoted by oxygen is difficult to achieve and is not practical in the

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drilling fluid system. The types of corrosion that are linked to the presence of oxygen are generally pitting-type corrosion and uniform corrosion (Makhlouf et al. 2018). Oxygen corrosion takes place according to the following equations: O2 + 2H2 O + 4e_ → 4OH

(1.10)

Fe+2 + 2OH− → Fe(OH)2(X)

(1.11)

1.5.10 Selective Leaching or Dealloying The removal of a specific element from an alloy because of corrosion is usually referred to as “selective leaching” (Sastri 2011). For instance, “dezincification” refers to the selective removal of zinc from brass especially those which exist in acidic medium. Also, this phenomenon is observed in other alloys such as chromium, iron, cobalt and aluminum. It is worth mentioning that adding small quantities of antimony, arsenic, phosphorus, or tin to 70/30 brass leads to lowering dezincification.

1.5.11 Microbial Corrosion Microbial corrosion involves the degradation of materials by microorganisms and their metabolites such as bacteria, molds, and fungi (Omran et al. 2013; El-Gendy et al. 2016; Omran et al. 2018). It takes place via attacking metals and coatings by acid byproducts, sulfur, sulfide or ammonia and hydrogen or via direct interaction between microbes and the metal under attack (Bahadori 2014). This type of corrosion will be further discussed in a detailed manner in the following chapter.

1.6 Engineering Materials 1.6.1 Carbon Steel Carbon steel is any type of steel that contains only trace amounts of elements other than carbon. It usually contains carbon content of approximately 35 wt%. This percentage facilitates welding. Carbon steel is usually classified into three types according to its carbon content. Steels with less than 0.15 wt% carbon are often referred to as low carbon steel. Steels with 0.25 wt% of carbon are often referred to as mild steel and characterized with high strength. While high carbon steels contain between 0.25–0.35 wt% carbon to achieve much higher strength than the previous two

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types (El-Taib Heakal and Elkholy 2018). Carbon steel is one of the most extensively used engineering material in pipelines. It is used in different fields such as transportation of petroleum products, water and chemicals, beside the manufacture of vessels that are used in gas and oil production systems. Carbon steel has several advantages including; low cost and excellent mechanical properties (Hegazy et al. 2016). Sulfate and chloride ions are extremely aggressive and have the ability to accelerate corrosion of pipelines made up of carbon steel. Formation water is also very corrosive to carbon steel. Formation water is also referred to as “produced water” which occurs naturally in gas and oil reservoirs. Formation water is considered as one of the most corrosive environments in oilfield industries due to the presence of large amounts of dissolved salts such as sulfate and chloride ions. In addition to corrosive ions, dissolved gases also exist in formation water such as carbon dioxide and hydrogen sulfide (Deyab and El-Rehim 2014; Migahed et al. 2015). According to El-Gendy et al. (2016), hydrochloric and sulfuric acids are the most widely used acids which are used to get rid of the undesired scales formed on steels and iron-based alloys. These acids are used for scale and rust removal, acid pickling, industrial cleaning, oil well acidification in oil recovery and in petrochemical processes (Finšgar and Jackson 2014). However, these acids are highly corrosive to metals and their alloys particularly carbon steel

1.6.2 Mild Steel Mild steel is known as plain-carbon steel. It is one of the most important construction materials that has been used during the last few decades. It is used in different industries because of its outstanding mechanical characteristics in addition to its relative low cost (Yadav et al. 2016; Mashuga et al. 2017). Mild steel has a wide range of technological applications but unfortunately it is poorly resistant to acidic corrosion which results in restraining its use in a wide range. According to Gopiraman et al. (2012), mild steel is not highly stable and can be degraded by mineral acids like HCl, H2 SO4 , HNO3 , etc. For example, acids like HCl is usually used in industrial acid cleaning, pickling, de-scaling, and in oil well-acidifying processes (Heydari et al. 2018). Mild steel corrodes very rapidly due to the aggressiveness of acidic solutions being used during these processes, particularly with the use of HCl. This leads to terrible consequences regarding the high costs and materials being consumed (Muralisankar et al. 2017).

1.6.3 Ferrous and Steel Alloys Approximately 94% of the total global utilization of metallic materials is either in the form of steels or cast irons and this applies mainly on oil and gas industries. Hence, the prime selection of an engineering material is usually iron cast or steel

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unless certain requirements are needed. Steel alloys are generally divided into three main categories and they are listed as follows: low alloy steel, high-strength low alloy steel and high-alloy steels. Low steel alloys contain nearly 3 or 4 of one or more alloying elements. It possesses advantages over carbon steel such as improved toughness and strength and it usually contains similar microstructures. High-strength low-alloy steel is a group of low alloy steels with a very small grain size with a tensile yield strength ranging from 350 to 360 MPa. High steel alloys require heat treatment that differs somehow from that of plain carbon steels.

1.6.4 Non-ferrous Metals 1.6.4.1

Aluminum

Aluminum possesses many important features that make it a great candidate to be used as an engineering material among which, low density, good corrosion resistance and good electrical conductivity. The reason behind the corrosion resistance of aluminum is the presence of a thin oxide film that is only few atoms in thickness, but has the capability to prevent permeation of oxygen and thereby protects the metal surface from further attacks. It is worth noting that highly pure aluminum is too weak to be used thus the incorporation of small quantities of iron enhances its strength in order to be beneficial as an engineering material.

1.6.4.2

Copper

Copper is one of the ancient types of metals that was known by mankind. Interestingly, one of its alloys, bronze, has been used for approximately more than 5000 years ago. Pure copper can be used for the manufacturing of wires needed for electrical windings; vessels, tanks and tubing for heat exchangers. Unfortunately, copper alloys are somehow expensive and that is the reason behind reducing their application in industries and their replacement with cheap materials. Copper can be alloyed with different metals such as zinc, tin, aluminum and nickel to produce brasses, bronzes, aluminum bronzes and capronickels, respectively. Interestingly, incorporation of small portions of chromium or berylium to copper results in fabrication of highly resistant alloys. Moreover, incorporation of tellurium into copper yields an excellent alloy which can be employed in machines.

1.6.4.3

Lead, Nickel and Their Alloys

Lead is recognized as a soft and malleable element which is highly resistant to corrosion. It has been used for the manufacture of water pipelines and waste disposal systems. The major consumption of lead is during the manufacture of lead- acid

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storage batteries. This accounts for approximately 30% of the annual world lead consumption. It is also used in fire-fighting systems. Pure nickel displays a marvelous corrosion resistance in presence of several alkalis and acids. Because of its low cost, it acts as a covering sheet for mild steel bases. Monel, incoloy, inconel and nimonic are among the main nickel-based alloys which are utilized in industry.

1.7 Corrosion Tests 1.7.1 Metal Sample Preparation The choice of metal specimens and metal surface preparation are very critical issues since any impurities and variations in the composition have adverse effects on incidence of corrosion (Olajire 2017). Metal composition should be related to real metals involved in corrosion problems. While, concerning sample preparation, the tested metal sample is degreased using organic solvents such as ethanol or acetone or hot alkaline in order to clean the surface and to remove any adherent impurities (El-Gendy et al. 2016, 2018). Second step depends on mechanical polishing with different series of emery paper with variable grades starting from 200 to 400 in order to remove rough spots and deep scratches from metal surface to get a homogeneous appearance of the tested surface (Qian et al. 2013). To achieve a mirror appearance, high grits are usually employed. Such high grits might reach up to 1200–1500 grits. Eventually, these metals should be then degreased, rinsed exhaustively and dried prior to any further use (Qian et al. 2013).

1.7.2 Corrosion Test Medium Usually natural seawater is considered the perfect test medium for laboratory testing (Olajire 2017). However, if sea water is not available, synthetic seawater solution of 3.5 wt% NaCl substitutes seawater water according to ASTM D1141 (2001). A typical composition of 10 L solution has the composition of 245.34 g NaCl, 77.8 g MgCl2 ·6H2 O, 40.94 g Na2 SO4 , 0.296 g SrCl2 ·6H2 O, 8.112 g anhydrous CaCl2 , 1.407 g NaHCO3 , 4.862 g KCl, 0.19 g H3 BO3 , 0.704 g KBr and 0.021 g NaF (ASTM D1141 2001). Usually such solution is deaerated with either CO2 or H2 S to simulate sour and sweet corrosion.

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1.7.3 Gravimetric and Electrochemical Measurements Corrosion rate can be evaluated gravimetrically by carrying out a comparison between weight loss of a metal specimen vulnerable to corrosion in presence and absence of inhibitor. Additionally, gasometric measurement can be carried out to measure the rate of hydrogen gas evolution. Besides, corrosion inhibition efficiency can be determined via certain electrochemical techniques such as potentiodynamic polarization, thermometric and linear polarization measurements and electrochemical impedance spectroscopy (EIS) (Olajire 2017).

1.8 Corrosion Mitigation Strategies 1.8.1 Paints and Coatings Since ancient times, the employment of pigmented organic layers referred to as “paints” was addressed for protecting metals against corrosion. The Roman author Pliny the Elder in 77 AD pointed out that a mixture of “ceruse” (a white lead carbonate), gypsum and tar (paint) would have protective potential against corrosion (Kendig and Mills 2017). Paints are extensively used for many reasons among which substrate decoration, protection against environmental degradation, appearance enhancement, surface deterioration prevention, smoothing surfaces and to block water passage to substrates (Smith 1973). They can be applied to various types of materials that are exposed to water, UV radiation, water, acids, soil, and/or other aggressive compounds. Among these materials; metals, wood, plastics, masonry, etc. As reported by Kumar et al. (2018), the cost of paints and coatings exceeded $129 billion in 2015. Moreover, in 2016 the cost increased to almost $132.2 billion and is expected to jump to $164.1 billion in 2021 because of a yearly rising percentage of 4.4% from 2016 to 2021. Hence, these numbers indicated the increasing need for protective coatings in diverse industrial fields. Specifically, 40% of the total direct expenses are ascribed to paints while 88% of this cost is ascribed to organic coatings that are used for protecting materials and equipment in marine environments against corrosion and biofouling. Paints support protection by forming a barrier that prevents or minimizes the effect of such deteriorating agents. There are two categories of paints: organic solvent based and water based paints. Water based paints are more favored because they are eco-friendly. Moreover, water based coatings have advantages such as low odor, easy cleanup, low yellowing, and ability of quick recoating (Overbeek et al. 2003). Nonetheless, water based paints have some disadvantages including; poor hiding power, low gloss, poor dry and wet adhesion, poor water and alkali resistance, and they are more decomposable than solvent based paints (Overbeek et al. 2003). Despite these deficiencies of water based coatings they are used worldwide as interior paints, particularly for ceilings and walls. Typical waterborne paint contains water, resin,

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pigments and other additives (Karaka¸s et al. 2015). The importance of water in paints is to ease coating application and film formation. Resin is a film-forming material and is the main constituent responsible for the chemical and physical characteristics of the paint, such as scratch resistance, adhesion, mechanical hardness and optical properties. Pigments include oxides or silicates. Prime pigments are responsible for giving color and opacity to the paint such as titanium dioxide or carbon black. Paint additives are any substance that is added in small magnitudes to develop or modify certain properties of the product during its manufacture, transport, storage and application. Over the years, researchers have tried to understand the mechanism behind corrosion protection using paints. Early guessing on the important features of a perfect paint was introduced by Newman who indicated that paints should be extremely homogeneous and possess high ability to get tightly bound to bare iron or steel surface along with being highly elastic (Newman 1896). Furthermore, Newman managed to introduce a suggestion concerning paints’ protective effect as paints inhibit the galvanic action by acting as an insulator. However, after years of research and experiences, scientists showed that there are four important themes which must be addressed in paints in order to yield a protective effect. These factors are related to the electrical properties, paint heterogeneity, effect of corrosion and adhesion loss and eventually their role in releasing corrosion inhibitors (Kendig and Mills 2017). The role of electrical properties was mainly based on the hypothesis proposed by Dr J.E.O Mayne which discussed the importance behind paints’ electrical properties particularly paints’ ionic resistance in explaining their role in metal protection from corrosion. Mayne (1952) observed that organic coatings as well as paints inhibit electrochemical reactions via the creation of high resistance pathways between microand macro- anodes and cathodes. Additionally, the role of paint heterogeneity plays a major role in designing protective paints. It is worth noting that localized differences in paints’ characteristics provides hint concerning the initiation and propagation of corrosion of a painted metal. Mayne and Scantlebury (1970) discovered locations which differ in electrical resistivity depending on environment ionic concentration either in a direct (D) or indirect (I) way. These regions showed to be correlated with degrees of cross linking (Mills and Mayne 1981). It was interesting that D regions appeared to be correlated with loci where corrosion is initiated. Scanning probe methods provided further confirmation of the heterogeneous nature of protective films. These scanning methods included scanning electrochemical impedance (Isaacs and Kendig 1980; Standish and Leidheiser 1980), scanning Kelvin probe (Stratmann et al. 1994) and scanning vibrating electrochemical technique (Roe and Zin 1980). Another important factor is the wet adhesion of the employed paint. It has been claimed that adhesion under conditions of actual corrosion regulates the longevity of coated metal. Eventually, paints serve as a perfect platform as carriers of inhibitors. The inhibiting pigments incorporated with paints aid in galvanic protection, metal passivation and alkaline buffering (Kendig and Mills 2017). Recently, smart coatings have been proposed as they aid in inhibitors’ release via electrochemical stimulation of any corrosion reaction. Nonetheless, one of the difficulties that face paints with inhibitors is that they are effective in inhibiting corrosion but they

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can be toxic. And since the old days till recent ones, researchers do their best to lessen if not end this problem. In 1908, Livache (1908) managed to design paint free from lead and instead environmentally friendly Zn/ZnO was incorporated within the paint. Additionally, several strategies have been done to remove hazardous solvents from paints such as hexavalent chromium. The most often employed pigments instead of chromates are phosphates (Bethencour et al. 2003) and rare earth-containing inorganics (Forsythe et al. 2008). Recently, conducting polymers (Wessling 1994) and inherently conducting polymers ICP hybrids (Sathiyanarayanan et al. 2007), vanadates (Zheludkevich et al. 2010), molybdates and organic/inorganic hybrids (Sinko 2001) are included as well. Coatings have been used for corrosion protection since long time ago. So many resources have been discovered and tested to develop formulations with anticorrosion effect in order to protect tools, equipment, artifacts, marine structures and other valuable objects from corrosive environment. For instance; clays (e.g., natural silica) or animal fat were employed to protect metals against corrosion and that was extremely helpful to avoid oxidation in iron-based artifacts (Montemor and Vicente 2018). Moreover, old coating formulations contained several mineral mixtures and extracts such as bee wax, gelatin, oil extracts from different fruits, plants and trees. Interestingly, some of the ancient additives are being developed and modified as a direction towards green chemistry. Coatings are categorized into two groups including; powder coatings and water based coatings. Powder coatings possess advantages as they do not include any volatile organics, able to reform thick films, exhibit very high corrosion protection and they are very easy to apply (Montemor and Vicente 2018). Basically these coatings are made up of nontoxic materials and low organic solvents. That type of coating is useful particularly in harsh environments such as for protecting offshore facilities. Nevertheless, some negative points still remain, such as the lack of flexibility concerning time and temperature. Additionally, powder coatings require well prepared surface to make sure that adhesion is strong enough and to guarantee long term corrosion resistance (Montemor and Vicente 2018). Still, certain features of powder coatings need significant developments. Among these features flow properties, being flexible to be applied as thin films, flexibility towards UV radiation and electron beam curing. Waterborne coatings specifically epoxy based ones are becoming extremely attractive, extensively applied, and currently represent a big part of local markets (Montemor and Vicente 2018). That type of coating is volatile and organic free; able to form films rapidly. Waterborne epoxy coatings are stable and can be stored for long periods. They can be applied in different thickness ranges, able to provide extreme corrosion protection and they are valid to be applied in harsh environments. Yet, some weakening points arise like reduced chemical resistance in extremes of pH i.e. highly acidic and highly alkaline conditions in addition to poor multi-substrate adhesion (Montemor and Vicente 2018). To overcome these disadvantages, siloxane based technology as well as chemical manipulation of epoxy matrices at the nanoscale level emerged as very potent routes to decrease such weakening points.

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Shao and Zhao (2010) managed to synthesize three kinds of silver coatings on stainless steel plates using AgNO3 based electroless plating solutions. Reaction was performed in three different periods 5, 15 and 30 min. It was noticed that increasing the coating time led to increase in the thickness of the tested coating. Moreover, corrosion rate decreased to some extent with increasing the coating thickness. Also, the number of adhered bacteria was much lower in case of the silver coating rather than that of bare stainless steel plates. Shao and Zhao illustrated the presence of a strong correlation between bacterial adhesion and total surface energy. It was noticed that the number of bacteria adhered to the silver coating with low surface energy was reduced than that of SS 316L with high surface energy. Vejar et al. (2013) investigated the antibiofouling capability of three hybrid sol-gel coatings for the protection of AA2024-T3 aluminum alloy against P. aeruginosa. Tetraethoxysilane (TEOS) was mixed with the following precursors (a) triethoxypropylsilane, (b) triethoxypentylsilane (TEPES) and (c) triethoxyoctylsilane (TEOCS) to produce the hybrid polymers. The three precursors differed from each other in the length of the aliphatic chain of one of the substituents. Scanning electron microscopy (SEM) was employed to study the morphology of the prepared polymers. Potentiodynamic polarization measurements evaluated the protection capability of the AA2024 alloy coated with the synthesized polymers. The electrochemical measurements revealed that the coatings inhibited the growth P. aeruginosa which was responsible for microbial corrosion. It was proven that there is a relation between the length of the aliphatic chain and the degree of protection as the longer the chain length, the greater will be the protective effect. Siloxane based technology continues to have strong contributions in developing coatings with volatile organic compounds (VOC) in order to replace the aromatic solvents. Siloxane based technology increases the mechanical properties to provide maximum corrosion protection (Montemor 2014). Brusciotti et al. (2013) investigated an epoxy-based framework to protect Mg alloy AZ31. Four different types of siloxanes were incorporated together with an epoxy resin and aided in achieving extremely high corrosion protection when the alloy was exposed to chloride containing solutions. In a recent study performed in 2016 and reported by Bera et al. (2016) and coworkers, a good compatibility between epoxy and aminosilanes was attained and resulted in improving coating properties. Lamaka et al. (2015) studied the role of aminosilane in coatings by using different electrochemical techniques and it was evidenced that corrosion resistance was because of the good chemical and mechanical characteristics of the epoxy coating. Same observations were reported by Jiang et al. (2015). Chrusciel and Lesniak (2015) reviewed that the incorporation of different siloxanes with epoxy coatings resulted in increasing protection against corrosion and weathering resistance of such reformed coatings. Similarly, it was found that siloxane modification with different organic matrices allowed the emergence of interesting and novel features for instance; anti-fouling, anti-dusting, anti-bacterial, self-cleaning, super hydrophobicity, anti-finger print, anti-fogging and repellence of ice. Besides, these films can be applied in thin films thus providing high anti-corrosion performance. Yet some drawbacks occur including; sensitivity to other additives.

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Claire et al. (2016) demonstrated that addition of ceramic nanoparticles (NPs), such as TiO2 , SiO2 , or ZrO2 , in different quantities to epoxy-based sol-gel synthesized coatings resulted in enhancing the mechanical properties as well as increasing corrosion protection due to the presence of a strong barrier against permeation of ions and water molecules. Moreover, graphene has been employed as filler to siloxanemodified coatings to enhance corrosion protection. Though the exact mechanism of action is not totally understood, positive results have been reported concerning its role in increasing corrosion protection (Okafor et al. 2015). Same results were reported for SiO2 NPs decorated with graphene (Ramezanzadeh et al. 2016). Also, it was observed that the addition of boehmite NPs resulted in increasing corrosion protection of coated aluminum alloy 2024 in aggressive environments because of the formation of a stabilized oxide layer (Tavandashti et al. 2011). Addition of acrylics, polyurethanes and polyesters to siloxane polymeric coating aided in corrosion protection (Montemor 2014). Self-healing coatings are very important functional coatings. Self-healing could be defined as “the partial or total recovery of specific functionalities of coating when imperfections, ageing, and other unexpected damages disrupt the coating function” (Montemor 2014). Self-healing is a very exciting and challenging feature that if existed can significantly increase protection against corrosion as well as endorsement of corrosion management approaches. Mainly two chief routes were proposed to improve self-healing coatings, the first focuses on repairing the polymeric matrices, i.e. recovery of barrier properties and the second one focused on inhibition/passivation of corroded areas i.e. protecting corrosion active sites. It is worth mentioning that self-healing is not a new concept and it was proposed many years ago. In 1965, Wlodek (1961) demonstrated the self-healing properties of an inorganic coating applied over columbium. Another research was conducted by Yasuda et al. (2003). In this study, the self-healing behavior of Al2 O3 · Nb nanocomposite was investigated over steel and it was found that Al2 O3 Nb nanocomposite had the ability to function as a sacrificial layer to prevent iron corrosion. The effect was correlated to “self-healing” activity (Yasuda et al. 2003). Nonetheless, the most famous example of self-healing is the one provided by chromate containing corrosion inhibitors as well as chromate-based surface treatments and coatings (Montemor and Vicente 2018). Zhao et al. (1998) employed different electrochemical and chemical characterization techniques to study the self-healing mechanism of chromate based coatings. Results indicated that chromate can be leached from the coating and migrate to a neighboring site of the metal alloy. It was found that Cr (IV) existed in the pits formed on the tested alloy. According to this study, deposition of chromate species was somehow selective for the corroded sites (Zhao et al. 1998). Regardless of the long term employment of chromates in coatings, the exact protection mechanism is still not fully understood. The lack of alternatives to chromates contributed to its extensive use over the years on expenses of human health as well as environmental safety. But in the last two decades, chromate uses have been much decreased in many industrial applications (Montemor and Vicente 2018). However, the regulations of registration, evaluation, authorization, and restriction of chemicals (REACH) are

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restraining the use of chromate-based coatings and also its replacement with green and environmentally friendly formulations.

1.8.2 Corrosion Inhibitors Many years ago, extensive efforts were devoted to find appropriate corrosion inhibitors of organic origin to aid in mitigation of corrosion in aggressive corrosive environments. Corrosion inhibitors are of special importance in environments containing acids, aldehydes, thioaldehydes, nitrogen-base materials, sulphurcontaining compounds to repair their side adverse effects. In neutral media nitrite, chromate, benzoate and phosphate act as good corrosion inhibitors. Inhibitors decrease or prevent the reaction of the metal with the surrounding media. Inhibitors are often easy to apply and have the advantage of in-situ application. They decrease the corrosion rate via: (i) (ii) (iii) (iv)

Adsorption of ions on metal surface, Decreasing or increasing the anodic and/or cathodic reactions, Reducing the diffusion rate for reactants to reach the metal surface, Decreasing the electrical resistance of the metal surface.

Several factors need to be taken into consideration when choosing an inhibitor like cost, amount, availability and safety to environment.Inhibitors are classified into three main types based on whether the anodic or the cathodic reaction is suppressed by the selected corrosion inhibitor. The three types are anodic, cathodic and mixed type inhibitors (Sastri 2011). First, the cathodic inhibitors prevent hydrogen evolution in acidic solutions and reduce oxygen in alkaline and neutral solutions. Usually, in order to be an effective cathodic corrosion inhibitor, the selected material should possess potential higher than that of hydrogen in acidic solutions. Examples of the cathodic inhibitors are silicates, inorganic phosphates, or borates in alkaline solutions, as well as carbonates of magnesium and calcium. They all block the active cathodic sites. Contrary, anodic inhibitors are efficient in solutions with pH range from 6 to 10.5 (close to neutral or basic media). Examples of effective anodic inhibitors are chromates, tungstates, molybdates and sodium nitrite. It is believed that such oxyanions aid in repairing the imperfections in the iron oxide passive film on metallic iron surface. It is important to mention that the inhibitor concentration is extremely important in case of using chromates or dichromate. While, mixed type inhibitors affect both the cathodic and anodic sites. Organic compounds function as mixed type corrosion inhibitors. The organic inhibitors become adsorbed on metal surface and function as a barrier to metal dissolution at the anode and as a barrier to oxygen reduction at cathodic sites. Usually, the protective functional groups in organic mixed type inhibitors involve amino, carboxyl and phosphonate groups. Organic inhibitors have the capacity to act as corrosion inhibitors as they have high electron density and basicity, they generally contain heteroatoms such as O, N, and S. Heteroatoms are the basic factors that aid in the adsorption process on the metal

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surface. Most organic inhibitors become adsorbed on metal surface by replacing water molecules on the surface and forming a compacted protective barrier. Moreover, when non-bonded lone pair and p-electrons exist in inhibitor molecules, this facilitates electron transfer from the inhibitor to the metal surface. The strength of the chemisorption bond relies on the electron density on the donor atom of the functional group as well as the polarizability of that group. Corrosion inhibition increases with increase in carbon number in the chain to approximately 10 carbons. This is because when the length of hydrocarbon chain is increased, a decrease in solubility occurs in aqueous solution. Nevertheless, presence of a hydrophilic functional group in the molecule might increase inhibitors’ solubility. It is worth denoting that the performance of an organic inhibitor is chiefly related to its chemical structure, electron density at the donor atom, electronic structure of the molecule, p-orbital character, and physicochemical properties along with the existed functional groups. The inhibition could be due to one of the following (i) adsorption of molecules or its ions on anodic and/or cathodic locations (ii) increase in cathodic and/or anodic over voltage, and (iii) the formation of a protective layer film. The basic role of an inhibitor is to form an obstacle by forming one or several molecular layers against the corrosive attacks. This protective action is often related to either chemical and/or physical adsorption. Sulphur, phosphorous, oxygen and/or nitrogen-containing heterocyclic compounds are considered to be efficient corrosion inhibitors. Hydrazine derivatives and thiophene offer great capacity to inhibit metal corrosion in acidic media. Inorganic substances such as chromates, phosphates, dichromates, silicates, borates, molybdates, tungstates, and arsenates act as effective corrosion inhibitors. Corrosion inhibitors are very useful in forming anti-corrosive coatings, but one of their major disadvantages is their toxicity. Consequently, several environmental regulations have restricted their application in industry. Among the alternative corrosion inhibitors, organic substances containing polar functional atoms such as sulphur, nitrogen, and/or oxygen. The resulting adsorbed film acts as a barrier that separates the metal from the corroding environment. The well-known hazardous effects of most synthetic organic inhibitors led to an urgent need to develop nonexpensive, non-toxic and eco-friendly inhibitors using natural products. This has increased the search for green corrosion inhibitors. Different commercial inhibitors are available under trade names. Such trade names provide very little information concerning their composition. Commercial corrosion inhibitor formulations consist of more than one inhibitor compound accompanied with other additives including; demulsifiers, surfactants, oxygen scavengers and film enhancers. Formaldehyde, polyphosphates, chromates and arsenic compounds are among the early employed corrosion inhibitors (Reiser 1966). Most of these types possess structures composed of long chain hydrocarbons (C18). The most commonly used corrosion inhibitors in petroleum industry belong to one of several classes of amides/imidazolines, nitrogen quaternaries, nitrogen heterocyclics, amides, imidazolines, salts of nitrogenous molecules with carboxylic acids, polyoxyalkylated amines and compounds containing S, O and P atoms (El-Gendy et al. 2016; 2018).

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Mechanism of Action

Corrosion inhibitors can be categorized into barrier and environmental inhibitors (neutralizing and scavenging). (a) Barrier Inhibitors Barrier inhibitors are known as film forming corrosion inhibitors and sometimes are referred to as interface inhibitors. Such kind of inhibitors form a protective barrier on metal surface via strong interactions such as chemisorption, electrostatic adsorption and π-orbital adsorption. Consequently, an observed reduction in penetration of corrosive substances occurs (Kelland 2014). Interestingly, barrier inhibitors are made up of two parts; one is the polar head which in turn reacts with metal surface while the other part is the hydrophobic part and it extends away from the metal surface. The hydrophobic part is responsible for further protection against aqueous species as it interacts with stream hydrocarbon molecules (Olajire 2017). They comprise one of the largest classes of inhibitive substances and they do not require any further interactions with acids to be effective. Interface inhibitors or film forming inhibitors are further classified into liquid- and vapor phase inhibitors which in turn can be categorized into anodic, cathodic or mixed-type inhibitors. The type of inhibitors depends mainly on the type of electrochemical reaction being blocked (Papavinasam 2011; Dariva and Galio 2015). They facilitate the development of a passivating film which inhibits anodic metal dissolution reaction, thus they are referred to as passivating inhibitors as well (Papavinasam 2011). The effective concentration of anodic inhibitors is dependent on both the concentration and the nature of the corrosive ions. Conversely, effect of cathodic inhibitors is usually attained by either decreasing reduction rate (cathodic poisons) or by precipitating on cathodic areas (cathodic precipitators). In case of cathodic inhibitors, protective film layers are established on cathodic sites against hydrogen in acidic conditions or a decrease in cathodic reaction rate by restricting oxygen diffusion to metal surface in case of alkaline solutions. But it should be noted that cathodic inhibitors can result in hydrogen embrittlement, hydrogen induced cracking (HIC), or sulfide-stress cracking (Papavinasam 2011). Therefore, hydrogen permeation studies are necessary to govern the efficiency of a cathodic inhibitor (Umoren et al. 2010). On the other side, cathodic precipitators increase the alkalinity at cathodic sites, thereby lead to precipitation of insoluble compounds on metal surface. Carbonates of magnesium and calcium are the most widely employed cathodic precipitators. Approximately 80% of organic compounds fall into the category of mixed-type inhibitors. Mixedtype inhibitors protect metals by three main routes involving; chemisorption, physical adsorption (physisorption) and film formation. Physisorption takes place by ionic or electrostatic interaction between the inhibitor and metal surface. Physically adsorbed inhibitors interact quickly. Nonetheless, the increase in temperature leads to desorption of physically adsorbed inhibitors. The chemically adsorbed inhibitors are the most efficient inhibitors. Chemisorption involves charge sharing or charge transfer between inhibitor molecules and metal surface. Increasing temperature in chemisorption result in an increase in adsorption and the inhibition performance

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becomes efficient. Chemisorption is slower than physisorption and is not completely reversible (Olajire 2017). Inhibition is effective only when the prepared films are nonsoluble, strongly adhered and when they are able to block any access of solutions to metal surface. Film formation by mixed-type inhibitors can be either conducting (self-healing films) or non-conducting. (b) Neutralizing Inhibitors Neutralizing inhibitors help in reducing the corrosive action of the produced acids or by minimizing the concentration of hydrogen ions in corrosive environments. Sodium hydroxide, ammonia, morpholin, polyamines and alkylamines are among the most commonly used neutralizing inhibitors (Olajire 2017). For instance, ammonia is an inexpensive neutralizing inhibitor. However, its insolubility in condensates as well as its quick evaporation affects its efficiency as an inhibitor (Camp and Phillips 1950). (c) Scavenging Inhibitors Scavenging inhibitors are employed in oil and gas production facilities to remove corrosive species. Sodium sulfite and hydrazine are among the most well-known scavenging inhibitors (Saji 2020).

1.8.2.2

Examples of Corrosion Inhibitors

(a) Surfactants as Corrosion Inhibitors Surfactant science is considered one of the attractive fields of science because of the massive applications in which they can be exploited for instance, detergents, corrosion inhibitors, drugs, demulsifiers, petroleum oil recovery as well as in nanotechnology science (Vashishtha et al. 2015; Falciglia et al. 2016; Lee et al. 2016; Zhang et al. 2017). Generally, surfactants constitute a class of chemical compounds that are made up of amphiphilic molecules; each one consists of hydrophilic (polar) head and hydrophobic (non-polar) tail (Brown et al. 2015; Asadov et al. 2017). Two exact surfactant monomers that are linked together through a covalent bond constitute a molecule of Gemini surfactant (Li et al. 2015; Tawfik 2015). Pérez et al. (2014) reported that these compounds were referred to as ‘Gemini’ after Menger and Littau in 1991. Three cationic Gemini surfactants with different hydrophobic spacer chain lengths designated as G-2, G-6 and G-12 were fabricated by Tawfik et al. (2016). These three compounds were tested for their corrosion inhibition capability of carbon steel in 1 M HCl corrosive medium. The effective compounds followed the order of G-12 then G-6 and then G-2. This was interpreted by the development of a more effective protective layer at the steel surface and therefore the degree of surface coverage was increased. This was achieved when the spacer chain length was increased. Park and Jeong (2016) managed to prepare four Gemini cationic surfactants containing ester group in the series α, ω-alkane-bis (Nmyristoyloxyethyl-N, N-dimethyl ammonium) bromide where the ester group is present in the terminal chains. The synthesized compounds were referred to as (16-3-16), (16-4-16), (16-5-16) and (16-6-16)

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with variable spacer chain lengths of 3, 4, 5 and 6, respectively. The prepared surfactants were evaluated for their inhibitive action on corrosion of low carbon steel in 1 M HCl using weight loss technique. Maximum inhibition efficiencies were 99.1, 98.7, 98.9 and 98.6%, respectively for (16-3-16), (16-4-16), (16-5-16) and (16-616), respectively at a concentration of 1 × 10−3 M. It was observed that inhibition efficiencies of these surfactants were not dependent on spacer length. Quaternary ammonium Gemini surfactant containing an ester spacer namely (diethyl hexanedioate) diyl-α, ω-bis (dimethyl myristyl ammonium) bromide designated as (14-DEHA-14) was successfully prepared by Zhang et al. (2015). Results revealed that the synthesized gemini surfactant acted as a good corrosion inhibitor of carbon steel in 1 M HCl with inhibition efficiency greater than 95% at a concentration of 5 × 10−5 M. The inhibition mode took place via chemical adsorption on the steel surface and followed Langmuir adsorption isotherm. Abd El-Lateef et al. (2016) synthesized three novel cationic Gemini surfactants symbolized as CHOGS8, CHOGS-12 and CHOGS-16 with different terminal chain lengths as octyl, dodecyl and hexadecyl, respectively. Their effect was studied on carbon steel in 15 wt% HCl. Data showed that the inhibition efficiency percentage (IE%) of these compounds increased with increasing inhibitor chain length as well as its concentration, where maximum IE% was attained at 200 ppm. It was found that IE% was 97.51% for CHOGS-8, 98.73% for CHOGS-12 and 99.61% for CHOGS-16. (b) Plant Biomaterials as Green Corrosion Inhibitors (Eco-friendly Corrosion Inhibitors) Use of chemical inhibitors such as chromates has been forbidden because of toxicity and the hazardous environmental effects they produce. Therefore, there was a strive to use environmentally friendly, non-toxic/less toxic extracts of naturally occurring plant materials and agro-industrial wastes as corrosion inhibitors and biocides (Sangeetha et al. 2011) (Table 1.1). However, extracts of such natural plant materials are easily biodegradable, which in turn limits the storage and long-term usage of them as corrosion inhibitors and biocides. Nevertheless, it is anticipated that the easily biodegradability can be prevented by the addition of sodium dodecyl sulphate and N-Cetyl –N, N, N-trimethyl ammonium bromide. Extracts of such plant materials involve the presence of a wide range of organic compounds and most of these compounds contain heteroatoms such as P, N, S and O. These atoms react with the corroding metal atoms via their electrons. Thus, a protective film is formed on the metal surface and corrosion is controlled and mitigated. Finally, some plant scientists warn from using them as corrosion inhibitors and biocides as the plant Kingdom will slowly diminish and metals will be protected at the cost of damage of plant kingdom. As there is a high demand for green chemistry all over the globe, therefore the development of green inhibition strategies, biocides and corrosion inhibitors is urgently required. Because of their biological and natural origin, plant extracts are regarded as green and sustainable materials to be employed as corrosion inhibitors to protect metals and alloys against corrosion in aggressive environments such as HCl, H3 PO4 , H2 SO4 and HNO3 (Chemat et al. 2012; El-Gendy et al. 2016; 2018).

Metal

Mild steel

Carbon steel

Carbon steel

Mild steel

Plant material

Alkaloid extract of Ochrosia oppositifolia

Rollinia occidentalis methanolic extract

Aqueous extract of Allium cepa

Saraca ashoka extract

0.5 M H2 SO4

1 M HCl

1 M HCl

1M HCl

Medium

Langmuir

Langmuir

Langmuir

Adsorption isotherms

Weight loss Langmuir measurements, potentiodynamic polarization measurements and EIS, SEM, FTIR, UV–Vis spectroscopy

SEM, EDS, XRD

Potentiodynamic polarization measurements, EIS, Weight loss measurements, UV–visible and IR spectrophotometric measurements, SEM surface analysis

Potentiodynamic polarization measurements, EIS, FTIR, SEM

Experimental measurements and characterization techniques

Table 1.1 Some Plant extracts investigated as green natural corrosion inhibitors

Mixed type inhibitor

Mixed type inhibitor

Mixed type inhibitor



(continued)

Saxena et al. (2018)

El-Gendy et al. (2018)

Alvareza et al. (2018)

Raja et al. (2013a)

Type of inhibitor References

26 1 Basic Corrosion Fundamentals, Aspects and Currently …

Metal

1018 steel

Mild steel

Mild steel

Plant material

Rice bran oil

Eriobotrya japonica

Primula vulgaris flower aqueous extract

Table 1.1 (continued)

1 M HCl

0.5 M H2 SO4

Brine-CO2 Saturated solution

Medium

FTIR, UV–Vis spectroscopy, SEM, atomic force microscope (AFM), contact angle measurements (CA), EIS and potentiodynamic spectroscopy

Weight loss method, electrochemical measurements, SEM

Electrochemical techniques such as potentiodynamic polarization, open circuit, linear polarization resistance, EIS, FTIR and TLC

Experimental measurements and characterization techniques

Langmuir

Langmuir

Langmuir

Adsorption isotherms





Cathodic type inhibitor

(continued)

Majd et al. (2019)

Zheng et al. (2018)

Salinas-Solano et al. (2018)

Type of inhibitor References

1.8 Corrosion Mitigation Strategies 27

Metal

Mild steel

Mild steel

Carbon steel

Plant material

Chinese gooseberry fruit shell acidic extract

Rape grist extract (Brassica napus)

Ginger extract

Table 1.1 (continued)

Saline water

Tap water

HCl

Medium

Langmuir

Adsorption isotherms

Stereo-microscope and – various electrochemical measures, FTIR and X-ray photoelectron spectroscopy (XPS)

Weight loss and – polarization techniques, linear polarization technique (LPR)

Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization tests, steel surface morphology examination via SEM, AFM and contact angle tests

Experimental measurements and characterization techniques

Mixed type inhibitor



Mixed type inhibitor

(continued)

Liu et al. (2019)

Vasyliev and Vorobiova (2019)

Dehghani et al. (2019)

Type of inhibitor References

28 1 Basic Corrosion Fundamentals, Aspects and Currently …

Metal

Mild steel

C38 Steel

Plant material

Juglans regia green fruit shell extract

Hydro-alcoholic extract of used coffee grounds

Table 1.1 (continued)

1 M HCl

3.5 wt% NaCl (saline solution)

Medium

Adsorption isotherms

Open circuit potential measurements, potentiodynamic polarization assay, EIS

Langmuir

Polarization, EIS and – electrochemical current noise analyses, FESEM, EDS, FTIR analyses

Experimental measurements and characterization techniques

Mixed type inhibitor



Bouhlal et al. (2020)

Haddadi et al. (2019)

Type of inhibitor References

1.8 Corrosion Mitigation Strategies 29

30

1 Basic Corrosion Fundamentals, Aspects and Currently …

Though, there are several parameters that should be taken into consideration during preparation of plant extracts. Mentioned below two of the most important parameters: (a) Solvents for extraction: solvents are diffused into plant tissues then solubilized and finally the existed phytochemicals are extracted (Nasrollahzadeh et al. 2014). As a result, choosing suitable solvents for extraction is very significant for efficient extraction. Extensive published reports recommended that water is the best solvent because of its simple structure, readily availability, non-hazardous nature and non-flammable properties (Sharghi et al. 2009; Duan et al. 2015; Varma 2016). Nonetheless, organic solvents such as methanol and ethanol may be required for preparation of some plant extracts. (b) Extraction temperature: temperature is an important parameter that affects plant extract preparation. It was noticed that less phytochemicals are obtained at very low temperature. In addition, phytochemicals become subject to decomposition at very high temperatures. Commonly, extraction is being accomplished in the temperature range of 60 to 80 °C in order to obtain best extraction yield (Mohamad et al. 2014). Plant biomaterials can act as green corrosion inhibitors in different environments including, acidic (hydrochloric and sulphuric acids), alkaline (sodium hydroxide and sodium sulphate) and saline environments. Hydrochloric acid (HCl) is ranked as the topmost consumed pickling acid in oil industry (El-Gendy et al. 2016). HCl is much preferred for pickling than the other types of acids because of the low time required for pickling as well as the high surface quality which is achieved at low temperatures. The recommended concentration for using HCl for pickling ranges between 5–15% (Umoren et al. 2019). El Hamdani et al. (2015) investigated the efficiency of the alkaloid extract of Retama monosperma (L.) Boiss. seeds (AERS) to mitigate corrosion in 1 M HCl medium via electrochemical and surface characterization techniques. Results revealed that this plant extract can be considered as an effective corrosion inhibitor for carbon steel in 1 M HCl with a maximum inhibition efficiency of 94.4% at 400 mg/l of AERS. Impedance results confirmed that using AERS reduced the charge capacitance and increased the function of the charge/discharge of the interface and consequently facilitated the formation of a protective layer over the steel surface. Polarization curves showed that AERS is a mixed type inhibitor. Adsorption of such alkaloid extract obeyed Langmuir adsorption isotherm. X-ray photoelectron spectroscopy (XPS) showed that the inhibition mechanism by AERS was mainly a physisorption mode of inhibition and the protective layer was made up of an iron oxide/hydroxide mixture with the incorporation of AERS molecules. Alstonia angustifolia var. latifolia (King et Gamble) belongs to Apocyanaceae family. It is extensively existed in tropical and sub-tropical regions of Malaysia. Raja et al. (2013b) studied the corrosion inhibition efficiency of the leaf extract of Alstonia angustifolia var. latifolia of mild steel in 1 M HCl. Several techniques were employed to study the corrosion parameters and for surface characterization such as impedance spectroscopy, potentiodynamic polarization, Fourier transform infrared (FTIR) analyses and SEM. Results demonstrated that the alkaloid extract of A. latifolia acted as a good corrosion inhibitor and exhibited maximum inhibition

1.8 Corrosion Mitigation Strategies

31

efficiency up to 80% at concentrations ranging between 3–5 mg/l of the tested extract. Polarization measurements indicated that the inhibitor acted as mixed type inhibitor. Results obtained from both electrochemical techniques were in good agreement and the inhibitor adsorption followed Langmuir adsorption isotherm. FTIR studies witnessed the existence of indole alkaloids and their involvement during the corrosion inhibition process. SEM images indicated the formation of a protective layer over the mild steel surface. Bouknana et al. (2014) demonstrated the effect of phenolic (OOMW-Ph) and non-phenolic (OOMW-NPh) fractions of olive oil mill wastewaters extract. Data showed that both tested compounds reduced the corrosion rate. The maximum inhibition efficiency reached and 89.1% for OOMW-Ph and OOMW-NPh, respectively. The increase in temperature led to decrease in the inhibition efficiency of both compounds. L-Citrulline is an organic compound with multiple functional groups including; amide, amine and carboxylic groups. It is usually referred to as a non-essential amino acid as it lacks a structural protein l-Citrulline. Watermelon (Citrullus lanatus) is one of the major natural sources containing l-Citrulline. Also, it occurs in minor amounts in other kinds of fruits and vegetables such as cucumbers, bitter melons, pumpkins, squashes and gourds (Kaore et al. 2013). The role of l-citrulline obtained from watermelon in inhibiting corrosion of mild steel in HCl solution was studied by Odewunmi et al. (2015). Electrochemical techniques such as electrochemical impedance spectroscopy (EIS), potentiodynamic polarization as well as weight loss techniques at 25 and 60 °C were employed to evaluate the corrosion inhibition effect. Results revealed that inhibition efficiency increased by increasing l-citrulline concentration. Furthermore, inhibition efficiency decreased with increase in solution temperature. Polarization data indicated that l-citrulline acted as a mixed type corrosion inhibitor. Nnaji et al. (2014) reported that cashew nut testa tannin (CASTAN) inhibited corrosion of aluminum in HCl solution. This was investigated using weight loss, UV/visible spectrophotometric and thermometric techniques. Adsorption CASTAN followed Langmuir isotherm in 0.5 M and 2 M HCl at 303 K while it followed Temkin isotherm in 0.1 M HCl. It also exhibited a physical type of adsorption on aluminum. It was categorized as a cathodic inhibitor. UV/visible spectrophotometric analysis revealed quercetin as a major component in CASTAN. Jokar et al. (2016) tested different concentrations (0.1–0.4 g/L) of Morus alba pendula leaf extract (MAPLE) as a new green corrosion inhibitor for carbon steel in 1 M HCl solution at different temperatures (25–60 °C). The inhibitor adsorption/desorption behaviors in the tested solution was studied using UV/Vis spectrophotometric analysis. Results showed that high inhibition efficiency of 93% was achieved using 0.4 g/l MAPLE at room temperature (25 °C). Flavonoid components such as morusin, kuwanonC and kuwanonG, phenolic acids and pyrrole alkaloids were found in the MAPLE. They were found to be responsible for its high corrosion inhibition efficiency. MAPLE acted as a mixed type corrosion inhibitor and the inhibition efficiency increased by increasing the inhibitor concentration. It was found that the adsorption obeyed Langmuir adsorption isotherm. Chevalier et al. (2014) investigated the corrosion inhibition efficiency of alkaloidic extract of Aniba rosaeodora on C38 steel in 1 M HCl using electrochemical

32

1 Basic Corrosion Fundamentals, Aspects and Currently …

techniques. The extract was found to act as a mixed type corrosion inhibitor and was efficient in retarding the dissolution of the metal in the studied corrosive environment. Nuclear magnetic resonance spectroscopy (NMR) and XPS revealed that anibine was the major existed alkaloid and the one behind the anti-corrosion property of Aniba rosaeodora alkaloidic extract. M’hiri et al. (2016) investigated the capability of orange peel extract to inhibit corrosion of carbon steel. Some phenolic compounds flavones were identified by high performance liquid chromatography (HPLC) in the orange peel extract such as hesperidin, narirutin, neohesperidin, naringin, didymin. While, tangeretin, sinensetin, 3, 4, 5, 5, 6, 7,–hexamethoxyflavone, nobiletin belong to polymethoxylated flavones. Three chemical compounds were selected because of their antioxidant properties. Naringin, ascorbic acid, neohesperidin as well as the crude extract of orange peels were chosen to carry out the electrochemical studies and surface characterization. Authors observed that, the crude extract exhibited higher corrosion inhibition than the selected antioxidant compounds. Ghazouani et al. (2015) reported that polyphenols mainly rutin, neochlorogenic acid, and chlorogenic acid were the active compounds in quince pulp extract (QPE) that aided in corrosion inhibition of carbon steel in 1 M HCl solution. They represent 84% of the total existed phenolic compounds. The polarization measurements indicated that the extract acted as a mixed type corrosion inhibitor. The maximum inhibition efficiency attained was 88% at 5 ×10−1 g/l. The adsorption obeyed Langmuir adsorption isotherm. QPE inhibition efficiency was temperature independent. In Anthemis pseudocotula extract, the highly potent anti-corrosive compound was found to be luteolin-7-O-b-D-glucoside. Minor concentration of 0.446 mM was found to achieve 94.8% protection to mild steel surface in 1 M HCl solution (Alkhathlan et al. 2015). Methanolic extract of Rollinia occidentalis along with pure solution of two acetogenins isolated from the same extract, called rolliniastatin-1 and motrilin were tested for their corrosion inhibition efficiency of carbon steel in 1 M HCl (Alvarez et al. 2018). Weight loss measurements were performed in the range of 298–328 K to determine corrosion rate and corrosion inhibition efficiency. It was noted that the extract and the acetogenins solution acted as good corrosion inhibitors for carbon steel in 1 M HCl solution. It was found that 1 g/l of the crude extract exhibited corrosion inhibition efficiency of 79.7% while 0.007 g/l of Motrilin and Rolliniastatin exhibited 59 and 72% protection, respectively. Additionally, potentiodynamic polarization measurements indicated that R. occidentalis and the two tested acetogenins acted as mixed-type inhibitors. The adsorption of both the methanolic extract of Rollinia occidentalis and the acetogenins solutions followed Langmuir adsorption isotherm. Rice (scientific name: Oryza sativa L.) is a principal cereal grain all over the globe and it is a major source of food. There are two types of rice, the first one with white hulls, and the other has colored hulls. The compound momilactone A can be isolated from rice hulls. Prabakaran et al. (2017) tested for the first time momilactone A as a corrosion inhibitor for mild steel in 1 M HCl solution. It was concluded that momilactone A is an effective corrosion inhibitor. One thousand ppm of Momilactone A was found to exhibit 88% corrosion inhibition efficiency for mild steel. Surface morphology studies using SEM assured the presence of a protective

1.8 Corrosion Mitigation Strategies

33

layer over the mild steel surface. The tested corrosion inhibitor affected the cathodic site and lowered H2 evolution. Ginger belongs to Zingiberaceae family which is widely distributed particularly over tropical and sub-tropical regions. Ginger has many advantages as it is cheap, safe, readily available, and can be used as a traditional medicine in some of Asian countries (Chan et al. 2008). Ginger extract components are divided into two categories, i.e. volatile and non-volatile components. The non-volatile constituents are chiefly phenolic compounds such as curcumin and 6-gingerol. The phenolic constituents can be easily adsorbed onto metal surface; thus they can contribute to corrosion inhibition. The massive aromatic ring in ginger extract increases the inhibiting performance of ginger extract owing to the presence of the p-electrons and oxygen atom (Nasibi et al. 2014). According to Liu et al. (2019), liquid chromatography-mass spectrometry (LC-MS) identified the phenolic constituents of ginger extract. Gingerol, 8-Gingerol, Cyclocurcumin, 1-hydroxy-1, 5-bis (4-hydroxy-3-methoxyphenyl) pentan-3-one, 1hydroxy-1, 5-bis (4-hydroxy-3, 5-dimethoxyphenyl) pentan-3-on, and arginine were the main phenolic compounds in ginger extract. The inhibition effect of ginger extract was studied by various techniques including; stereo-microscopic analysis, electrochemical measurements and XPS. Results obtained from stereo-microscope in addition to the electrochemical studies indicated that the ginger extract was an efficient corrosion inhibitor in lowering chloride causing corrosion. The ginger extract acted as an effective mixed type corrosion inhibitor and exerted its corrosion inhibition effect by developing a carbonaceous organic film at both anodic and cathodic sites of the steel surface. Data from Attenuated Total Reflection-Fourier Transform Infrared (ATR-FTIR) and XPS demonstrated the establishment of the carbonaceous organic film. Eriobotrya japonica thunb belongs to the Rosa genus which is widespread in most of Southern China. E. japonica leaves are used medicinally to treat cold, cough, phlegm, chronic bronchitis, gastro-enteric disorders and high fever (Matalka et al. 2016). Electrochemical and surface characterization techniques were employed to study the anti-corrosion properties of hot water extract of E. japonica thunb leaves for carbon steel in HCl as reported by Zheng et al. (2018). The results showed that the extract formed a protective barrier layer on carbon steel surface by a physical adsorption mechanism. Accordingly, the cathodic hydrogen evolution and anodic dissolution reactions were prevented. E. japonica Thunb leaf extract (EJTLE) acted as a mixed-type corrosion inhibitor. The chemical composition of EJTLE largely consists of flavonoids, oleanolic acid and ursolic acid. It is worth mentioning that these chemical components displayed an anti-corrosive effect because of their heterocyclic structures as they are organic compounds containing heteroatoms such as O, S and N. Such heterocyclic compounds have effective adsorption centers. A study presented by El-Gendy et al. (2016) showed the corrosion inhibition effect of four domestic waste water extracts on C-steel in 1 M HCl solution as well as evaluating their biocidal activity against sulphate reducing bacteria (SRB). The studied aqueous extracts were the outer brown peels of onion (A), outer peels of garlic (B), orange (C), and mandarin (D) peels. It was found that they remarkably decreased the corrosion rate of carbon steel alloy in 1 M HCl. The four tested green corrosion

34

1 Basic Corrosion Fundamentals, Aspects and Currently …

inhibitors acted as mixed inhibitors (pickling inhibitors). The inhibition efficiency decreased in the following order: C > B > A > D with the increase of each extract concentration as revealed by the potentiodynamic polarization measurements. The SEM micrographs revealed the differences that took place after immersion of C-steel for 35 days in 1 M HCl solution in presence and absence of the green inhibitors. The visual observation confirmed that C-steel surface was highly destroyed with presence of pitted areas. While in presence of the green corrosion inhibitors, the pits disappeared remarkably and the C-steel was almost free from corrosion at 3000 mg/l of each extract. A mechanism of inhibition was suggested based on the chemical structure of the tested extracts. The chemical composition of onion peels (A) extract contains catechol quercetin (3, 5, 7, 3 , 4-pentahydroxy flavone), a protocatechuic acid, quercetin-3-glucoside, and some tannins. Garlic peels (B) extract involves the presence of allyl-propyl disulfide (C6 H12 S2 ), diallyl disulfide, (C6 H10 S2 ), and two extra sulfur-containing compounds along with proteins and carbohydrates. Additionally, the major constituents in orange and mandarin peel (C and D) extracts are eugenol, d-limonene, 4-vinyl guaiacol and other phenolic compounds (Omran et al. 2013). Interestingly, these compounds contain heteroatoms such as sulfur, oxygen, or nitrogen atoms, which may act as adsorption centers. The polarization measurements indicated that the tested extracts could inhibit corrosion via blocking the existed cathodic and anodic sites on metal surface. As demonstrated by AbdelGaber et al. (2009), this process could take place through: (1) electrostatic attraction forces between the positively charged protonated nitrogen atom and the negatively charged C-steel surface (cathodic sites), (2) dipole interaction between unshared electron pairs of oxygen atoms or π electrons interaction with the vacant, low-energy d-orbital of Fe surface atoms (anodic sites), and (3) a combination of all of the above (mixed type). The presence of high amounts of tannins facilitates the formation of a passivating layer on metal surface (Chaubey et al. 2015). Corrosion inhibition of low carbon steel in 1 M HCl was studied by Khadom et al. (2018) in absence and presence of leaf acidic extract of Xanthium strumarium as a green corrosion inhibitor. Weight loss technique was used to study the effects of temperature and inhibitor concentration. The inhibition efficiency was found to increase with increase in inhibitor concentration and temperature. The maximum inhibition efficiency was 94.82% at optimum concentration of 10 ml/l. The adsorption of X. strumarium leaf extract was found to follow Langmuir adsorption isotherm model. The adsorption of X. strumarium leaf extract was found to be a mix of chemical and physical adsorption. FTIR analysis showed that X. strumarium leaf extract contains a mixture of compounds such as amines, amides, organic acids and aromatic compounds. SEM micrographs showed that there was severe damage, clear cavities and pits on the surface of low carbon steel surface in absence of the inhibitor while less pits and cracks appeared in the treated surface. Henceforth, it was confirmed that a protective inhibition layer was made on low carbon steel surface suggesting its corrosion inhibitive effects. A study was proposed by Idouhli et al. (2019) to evaluate the capability of Senecio anteuphorbium ethanolic extract to act as a green corrosion inhibitor for S300 steel. The inhibitory effect of S. anteuphorbium extract was tested in 1 M HCl by using the

1.8 Corrosion Mitigation Strategies

35

potentiodynamic polarization and EIS. S. anteuphorbium extract acted as mixed-type inhibitor. The inhibition efficiency increased with increasing the extract concentration till reaching a maximum of 91% at a concentration of 30 mg/l. The tested inhibitor obeyed Langmuir adsorption isotherm. Different kinetic parameters were studied such as activation energy, enthalpy and entropy. Values of activation energy indicated that the adsorption mechanism was physico-chemical adsorption. FTIR spectra detected some functional groups with hetero-atoms. Sulphuric acid is another essential industrial acid like HCl. H2 SO4 is inexpensive compared with HCl. H2 SO4 is used for the manufacturing of many fertilizers such as phosphates, ammonium phosphates and calcium dihydrogen phosphate fertilizers (Umeron et al. 2019). The second biggest application of sulphuric acid is during metal processing such as acid pickling and cleaning. The effectiveness of H2 SO4 as a pickling agent is tremendously dependent temperture. The recommended H2 SO4 concentration for pickling is in the range of 5–10% (Maanonen 2014). As previously mentioned, adding corrosion inhibitor(s) to acid solution is necessary to protect the metals and to retard corrosion in corrosive environments. However, some reports indicated that plants extracts are more efficient in inhibiting HCl corrosion more than in H2 SO4 medium. For instance, Benahmed et al. (2015) reported that 500 ppm Bupleurum lancifolium (Apiaceae) inhibited carbon steel corrosion in H2 SO4 solution by 80% while it inhibited corrosion in HCl medium by 92.2%. Umoren et al. (2015) deployed that the inhibitive effectiveness of strawberry fruit extract for mild steel was better in HCl medium than in H2 SO4 solution. Other published reports aligned with such results were reported by Odewunmi et al. (2015), Swaroop et al. (2016), Prabakaran et al. (2017), Tasic et al. (2018) and Chen and Zhang (2018). This clearly distinguished between the influence of chloride and sulphate anions on the adsorption process of organic inhibitors. It is clearly known that chloride ions are less hydrated than sulphate ions and have a powerful tendency to be adsorbed on metal surface in comparison with sulphate ions (Odewunmi et al. 2015). Corrosion inhibition of mild steel using ethanol extract of Piper guinensis (EEPG) was studied by Ebenso et al. (2008) via gravimetric, thermometric and gasometric techniques. Piper guineensis is an African bush pepper and is cultivated in different regions in Nigerian, Malaya Island, India and some West African countries. It is worth denoting that fruits, roots and leaves of this plant are extensively used in treating asthma, bronchitis, fever and pain in abdomen and haemorrhoidal infection treatment. The fresh fruits of P. guineensis are often eaten raw for their spicy taste. Additionally, when fruits are dried, grinded and sieved; the resultant powder is further added to tea or coffee (Daglip 2004). Inhibition efficiency of the tested extract was found to vary with temperature, inhibitor concentration, and time. The obtained thermodynamic data revealed that adsorption of EEPG on mild steel surface followed Langmuir adsorption isotherm and a physical adsorption mechanism took place. Hassan et al. (2016) investigated the effect of Citrus aurantium leaf extract as a green corrosion inhibitor for mild steel in 1 M H2 SO4 . Effect of time, temperature and inhibitor concentration was studied using gravimetric techniques. The findings revealed that the leaf extract of C. aurantium acted as an inhibitor for mild steel in H2 SO4 and exhibited an anti-corrosion potential which was indicated by the lowering

36

1 Basic Corrosion Fundamentals, Aspects and Currently …

of the corrosion rate. The inhibition efficiency was found to increase with increase in inhibitor concentration and to decrease with increase in temperature. High inhibition efficiency was obtained and reached 89% at 40 °C and by using 10 ml/l inhibitor concentration. The adsorption of C. aurantium leaf extract was found to obey Langmuir adsorption isotherm. A physical adsorption between the charged molecules of C. aurantium leaf extract and the charged metal surface took place as the values of adsorption free energy were roughly 20 kJ/mol. This was indicative to the occurrence of physical adsorption between charged molecules and a charged metal. Finally, SEM and FTIR were employed to examine surface morphology and molecular structure of the tested inhibitor. SEM images revealed that the surface of mild steel was profoundly corroded in presence of 1 M H2 SO4 . Contrary, in presence of C. aurantium leaf extract, the surface condition was much better, suggesting that the metal surface was protected by an adsorbed layer from the tested green corrosion inhibitor. NaOH is a strong base with plenty of industrial applications. It is used in wood pulping, paper making, fiber generation, tissue digestion, etc. Moreover, it is used as an esterification and transesterification reagent, in food preparation as well as in alkaline pickling and cleansing (Maanonen 2014). Another significant application of NaOH is in manufacturing of air/metal batteries (Egan et al. 2013; Yisi et al. 2017). According to Singh et al. (2016), mitigation of aluminum corrosion in air battery is essential as metal corrosion poses extreme danger. The corrosion inhibiting effect of Piper longum water seed extract was investigated by Singh et al. (2016). The seed extract was evaluated for mitigation of aluminum corrosion in 1 M NaOH solution using EIS, potentiodynamic polarization and gravimetric techniques. Data showed that P. longum extract was an effective corrosion inhibitor, and the corrosion inhibition efficiency obtained from the weight loss experiments were confirmed by the polarization measurements. The extract acted as a mixedtype corrosion inhibitor as it suppressed both of the cathodic and anodic reactions on the metal surface. Other published reports confirmed the efficiency of using plant material extract as green corrosion inhibitors as reported by Irshedat et al. (2013) and Bataineh et al. (2014). According to Chaubey et al. (2015, 2017) Pisum sativum, Solanum tuberosum, Citrus reticulata, Kalmegh, and Neolamarkia Cadamba extracts achieved 80% protection of aluminum surface in 1 M NaOH solution. Bataineh et al. (2014) and Irshedat et al. (2013) demonstrated that Sinapis alba and Lupinus varius L. extracts suppressed aluminum corrosion in 1 M NaOH corrosive medium by 97.98% and 93.73%, respectively. Sodium chloride (NaCl) is a multipurpose salt and it has endless applications and uses. In petroleum and gas industries, NaCl is an important chemical in drilling fluids. It aids in increasing the density of drilling fluid and reducing well gas pressures (Lyons et al. 2016). Multiple research investigations focused and discussed metallic corrosion in NaCl media (Chen and Zhang 2018; Tasic et al. 2018). Different plant extracts were studied and evaluated as green corrosion inhibitors in NaCl solution including; Santolina chamaecyparissus (Shabani-Nooshabadi and Ghandchi 2015), Azadirachta indica (neem) (Swaroop et al. 2016), Anise (Pimpinella anisum),

1.8 Corrosion Mitigation Strategies

37

Caraway (Carum Carvi), Cumin (Cuminum cyminum) and Hibiscus (Hibiscus sabdarriffa) (Nagiub 2017). Recently, application of compounds and ionic solutions synthesized from multicomponent reactions (MCRs), microwave and ultrasound waves and various plant extracts emerged as green routes for inhibiting metal corrosion. The employment of plant extracts as metallic green corrosion inhibitors is recommended for future research because they have many advantages including; low cost, biodegradability, ease of availability, eco-friendliness, biocompatibility and high efficiency. Yet, several aspects need to be taken in consideration prior to their application in the real environments and fields. Before their application in real environment, it is necessary to be aware of their toxicity; biodegradability and bioaccumulation to comprehend their safety. It is established that only few particular components of a plant extract are in charge for inhibiting metallic corrosion and as a result it is strongly recommended to separate such phytochemicals. Isolation and identification of plant extract phytochemicals can be easily attained via HPLC-MS and GC–MS techniques. Furthermore, extraction methodologies of the extract are one of the most important aspects as processing time and high processing temperature retard their real application. Additionally, the effect of solvents which may be used for extract preparation on the surrounding environment needs to be taken into account as organic solvents are extremely toxic to humans and environment. (c) Amino Acids Amino acids are completely soluble in aqueous media, environmentally friendly compounds, and can be produced in high purity at low cost. Some reports implied the use of amino acids for corrosion inhibition of iron (Kandemirli and Bingul 2009), copper (Amin and Khaled 2010), aluminum alloy (Wang et al. 2016) and carbon steel (Zhang et al. 2016). Table 1.2 emphasizes several examples of amino acids which have corrosion inhibition potential.

1.8.3 Cathodic Protection Sir Humphrey Davy was credited for the first application of cathodic protection which dated back to 1824, long before the foundation of the theory itself (Groysman 2017). The basic principle of cathodic protection is to minimize corrosion by reducing the difference in potential between anode and cathode. This can be attained by applying a current to the structure that needs to be protected (e.g. pipelines) from an outside source. By applying enough current, the whole structure becomes one potential; and hence anodic and cathodic sites will no longer exist (Powell 2004). It is usually used in combination with coatings. Cathodic protection can be designed to eradicate both oxygen-controlled and microbiologically influenced corrosion (Popoola et al. 2013). Cathodic protection can be applied by either one of the two methods; Sacrificial or (galvanic) anode cathodic protection (SACP) or by impressed current cathodic protection (ICCP). The main difference between both techniques is that

Cassava fluid

Aspartic, glutamic acid, alanine, asparagine, glutamine, leucine, methionine, threonine

Nitric solution

NST-44 carbon steel

Glutamic acid, cysteine, glycine

HCl solution

H2 SO4

Serine, threonine, glutamic acid

0.5 M HCl

Lead and its alloys

Aspartic acid, glutamic acid, asparagine, glutamine

0.5 M HCl

Copper

Leucine, alanine, methionine, glutamic acid

Glutamic acid, alanine, valine, glycine, histidine, cysteine

Glycine, alanine, leucine, histidine, cysteine,

Aqueous chloride solutions

Cu–Ni alloys

Inhibitor

Medium

Metal

Weight loss immersion method and optical microscopic techniques

Polarization and impedance techniques

Weight loss and electrochemical polarization measurements

Electrochemical impedance spectroscopy, cyclic voltammetry, and quantum chemical calculation

Potentiodynamic polarization and electrochemical impedance Spectroscopy

Polarization and impedence techniques

Experimental procedures and characterization techniques

Table 1.2 Examples of some amino acids that exhibit anti-corrosion inhibition properties

Kiani et al. (2008)

Barouni et al. (2014)

Zhang et al. (2011)

Zhang et al. (2008a, 2008b)

Badawy et al. (2006)

References

(continued)

Alanine showed the Highest IE% (50%) while glutamic Alagbe et al. acid showed the least IE% with less than (23%) (2009)

Glutamic acid > alanine > valine > glycine > histidine > cysteine

The strongest protective effect took place by methionine (80.38%)

glutathione > cysteine > cysteine + glutamic acid + glycine > glutamic acid > glycine

Threonine and glutamic acid had good IE%

Glutamine > asparagine > glutamic acid > asparagine

Cysteine was the best corrosion inhibitor

Result

38 1 Basic Corrosion Fundamentals, Aspects and Currently …

Glutamic acid

0.5 M HCl

HCl solution

HCl solution

M3 copper

Aluminum

Mild steel

Glutamic acid

0.5 M HCl

Steel

2-(3-(carboxymethyl)-1H-imidazol-3-ium-1-yl) acetate (AIZ-1), 2-(3-(1-carboxyethyl)-1H-imidazol-3-ium-1-yl) propanoate (AIZ-2) and 2-(3-(1-carboxy-2-phenylethyl)-1H-imidazol-3-ium-1-yl)-3-phenylpropanoate (AIZ-3)

2-amino-4-(4-methoxyphenyl)-thiazole (MPT)

1 M HCl

0.5 M H2 SO4 , 1 M HCl

Glycine, threonine, phenylalanine, glutamic acid

Glycine, threonine, phenylalanine, glutamic acid

Glycine, Laspartic acid, L-glutamic acid, their benzenesulphonyl derivatives

0.6 M NaCl solution

Brass (made up of copper and zinc)

Inhibitor

Medium

Metal

Table 1.2 (continued)

Potentiodynamic polarization, EIS, UV-Vis spectrophotometer

Potentiodynamic polarization, EIS, SEM, AFM and energy-dispersive X-ray spectroscopy (EDX)

Weight loss, gasometric and thermometric methods

Linear polarization, potentiodynamic polarization, EIS

Electrochemical methods

Electrochemical methods



Experimental procedures and characterization techniques

Xhanari and Finšgar (2016)

Zapata-Lori and Pech-Canul (2014)

Makarenko et al. (2011)

Ranjana and Banerjee (2010)

References

Inhibition of anodic corrosion of mild steel in HCl solution and cathodic corrosion in H2 SO4 solution

Gong et al. (2019)

AIZ-1 acted as cathodic type inhibitor while AIZ-2 and Srivastava et al. AIZ-3 behaved as mixed type inhibitors (2017)

Good corrosion inhibitor

Mixed-type inhibitor

Glutamic acid achieved 53.6% protection

Glutamic acid failed to form a blocking barrier

Glutamic acid (59.5%) > aspartic acid (47.7%) > glycine (32%) and the same trend is followed for benzenesulphonyl derivatives

Result

1.8 Corrosion Mitigation Strategies 39

40

1 Basic Corrosion Fundamentals, Aspects and Currently …

ICCP depends on using an external power source with inert anodes, while SACP provides protection by using the naturally occurring electrochemical potential difference between the different metallic elements. SACP is based on the use of sacrificial anodes as they are sacrificed i.e. being dissolved as anode, and turn the metallic construction to cathode which does not corrode. The second method of cathodic protection (ICCP) is based upon the connection to the negative pole of the rectifier and the use of impressed electric current. This method is sometimes referred to as “an active method of cathodic protection”. Cathodic protection is one of the widest spread techniques to protect submerged and underground metallic structures and equipment against corrosion. It is worth mentioning that, cathodic protection deals only with the external surface that is not in contact with the flowing media or stored inside the structure that needs protection like gas, oil, fuel, or water. Several factors might cause implementation to cathodic protection including; high temperatures, destroyed shielding and coatings, microbial attack, etc. (Groysman 2017). It is important to note that cathodic protection does not work when one of the following components is missing; an anode, a cathode, an electrolyte, and a complete electrical circuit. Robert Kuhn was the first engineer who applied cathodic protection on pipelines for the transportation of natural gas in the U.S. in 1928 and in 1930s (Heidersbach 2011). It is important to keep in mind that the corrosion rate of cathodically protected structure never reaches zero but very low value which makes it acceptable for safe use without corrosion risk. However, cathodic protection can cause the following problems; debonding of coatings, hydrogen embrittlement and corrosion of aluminum as hydroxyl ions formed during cathodic protection are destructive to aluminum.

1.8.4 Use of Corrosion Resistant Alloys In order to maintain and ensure smooth operations as well as safe production of products in oil and gas industries, it is essential to select material that can be highly resistant to corrosion and to excel the less resistant materials. Use of corrosion resistant alloys (CRAs) is an advanced technology that is very suitable to the requirements needed in areas of exploration and production. CRAs are superior alloys with outstanding corrosion resistance features. They possess the potential and the strength to resist harsh working conditions such as high temperature and pressure (Makhlouf et al. 2018).

1.9 Conclusions Constructions and metallic equipment in gas, oil and refinery plants are in continuous contact with natural gas, petroleum products, fuels, crude oils, water, solvents, water, atmosphere, and soil. This close contact results in the appearance of the destructive

1.9 Conclusions

41

damage of corrosion. Both of crude oil and natural gas may carry a number of highimpurity products which are extensively corrosive. Carbon dioxide (CO2 ), hydrogen sulfide (H2 S), and free water are among the most corrosive reagents in oil and gas wells and pipes. Corrosion leads to material degradation and loss of mechanical features such as ductility, strength, impact strength, and so on. Hence, this leads to material loss, reduction in thickness, and ultimate failure. Usually, corrosion mitigation has been managed by various methods such as cathodic protection, reduction of metal impurity content, process control, application of surface treatment techniques (i.e. paints and coatings), as well as incorporation of suitable alloys, and use of corrosion inhibitors. Nevertheless, the use of corrosion inhibitors has proven to be the best and cheapest methodology for corrosion inhibition and prevention. These inhibitors reduce the corrosion rate and consequently prevent financial losses in industrial vessels, equipment, or surfaces. Inorganic and organic inhibitors are hazardous and expensive. Accordingly, recent focus has been directed towards the development of environmentally benign corrosion inhibitors like plant biomaterials and amino acids. Indeed, material and coating selection are very important factors that can effectively eradicate corrosion, protect environments, and the working personnel.

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Chapter 2

The Catastrophic Battle of Biofouling in Oil and Gas Facilities: Impacts, History, Involved Microorganisms, Biocides and Polymer Coatings to Combat Biofouling Abstract Biofouling is an ancient undesirable phenomenon that takes place in several disciplines. Biofouling refers to the harmful effects which result from the microbial, algal and invertebrate colonization of man-made surfaces. Biofouling is classified into two main categories including; microbial and macrobial biofouling. Both exert deteriorating impact on environmental, health, industrial and safety disciplines. Biocides are usually employed to combat and treat the devastating effects which result from biofouling occurrence. Biocides are divided into oxidizing and non-oxidizing biocides. Nonetheless, due to the high toxicity of such chemically synthesized biocides, new and eco-friendly formulations were explored by several researchers. Biomimetic inspired anti-foulants have been under study. Different compounds have been extracted from plant biomaterials, micro- and macro-algae, seaweeds, microorganisms and bacteriophages. Such compounds proved to display anti-biofouling effect. This chapter highlights the different fields that might be susceptible to biofouling including; marine, oil and gas industrial sectors. This chapter explores the deleterious consequences of biofouling. Moreover, biofouling types are investigated in details, factors which affect the phenomenon of biofouling as well as the common analytical techniques that are employed for the assessment of microbial corrosion. This chapter also emphasizes the-state-of the-art of the recent investigated trends that are employed to eradicate biofouling. Keywords Microbial and macrobial biofouling · Sulphate reducing bacteria · Assessment · Prevention and control · Biocides · Green biocides

2.1 Introduction Since the manufacturing of boats and using them by man for travelling, humans began to suffer from biofouling and this was the starting point of the battle of biofouling. In 1952, Anon reported that there were documents dated back to the Greek and Roman civilizations, that clarified the use of copper or lead as a covering outer layer to protect wooden boats (Anon 1952). Biofouling is defined as “the detrimental deposition of a biological growth by both micro- and macro-organisms along with other © Springer Nature Switzerland AG 2020 B. A. Omran and M. O. Abdel-Salam, A New Era for Microbial Corrosion Mitigation Using Nanotechnology, Advances in Material Research and Technology, https://doi.org/10.1007/978-3-030-49532-9_2

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constituents of natural water that causes defects in the performance and efficiency of industrial equipment and operations” (Rao 2015). The damaging attachment of either living or non-living constituents to either the surface or the inner parts of system operations is a global phenomenon (Mikhaylin and Bazinet 2016). The incidence of such phenomenon is a huge problem that faces researchers and industrial personnel in different fields including; oil, gas, chemical, medical, pharmaceutical, agricultural, and food domains. Biofouling occurs due to the interaction between water and any submerged surface which makes it vulnerable to colonization by microorganisms (Debiemme-Chouvy and Cachet 2018). Different constructions are susceptible to biofouling such as ship hulls, engines, marine platforms and equipment. Marine biofouling represents a massive problem that faces navigation and marine infrastructures and accordingly it leads to an increase in marine structure fatigue, fuel consumption as well as biocorrosion (Telegdi et al. 2017). It also results in disastrous consequences as well as major economic losses. According to Townsin (2003), 10% reduction in speed occurs because of the fouling in ship hulls. Moreover, the fuel consumption increases to approximately 40% for any fouled vessel; hence leads to high fuel consumption whose costs may reach up to 20 billion Euros/year. Besides, greenhouse gas emissions may reach up to 20 million tons/year. Railkin (2004) and Jones (2009) reported that nearly 3.3 million barrels were lost because of biofouling. Ships, pontoons, buoys, offshore structures, seawater cooling systems, oil installations, underwater cables, aquatic instruments and platforms are among the structures that can be vulnerable to biofouling. According to Lebret et al. (2009a), areas with high aeration such as a ship’s waterline and wheels suffer from high rates of biofouling. Additionally, biofouling (i.e. micro- and macro-biofouling) can majorly affect petroleum industries as demonstrated by Omran et al. (2013) and El-Gendy et al. (2016). The undesirable colonization of man-made surfaces by microorganisms such as bacteria, yeast, fungi, microalgae and invertebrates leads to fatal biodeterioration to surfaces. Yebra et al. (2004) demonstrated that the biofouling process is comprised of several steps, starting from the initial conditioning of the surface via organic and inorganic molecules to the colonization of microorganisms (microbial biofouling) and eventually, the establishment and growth of macroorganisms (macrobial biofouling). From the industrial perspective, biofouling affects heat exchangers and membranes and hence results in reducing their efficiency. Furthermore, drinking water systems become contaminated with microbial pathogens. Frictional loss and contamination of produced fuels take place as well. Accordingly, severe hazardous effects on working personal might occur. In addition, from the medical point of view, biofouling can affect different medical implants such as teeth, orthopedic, contact lenses, catheter and dental implants which result in fatal consequences such as eye and urinary tract infections, periodontal diseases, gingivitis and ventilatorassociated pneumonia. And so, biofouling has huge negative impacts upon human health, environment and worldwide economy. Eradication of both corrosion and biofouling still represents a major challenge that faces researchers and engineers. Different mitigation strategies are employed including; the use of paints and coatings, employment of corrosion inhibitors and biocides. The application of biocides is the most practical strategy for biofouling

2.1 Introduction

49

mitigation. Literature survey directs attention to several studies to address this issue (Murthy et al. 2005; Kaur et al. 2009; Bautista et al. 2016; Deyab 2018). When an industrial system such as an operating industrial unit is infested with biofouling, urgent control becomes difficult and costly. Clare (1998) demonstrated that different methodologies such as screens of various structures and sizes, heat treatment and employment of biocides aid in the prevention and the control of biofouling. Additionally, chlorination is one of the most effective anti-biofouling methodology which proved its efficacy, low cost and availability. Chlorine has been utilized to control the growth of both slime and macrofouling organisms. Chlorine is an oxidizing agent which diffuses throughout the microbial cell wall, thus results in enzyme denaturation and prevention of any further metabolic activities (Rao 2015). Moreover, it has a lethal effect on barnacles and mussels as it reduces their growth. In case of bivalves, chlorine cuts off the food and oxygen supply (Rajagopal 2012). Chlorine is a gas that is added before the condenser section in a dispenser unit and also at the beginning of the pre-condenser section to attain residual chlorine in the range of 1.5–2 mg/l when used occasionally and 0.5 mg/l when used continuously to control the settlement of barnacle larvae and mussels. Chlorination is considered the main methodolgy for controlling the growth of fouling organisms in most cooling systems (Rajagopal 2012). In addition to chlorine, different biocides are utilized in biofouling control including; chlorine dioxide, bromine, bromine chloride, ozone in addition to organic biocides (Petrucci 2005; Sweta et al. 2013). Majority of these biocides are deployed in self-polishing coatings, depletion paints and metal embedded polyacrylicresins to tackle micro-fouling (Fathima et al. 2017). However, it is noteworthy that the broadspectrum biocides like tributylin (TBT), diuron, tetrakishydroxymethyl phosphonium sulfonate, benzyl trimethyl ammonium chloride and formaldehyde, glutaraldehyde, etc. are extremely toxic to the aquatic fauna and non-target benthic organisms (Fitridge et al. 2012). The consequences of the chemical based biocides are so intense that most of the marine regulatory bodies like the international maritime organization, biocidal product regulation (EU 528/2012) etc., have banned their application (Tralau et al. 2015). Henceforth, exploring anti-biofouling properties of natural sources and nanoparticles (NPs) as better alternatives for these toxic chemicals is the need of the hour (Carvalho et al. 2017; Pugazhendhi et al. 2018). Though, an increased environmental concern regarding its ecological impact has resulted in decreasing the levels of the used chemical biocides (Rao 2015). It is important to keep in mind that employment of a particular control strategy may not be effective for a long time use. And so, a regular alteration of the biocide type and dosing amount must be taken into consideration.

2.2 Definition and Impacts of Biofouling Microorganisms are abundant in nature and are present everywhere i.e. air, soil and water. Microorganisms involved in biofouling, biodeterioration, and biocorrosion are usually extremophiles, meaning that they tolerate extreme conditions such

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as extreme variations in temperature, pH, pressure and metal concentrations. As mentioned earlier, corrosion is defined as “the destruction or deterioration of metals and alloys by chemical or electrochemical reactions”. Contrary, the participation of microorganisms in metal corrosion is referred to as “biocorrosion or particularly as microbial corrosion” (Omran et al. 2013). Microbial corrosion or biocorrosion can be defined as “electrochemical processes in which microorganisms initiate, accelerate, or facilitate anodic and/or cathodic reactions”. Usually, microbes serve as electrochemical catalysts in microbial corrosion. Microbial corrosion begins and remains sustained under variable conditions such as oxic, anoxic, acidic, neutral, or alkaline conditions. Localized corrosion attacks can be a result of microbial corrosion such as dealloying, pitting, under deposit, crevice, galvanic, stress corrosion, and hydrogen cracking. Biofouling is the general term and is referred to as “the undesirable adhesion and accumulation of micro- and macro-organisms on submerged structures e.g., as in sea water” (Liengen et al. 2014). Biofouling takes place via micro- and macro-organisms which act as foulants as they become firmly adhered and attached to surfaces. Microbiofouling occurs due to adhesion of microorganisms such as bacteria and then it is followed by macrobiofouling which occurs due to the adhesion of fungi, algae, sea urchins, shells, etc. The US oil and gas disciplines suffer from severe costs which reach approximately $1.372 billion per year due to biofouling according to the National Association of Corrosion Engineers (Campbell 2017). Microbial corrosion has been evaluated to account for more than 40–50% of all internal corrosion problems. Numerous problems accompany the presence of microorganisms in oil and gas industries including; reservoir souring, rock porosity plugging leading to loss of production, formation damage, formation of emulsion with and decreased flow-line and pipeline lifetime (Enzien et al. 2011). Biofouling causes severe consequences for medical, marine and industrial sectors leading to health risks, economical losses and environmental hazards. Listed below the devastating effects of biofouling in the medical, marine and industrial sectors.

2.2.1 Medical Sector It is estimated that 45 percent of hospital infections are relevant to biofilm established on medical devices. Catheters are one of the most commonly used medical devices and are very susceptible to infection (Chan and Wong 2010). Two types of medical devices can be affected by biofouling and they are classified into two main categories including; permanent and temporary devices (Bixler and Bhushan 2012). Generally, the permanent device is the device that is implanted and intended to be used for long time (non-disposable), whereas a temporary device is used for short-term use only (disposable) (Bixler and Bhushan 2012). It has been reported that patients can get an infection from clinical implants e.g. urethral catheter, tracheal tube or vascular catheter. Bixler and Bhushan (2012) demonstrated that infections can also occur via the ventilator, thereby leading to ventilator-associated pneumonia. A surgical replacement is usually essential to treat the biofilm infections on medical

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devices which in turn may result in increase of antibody resistance and mortality risk. For instance, infections caused by pathogenic methicillin-resistant Staphylococcus aureus (MRSA) are one of the horrible infections due to its resistance to methicillin (Gajdács 2019). Using antibiotics to eradicate biofilms is usually useless and this may lead to complex medical conditions such as cystic fibrosis. Besides, thrombosis may occur because of protein fouling on biological implants. Fastener implants as well as bone plates are essential for patients suffering from severe trauma after a catastrophic injury. Such medical implants are vulnerable to biofilm formation due to the presence of microorganisms such as S. aureus around the contaminated wound area (Khatoon et al. 2018). It is worth noting that when these implants become infected they can be no longer treated with antibiotics and rather they must be replaced. Dental implants can be a source for infection particularly during surgeries. Dental plaque biofilm is made up of a varied collection of microorganisms in the oral cavity, with several bacterial species such as S. mutans. Dental decay occurs because of the growth of plaque on teeth, gum, tongue and cheeks leading to periodontal disease. Microorganisms living in saliva colonize tooth enamel, dental implants and cementum. Plaque can be also formed inside teeth sockets where microorganisms are protected from the usual cleaning mechanisms such as saliva, chewing, mouth brushing and rinses.

2.2.2 Marine Sector The most noticed type of biofouling is existed in the marine environment. Ships, sonar devices, buoys, supports, offshore infrastructures, platforms, oil installations, underwater cables, acoustic equipment, seawater cooling structures and marinas are usually subjected to incidence of biofouling. Biofouling begins when ocean-going ships are immersed in the sea water. First, bacteria and unicellular microorganisms settle and start forming slimy layers (Hakim et al. 2019). Afterwards, numerous chemical secretions are released which in turn trigger multicellular and macrofouling species to settle down, thus leading to the occurrence of biofouling. Biofouling leads to increase in ship fuel consumption and consequently leads to increase in greenhouse emissions such as CO2 , SO2 and NOx (Dobretsov 2009). The massive release of greenhouse emissions due to biofouling result in climate changes. With regards to environmental safety, infected marine structures bear biofouling organisms which can be transported from one place to another leading to the invasive spread of foulers (Hakim et al. 2019).

2.2.3 Industrial Sector Industrial fouling can have severe consequences upon different industrial sectors ranging from nuclear power plants to petroleum industry and food production (Somerscales and Knudsen 1981; Walker et al. 2000; Chan and Wong 2010; Omran

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et al. 2013, 2018). Decrease in heat transfer efficiency along with the high consumption of energy friction is among the impacts caused by biofouling (Richardson 1984). Biofilms can also harbor hazardous pathogenic microorganisms in drinking water systems. Unfortunately, most water supplies even stainless steel pipes are vulnerable to biofilm formation (Lebret et al. 2009b). Pipeline failure usually occurs during oil and gas operations because of the microbially influenced corrosion. It is estimated that more than 40–50% of such failures are brought about by microorganisms. Microbial corrosion has been detected in oil and gas treating facilities like refineries, pipeline system, gas fractionating plants and storage terminals. Besides, oil souring takes place owing to the release of H2 S.

2.3 Microbial Biofouling Microbial biofouling or microbial corrosion is one of the extremely mysterious problems in corrosion science and engineering due to the difficulties which result from the existence of living micro- and macro-organisms (Telegdi et al. 2017). It denotes to the probability that microorganisms may be responsible for the deterioration of metals and alloy materials. It is worth noting that water must be present even at very low quantities (Little and Lee 2014). Borenstein (1994) defined microbial corrosion as “the deterioration of a metal by corrosion processes that occur when microorganisms or any of their metabolites exist” (Brondel et al. 1994). According to Mahat et al. (2012), microbial corrosion is a serious problem in many industries, such as chemical processing, aviation, petrochemical, oil, gas, nuclear power, water distribution, cooling water systems, storage and underground tanks, ships, medical devices, rail systems, and the storage facilities of nuclear waste. Microbial corrosion is an important reason for petroleum and gas pipeline failure in the petroleum sector. Although, it is still difficult to distinguish between the normal cases of corrosion and the microbial corrosion, some authors reported that 20% of all pipeline corrosion is mainly due to microbial corrosion (Flemming 1996; Beech and Gaylarde 1989; Li et al. 2018). In Egypt, petroleum industries suffer from corrosion induced by microorganisms. Ateya et al. (2008) reported that Gulf of Suez Petroleum Company (GUPCO) spends more than $ 1 million per year to combat microbial corrosion. This was attributed to microorganisms which were found in the treated seawater used that was for injection into the producing wells to enhance oil recovery. To determine whether corrosion is due to microorganisms or not, various circumstances have to be considered (Lutey 1995) including: • • • •

Pitting corrosion is the most typical form in microbial corrosion, Presence of slime, Presence of hydrogen sulphide (H2 S), Presence of fungal and/or bacterial populations.

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For better understanding, to sustain microbial corrosion and its impact on pipelines, tanks, reservoirs and metallic structures, it is necessary to identify the microorganisms responsible for microbial corrosion, their types and their detrimental impact on metals. As mentioned earlier microbial corrosion is existed since a long time ago, but the involvement of microorganisms, their metabolites, extracellular polymeric substances (EPS) and aggressiveness have severe consequences on materials particularly metals. The presence of metabolites (organic acids, sulfides) along with EPS cause localized corrosion. Severe biocorrosion is usually accompanied by the presence of more than one type of corrosion causing microbes altogether. These corrosion causing microorganisms include; methanogens, sulfur-oxidizing bacteria, acid-producing bacteria, iron oxidizing bacteria, iron reducing bacteria, manganese-oxidizing bacteria and sulphate reducing bacteria.

2.3.1 History of Research on Microbial Corrosion It was until the latest of the 19th century when the role of microorganisms in corrosion was investigated. Garrett (1891) was the first to report that microorganisms might be responsible and involved in corrosion. He suggested that the interaction of bacterial metabolites with a lead cable resulted in corrosion of incidence of corrosion. In 1910, Gaines correlated the destructive activity that might occur because of the microbial activity and the presence of sulfur as a corrosion product (Gaines 1910). Microbial corrosion first appeared in Castgill aqueduct in the United States. In 1934, the “Cathodic Depolarization Theory” (CDT) theory was suggested by both von Wolzogen Kuhr and va der Flugt. This theory explained the electrochemical reaction of microbial corrosion. Afterwards, since 1934 and till the 1960s, many reports were published investigating practical cases that assured the involvement of bacteria in incidence of corrosion (Videla and Herrera 2015). In 1960s and the early of 1970s, scientists focused their corrosion research towards microbial corrosion (Javaherdashti 2008). During this period, experiments depending on electrochemical techniques, such as polarization measurements were employed to study microbial corrosion. By the 1980s, research on microbial corrosion reached its major advancement. This occurred because of the cooperation between different science branches including metallurgy, materials science, microbiology and chemistry. By the 1990s, some new techniques allowed researchers to monitor bacterial adhesion to the affected metal surface. Nonetheless, major research started during the middle of the last century when it was believed that microbial corrosion could be really existed.

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2.3.2 Mechanism and Microorganisms Involved in Biotic/Aerobic Microbial Corrosion Aerobic microbially influenced corrosion includes different complex chemical and microbial processes because of the metabolic activities of different groups of microorganisms which exist in aerobic environments. As the name implies, aerobic microbes consume oxygen and produce metabolic by-products which serve as nutrients for anaerobes thereby creating anaerobic niches. Iron is known to have two oxidative states namely ferrous (Fe+2 ) and ferric (Fe+3 ) (Gu et al. 2018). When molecular oxygen (O2 ) is available, it contributes to the oxidation of metallic iron (Fe). The metal area below the microbial colonies acts as an anode, while the area that is far away from the colonies and in which oxygen concentration is relatively high, serves as the cathode. Afterwards, electrons start to flow from the anodic site to the cathodic site where corrosion is initiated, leading to iron dissolution. Depending on the type of existed bacteria and the nature of the chemical reactions, the dissociated metal ions produce ferrous hydroxides, ferric hydroxide, and other Fe-containing minerals. The distance between both the anodic and the cathodic sites are influenced by the surrounding electrolytes. Moreover, contaminants and impurities within metal matrices stimulate corrosion by initializing the formation of differential cells and accelerated electrochemical reactions (Gu et al. 2018). Under aerobic conditions, corrosion products form “tubercles” which are known to be one of the most aggressive forms of corrosion. It seems to occur due to the formation of differential oxygenconcentration cells on material surfaces. Tubercles are composed of three layers; inner, middle and outer ones. Generally, the inner layer is a green one and it almost contains ferrous hydroxide (Fe[OH]2 ), whereas the outer layer contains orange ferric hydroxide (Fe[OH]3 ). In between these two layers, magnetite (Fe3 O4 ) forms a black layer (Lee et al. 1995). The overall reaction is summarized in Eqs. (2.1–2.3): Fe0 → Fe+2 + 2e− (Anode)

(2.1)

O2 + 2H2 O + 4e_ → 4OH− (Cathode)

(2.2)

1 2Fe+2 + O2 + 5H2 O → 2Fe(OH)3 (T uber cle) 2

(2.3)

Different types of microorganisms are involved in aerobic microbial corrosion including:

2.3.2.1

Sulfur-Oxidizing Bacteria (SOB)

Sulfur-oxidizing bacteria (SOB) are aerobic and phototrophic/chemolithotrophic bacteria which aid in the biological oxidation of sulfides. Photoautotrophic SOB depends on light energy for their metabolism. Nonetheless, chemolithotrophic SOB

2.3 Microbial Biofouling

55

acquire their energy via oxidation reactions at which oxygen (oxic microbial species), nitrites or nitrates (anoxic microbial species) serve as electron acceptors. According to Janssen et al. (1998), SOB are characterized by the utmost rates of sulfide oxidation, low nutritional requirements and tremendous high affinity towards oxygen and sulfides. Accordingly, these features allow them to effectively compete with the chemical oxidation of sulfides in both the natural environment and bioreactors. SOB oxidizes H2 S to elemental sulfur; meanwhile, CO2 is reduced and combined with organic compounds. The strength of the required applied light energy chiefly relies on the sulfide concentration and is expressed by van Niel curve (Cork et al. 1985). This curve expresses the intensity of light energy that is needed for sulfides to be oxidized to elemental sulfur. When sulfide concentration is high at a certain light intensity, it accumulates within the photoreactor. Vice versa, when sulfide concentration is lower than a certain light intensity, they are oxidized to sulfates. The hydrogen source for these bacteria is usually hydrogen sulfide or molecular hydrogen. Phototrophic SOB are categorized into green sulfur-oxidizing bacteria (GSOB) and purple sulfuroxidizing bacteria (PSOB) (Pokorna and Zabranska 2015). Both depend on light and CO2 for the formation of new cell materials along with inorganic nutrients such as ammonium salts e.g. sulfates, phosphates or chlorides. GSOB oxidize sulfides to elemental sulfur through to sulfates. It is worth mentioning that GSOB can perform its function at extremely low light intensity conditions and under anoxic conditions, but they do not propagate in darkness. GSOB include several species such as Chloroherpeton, Chlorobium, Pelodictyon, Prosthecochloris and Ancalochloris. Contrary, PSOB include Chromatium, Allochromatium, Thiorodococcus, Thioalkalicoccus, Thiocystys, Thiococcus, and Thiospirillum. The produced sulfur is stored as rounded shaped particles within the cells. Successively, oxidation takes place and produced sulfates are released from the cell. PSOB are able to consume organic compounds, and therefore they are considered as facultative photolithotrophic bacteria. Additionally, SOB such as Thiorhodospira, Ectothiorhodospira and Halorhodospira are able to produce sulfur outside the cell. Chemolithotrophic SOB are colorless. They use CO2 as a carbon source for the assembly of new cell materials. They are Gram negative bacteria. Their optimum temperatures vary from 4 to 90 °C and pH values vary from 1 to 9. According to Cattaneo et al. (2003), chemolithotrophic SOB depend on the energy derived from the reduction of inorganic sulfur compounds such as elemental sulfur, thiosulfates, hydrogen sulfide or sulfites and in certain cases they utilize organic sulfur compounds e.g. dimethyl sulfide, methane thiol or dimethyl disulfide. Chemolithotrophic SOB consist of two divergent clusters; small short rods of the genus Thiobacillus (T. denitrificans, T. thioparus, or T. thiooxidans) and long filamentous bacteria of the genera Thiothrix and Beggiatoa. The group of long filamentous bacteria oxidizes H2 S to S0 , which is then stored inside the cell, and it can be subsequently oxidized to sulfates. Thiobacillus sp. is the most investigated genus in SOB. Thiobacillus sp. grow at different pH variations as illustrated in Table 2.1. Thiobacillus sp. was reported by Pokorna and Zabranska (2015) to be the reason behind the biodeterioration of concrete sewers. This was because of the secreted sulfuric and sulfurous acids which are extremely destructive to concrete.

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Table 2.1 pH variations for Thiobacillus sp.

2.3.2.2

Thiobacillus sp.

pH range

T. thiooxidans

2.0–3.5

T. ferrooxidans

1.3–4.5

T. denitrificans, T. novellus

6–8

T. thioparus

5–9 (optimum 7.5)

Manganese and Iron Oxidizing Bacteria (MOB and IOB)

Iron and manganese bacteria are groups of aerobic bacteria which utilize ferrous and/or manganous ions via oxidation respectively. Usually ferric (brown) and/or manganese (pink) salt deposits are secreted and they are mainly hydroxides. It has been speculated that such hydroxides shift the corrosion potential of passivated metals to noble direction, leading to an increase in corrosion potential (Chan et al. 2011). Sphaerotilus, Gallionella, Crenothrix and Leptothrix are among the most common genera in iron oxidizing bacteria (IOB) (Ehrlich 1996). Both IOB and manganese oxidizing bacteria (MOB) produce the highly aggressive ferric chlorides which result from the oxidation of ferrous to ferric ions. Stainless steel and carbon steel are the most susceptible metallic structures to the severe effects of IOB and MOB as demonstrated by Telegdi et al. (2017). Kielemoes et al. (2002) proved that different microbial communities were present in the brackish water in the Canal of Ghent-Terneuzen. These microbial communities were responsible for biofilm formation and biocorrosion. Microscopic and denaturing gradient gel electrophoresis (DGGE) analyses of this water revealed the existence of metal-depositing Leptothrix- manganese oxidizing bacteria. 316L stainless steel was used to study the biofilm formation in a pilot scale system fed with the brackish surface using an alternating flow/stagnation/flow regime. Large amounts of iron and manganese were revealed via the chemical identification of the biofilm. DGGE indicated the presence of microorganisms in the deposition and accumulation of ironand manganese oxides within the biofilm. In 2004, Chamritski and coauthors tracked the influence of IOB on stainless steel. UNS S30403 was the used type of stainless steel (SS). UNS S30403 was exposed to natural spring water in New Zealand. Results showed that maximum open-circuit potentials exceeded 200 mVSCE , which was very close to the values typically caused by microbially influenced ennoblement. A biofilm was formed on the surface of UNS S30403 SS which showed the presence of a mixture of α-FeOOH, γ-FeOOH, and Fe3 O4 or γ-Fe2 O3 . Authors emphasized that UNS S30403 SS was not exposed to microbial corrosion by the effect of iron-oxidizing bacteria alone. They claimed that other types of bacteria were likely to be involved like MOB.

2.3 Microbial Biofouling

2.3.2.3

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Slime Forming Bacteria

The most common bacteria in this group are the genera of Pseudomonas, Escherichia, Flavobacterium, Aerobacter and Bacillus (Borenstein 1994). Slime formers exist in oxic and anoxic circumstances. They cause microbial corrosion through the production of a slimy layer on the surface of the metal. Their thick slime also stimulates anaerobic conditions in which corrosive anaerobes can live. Pseudomonas species are the most prevalent bacterial species in industrial water systems. Pseudomonas species particularly P. fluorescens and P. aeruginosa produce high amounts of exopolysaccharides that aid in their adherence, thus leading to the subsequent colonization on metallic surfaces. P. aeruginosa is a Gram-negative motile rod bacterium which is widely distributed in nature (Mansouri et al. 2012). Moreover; P. aeruginosa is a predominant microbial species in aquatic environments that is responsible for microbial corrosion in steel surface. San et al. (2014) demonstrated that Pseudomonas sp. are usually involved in corrosion processes and are recognized as the pioneer colonizers during biofilm formation. Mahat et al. (2012) reported that P. aeruginosa had the tendency to increase the corrosion rates of mild steel and metallic alloys in aquatic environments. In a recent study, Khan et al. (2019) investigated the highly corrosive and severe deterioration effects caused by the marine aerobic bacterium Pseudomonas aeruginosa on pure titanium. The obtained results assured the acceleration of biocorrosion by the biofilm induced by P. aeruginosa. Electrochemical tests were carried out to detect the effect of P. aeruginosa on titanium. The polarization curves showed an increase in corrosion current density (icorr) and electrochemical impedance spectroscopy (EIS) showed a decrease in charge transfer resistance (Rct ). Moreover, the surface of titanium was investigated using scanning electron microscope (SEM), confocal laser scanning microscope (CLSM) and X-ray photoelectron spectroscopy (XPS). Observations showed that titanium was vulnerable to microbial corrosion and was not immune against it because of the occurrence of pitting corrosion. The acceleration of corrosion was suggested to be due to the formation of Ti2 O3 oxide film, which is an unstable oxide that leads to defects in the passive film and accordingly leads to the occurrence of localized pitting corrosion.

2.3.2.4

Acid-Producing Bacteria (APB)

Acid producing bacteria (APB) secrete organic acids such as butyric and acetic acids and inorganic acids such as sulfuric acid which are considered as one of the most corrosive metabolites (Xu et al. 2016). Organic acids are very weak acids but can be very corrosive because organic acids tend to have a buffering power to supply more protons (Kryachko and Hemmingsen 2017). Additionally, they produce fatty acids which are mainly consumed by sulfate reducing bacteria to support their growth. They cause a drop in the pH of the surrounding environment because of the produced acids. That explains why the area beneath a biofilm can be very lower in pH than that of the bulk fluid. Proton attacks become thermodynamically desirable particularly when

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combined with iron oxidation. In such case, planktonic cells can cause corrosion by generating protons to maintain the acidic environment. APB become fermentative bacteria in absence of oxygen because acids are common products in anaerobic fermentation. Aerobic APB include genera such as Acidithiobacillus spp. They are usually responsible for bioleaching because of their autotrophic growth. They can result in decreasing the pH as low as 1 (Gu et al. 2018). Dong et al. (2018) reported that Acidithiobacillus caldus caused severe corrosion to a high-quality stainless steel. Henceforth, precautions must be taken into account to prevent APB corrosion against stainless steel walls.

2.3.2.5

Fungi

Fungi are eukaryotic microorganisms which are abundant worldwide. Fungal cells are much larger than bacterial cells and grow in the form of dense mats. Filamentous fungi are aerobic in nature and are involved in biodeterioration but still few studies are reported about fungi and their role in microbially influenced corrosion. Fungi generate organic acids which in turn lead to a decrease in pH of the surrounding environment. Fungi are commonly known to produce organic acids such as citric acid and therefore they are capable of contributing to microbial corrosion. These organic acids can lead to either pipeline’s cracking or corrosion or serve as nutrients to support the growth of other microbes such as sulphate reducing bacteria. Thus, metals can be directly affected by acid corrosion. Additionally, oxygen concentration cells are generated in the metal areas covered with oxygen-depleted fungal mats and those areas where no fungi exist. The resultant electrochemical cell leads to metal dissolution beneath the fungal mat. A further complication can take place when anaerobic microorganisms such as sulfate reducing bacteria which proliferate in the oxygen-depleted zones beneath the fungal mats. Hence, metals can be deteriorated by the combination effect of acid corrosion as well as sulfide corrosion (Usher et al. 2014). Fungi causing biocorrosion involve Fusarium sp., Penicillium sp. and Aspergillus niger. But so far, Cladosporium resinae is the most troublesome fungal genus causing severe problems to the engineering systems. It is now classified as Hormoconis resinae. It produces spores that can tolerate extreme factors. H. resinae causes severe problems in fuel storage tanks as well as aluminum fuel tanks of aircrafts. It was noticed that brown slimy mats of H. resinae covered large areas of aluminum alloy, causing pitting corrosion and intergranular attacks because of the production of organic acids (Stott and Abdullah 2018). According to Cojocaru et al. (2016) and Lugauskas et al. (2016), fungi are involved in microbial corrosion of various metals such as carbon steel, copper, aluminum and stainless steel. Qu et al. (2015) reported that Aspergillus niger was responsible for microbial induced pitting corrosion in magnesium alloy.

2.3 Microbial Biofouling

2.3.2.6

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Archaea

Archaea are known to lack membrane bound organelles and nucleus like bacteria (Gupta 1998). But unlike bacteria their cell walls do not have peptidoglycans (Willey et al. 2009). Some archaea are sulfate or nitrate reducers (Li et al. 2016) and some are methanogens (Thauer et al. 2008).

2.3.3 Mechanism and Microorganisms Involved in Abiotic/Anaerobic Microbial Corrosion Underground structures and pipelines are described to be quite susceptible to biological corrosion which is thought to occur by different groups of anaerobic microorganisms including:

2.3.3.1

Sulfate Reducing Bacteria (SRB)

SRB is a general term for bacteria which obtain energy for growth via oxidation of organic compounds or hydrogen (H2 ) or via reduction of sulfate (SO−2 4 ) to H2 S. Most common species are mesophilic and grow at temperature ranging between 20 and 30°C; however, they can also survive at approximately 50–60°C. Most SRB prefer a neutral environment and their growth is generally inhibited at acidic pH values lower than 5 or at basic pH higher than 9. Microorganisms belonging to SRB are divided into four subgroups: proteobacteria (Desulfovibrionales, Desulfobacterales, Syntrophobacterales), firmicutes, thermodesulfobacteria, and archaea. The taxonomic classification of SRB was essentially established in 1960s based on their cell morphology and the ability to form spores. Though, SRB are a group of prokaryotes with different types of cell morphology (e.g. rods, cocci, vibroid, oval, filaments and cell aggregates), these bacteria were first classified into two main genera on the basis of their morphology: the rod-shaped spore forming genus of Desulfotomaculum and the vibrio-shaped non spore-forming genus of Desulfovibrio. Other genera were later on discovered such as Desulfobacter, Desulfobacterium, Desulfosporomusa, Desulfosarcina, Desulfococcus, Desulfosporosinus and Desulfonem. SRB are abundant in natural habitats such as fresh and marine water sediments, inside oil wells and within underground pipelines. SRB occur in oil production facilities where these bacteria lead to severe economic losses due to iron corrosion in the absence of air. SRB are proposed to be the key players of anaerobic microbial corrosion, especially in environments with high concentrations of sulfate such as seawater. SRB are the most troublesome groups of microorganisms among all the microorganisms involved in microbial corrosion of steels and other metals in gas, oil and shipping domains. Souring of oil reservoirs during acidulation, secondary

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oil recovery and plugging of petroleum reservoirs are among the devastating consequences due to presence of SRB (Korenblum et al. 2013). According to Walch (1992), the sulfate reductive activity of SRB was found to be responsible for more than 75% of biocorrosion in productive oil wells and for more than 50% of failures of buried pipelines. Wang et al. (2017) reported that the presence of SRB promoted the occurrence of stress corrosion cracking (SCC) of X80 pipeline steel. It was observed that at day eight of growth, SRB reached the maximum number of cells of approximately 1.42 × 103 cells/g and the corrosion behavior was extremely serious at this point. There are many suggested theories for the aggressive corrosive effects of SRB including; the classical theory by Von Wolzogen Kuhr and Van der Vlugt (1934). Von Wolzogen Kuehr and Van der Vlugt (1934) proposed a mechanism for the role of SRB in microbial corrosion. This theory demonstrated that cathodic depolarization occurred via the oxidation of cathodic hydrogen. When the metal is subjected to water, it becomes polarized via the loss of positive metal ions (anodic reaction). The water-derived protons are reduced by the electrons in absence of oxygen (cathodic reaction), leading to the production of H2 S. SRB are thought to utilize the formed hydrogen, thereby leading to iron oxidation. This mechanism increases the anodic metal dissolution and accordingly corrosion byproducts are formed such as iron sulfide (FeS) and iron hydroxide (Fe (OH)2 ). According to this theory, bacteria secrete an enzyme namely hydrogenase and consume the cathodic hydrogen; therefore, the removal of hydrogen from the surface of the metals is considered the chief influence of SRB on corroding metal surface. There were other suggested theories such as galvanic corrosion between both the ferrous sulphide film and the steel beneath that film (Stümper 1923). In 1971, King and Miller suggested that there might be a combining effect of hydrogenase and the produced iron sulphide (King and Miller 1971). Iverson (2001) suggested that the presence of phosphorous metabolites might lead to severe microbial corrosion. The electrochemical reaction of SRB involves reactions at the anodic and cathodic sites (Eqs. 2.4–2.10). At the anodic site, iron is converted to iron ion particles (Fe2+ ) that become separated from the surface and the electrons (e– ) become loose and move to the cathodic site. A pit is formed due to the detachment of iron ion particles at the anodic site. These (Fe2+ ) react with the sulfide (S2– ) produced by SRBs to form iron sulfide (FeS). On the cathodic site, electrons move to the surface and react with hydrogen ions (H+ ) to form hydrogen gas (H2 ). The hydrogen ions shift the pH level towards acidic conditions within the biofilm. The hydroxide ions react with iron ion particles to form iron hydroxide (Fe (OH)2 ), or rust (Fig. 2.1). Anode: 4Fe → 4Fe+2 + 8e−

(2.4)

8H+ + 8e− → 8H

(2.5)

Cathode:

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Fig. 2.1 Schematic representation of SRB attack on a buried pipeline

Cathodic depolarization: −2 + 4H2 O SO−2 4 + 8H → S

(2.6)

8H2 O → 8H+ + 8OH−

(2.7)

Fe+2 + S−2 → FeS

(2.8)

3Fe+2 + 6OH− → 3Fe(OH)2

(2.9)

Ionization of water:

Corrosion products:

The overall reaction of corrosion: − 4Fe + SO−2 4 + 4H2 O → FeS + 3Fe(OH)2 + 2OH

(2.10)

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2.3.3.2

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Nitrate Reducing Bacteria (NRB)

Addition of nitrate to injection waters is a commonly used strategy to mitigate the negative impact of sulfide produced in oil fields which results from the existence of SRB (Suri et al. 2017). Volatile fatty acids, mixtures of acetate, butyrate, propionate and low molecular weight hydrocarbons such as alkyl benzenes are preferred oil organics for nitrate reduction by NRB (Fida et al. 2016). NRB are also referred to as denitrifiers and they are also important members of the anaerobic microbial community. They are a group of bacteria that reduce nitrates or nitrites to nitrogen-containing gases. Recently, it has been realized that NRB have a major role as SRB in microbial corrosion (Wan et al. 2018). Xu et al. (2013) demonstrated that Bacillus licheniformis biofilm on carbon steel was found to be more corrosive than the biofilm of a sulfate reducing bacterium D. vulgaris within 7 days’ experimental test. Therefore, nitrate injection should be monitored carefully to avoid the entrance of nitrate to pipelines. Al-Nabulsi et al. (2015) conducted a study to reveal the main cause of premature cracking failures that were detected in different firewater hydrants handling untreated seawater. The microbial diversity collected from the failed materials was detected via quantitative polymerase chain reaction (qPCR). Scanning electron microscopy, coupled with energy dispersive X-ray spectroscopy (EDS) was used to interpret the corrosion mechanism. The qPCR data showed that the dominated microbial communities belong to NRB with limited presence of other corrosion causing microorganisms like SRB. Two distinctive failure modes were detected namely; stress corrosion cracking (SCC) and selective leaching (dezincification). SEM observations showed the formation of intergranular corrosion with preferential attack on grain boundaries. EDS confirmed the depletion of zinc on the examined fracture surface grains. Cracking of copper alloy C86300 took place because of the produced ammonia secreted by the metabolic activities of NRB. Etiquea and co-workers manifested the role of NRB in another study (Etique et al. 2018). The main goal of the study was to investigate the corrosion influence of Klebsiella mobilis as a model for NRB on carbon steel coupons. Firstly, corrosion bilayers were created by anodic polarization at three different conditions involving; (i) 0.05 M NaCl + 0.5 M NaHCO3 , 200 μA cm−2 , 72 h at 25°C; (ii) 0.01 M NaCl + 0.01 M NaHCO3 , 50 μA cm−2 , 168 h at 80°C; (iii) 0.05 M NaCl + 0.1 M NaHCO3 , 500 μA cm−2 , 72 h at 80°C. Raman spectrometer, X-ray diffraction (XRD) and SEM/EDS highlighted the formation of a bilayer chiefly composed of siderite in the outer layer and magnetite in the inner layer. Once these corrosion bilayers were formed, the carbon steel coupons were incubated with K. mobilis for a period of three weeks under anaerobic conditions. It was found that, the inner stratum of magnetite was indirectly changed into mackinawite (and greigite) via the reduction of sulphate to sulphide by K. mobilis. K. mobilis reduced sulphate to sulphide in order to fulfil its needs in sulphured amine. Yuk et al. (2020) isolated NRB from oil field water and was identified as Marinobacter YB03. The carbon sources and electron donor preferences of YB03 were toluene, m, p-xylene, and volatile fatty acids (VFAs). Marinobacter YB03 was found to promote souring and corrosion. Pitting corrosion was noticed on day 90.

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2.4 Macrobial Biofouling Macrobial biofouling is referred to as “the deposition and growth of macro-organisms as a result from the development of microbial biofouling” (Jakob et al. 2008; Shan et al. 2011). Macro-biofouling attracts many concerns just like microbial biofouling as ships; instruments; offshore structures and oceanographic equipment are the most affected (Omran et al. 2013). Many macrofouling organisms are involved and they belong to several types ranging from plant or animal kingdoms, and they are generally categorized into “soft” and “hard” foulers. The presence of a shell or a calcareous tube is characteristic to the hard foulers such as calcareous algae, barnacles, mussels, oyster, encrusting sponge and tubiculous worms (Omran et al. 2013). This shell aids in protecting the body within. Contrary, the soft species do not possess such protection and they include bryozoan, sponges, seaweed, soft coral and anemones. In case of mussels, they are usually found at a depth which may reach up to 20 meters deep. Species of barnacles usually exist at a depth ranging from 60 m up to 210 m. Hydroids, algae and anemones are found in a large depth range. Sometimes such macro-foulers reach very big size. Bryozoans are considered one of the macrobiofouling organisms. Bryozoans such as Bugula neritina form flexible colonies and when they become adults they release sexually produced larvae. These larvae become attached and start forming new colonies by asexual budding (Mihm et al. 1981). Larvae start to attach themselves after selecting a suitable substrate. Afterwards, they secrete bioadhesive materials enriched with mucopolysaccharides (mucin) (Loeb and Walker 1977). Larval attachment of B. neritina prefers the subtidal habitats and substrates containing biofilms in addition to clean surfaces (Dahms et al. 2004; Dobretsov et al. 2006). Biofouling occurs as illustrated in Fig. 2.2. Primary colonizers which settle first on the surface include microorganisms like bacteria e.g. Thiobacillus sp., Pseudomonas sp., Desulfovibrio sp. and microalgae such as Oscillatoria sp. and Navicula sp. They are the pioneering microorganisms that exist on unprotected surfaces after less than few hours of immersion. These microorganisms are associated with biocorrosion/microbial biofouling which occurs as a result of synergistic interactions between the metal surface, microbial cells, microbial metabolites and the abiotic corrosion products. Microbial metabolites include volatile compounds such as ammonia, hydrogen sulfide, inorganic and organic acids. Secondary colonizers involve spores of macro-algae and protozoa. Particular environmental and technical damage of man-made structures are usually linked to algal fouling. Tertiary colonizers are the hard macro-biofoulants which settle on the surfaces after 2– 3 weeks. A high variety of organisms are usually observed, the main ones are: mollusks (mussels, clams, gastropods, etc.), barnacles, bryozoans, cirripeds, polychaetes, hydrozoans, bryozoans and ascidians. These are the principal organisms that lead to the establishment of what is referred to as “macrobial biofouling”.

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Fig. 2.2 Steps of Biofouling process

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2.5 Factors Affecting Biofouling Process

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Table 2.2 Factors which affect the biofouling process Factor

Influence

Geographic location

Fouling is more favorable and more intense in tropical regions possibly due to the warm temperature of seawater thus leading to continuous breeding

Season and temperature

Seasons and temperature play a vital role in the fouling process. It is noticed that most of spawning and fouling growth occur from April to September. An increase in community growth rate is generally observed with an increase in temperature. Whilst during winter in temperate and cold waters, some soft marine species die. Nevertheless, some species may be adapted to the environmental factors and survive

Water current and tidal conditions The water currents aid in supplying the organisms with great amounts of oxygen and nutrients. The settlement and growth of some organisms is strongly dependent on water currents. For instance, algae are influenced by the degree of exposure to water waves Water salinity

The total salinity of seawater is approximately 35% while in rivers salinity reaches about 10%. For instance, some organisms such as tubeworms are fairly tolerant to a wide range of salinity (2–40%)

Light

The phytal system is greatly influenced by light. For example, algae avoid extreme light, so they normally develop in depth ranging from 10 to 20 m beneath the water surface. However, the light intensity is influenced by water turbidity along with the presence of natural organic materials, planktons or because of human activities

2.5 Factors Affecting Biofouling Process Biofouling formation is a net result of the combination of some chemical and physical parameters which are discussed in Table 2.2.

2.6 Metals Susceptible to Biofouling Yet there is no known metal that can fully resist biofouling and biofilm formation. Listed below some of the metals and alloys that can be affected by biofouling.

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2.6.1 Copper and Its Alloys There is an ultimate belief that copper and its alloys are toxic to microorganisms and are consequently not susceptible to microbial corrosion (Stott and Abdullahi 2018). However, it is unfortunately not right. Copper and its alloys are regularly used in pumps, heat exchangers, condensers and valves. Extracellular metabolic products secreted by microbial corrosion involved microorganisms corrode copper-based alloys via selective dissolution, differential aeration, pitting, and stress cracking. For instance, SRB produce sulfide-rich scales on copper alloys which lead to tubercle formation. Acidithiobacillus sp. are highly tolerant to copper ions. It is worth mentioning that ammonia produced by microbially corrosion causing bacteria causes SCC of numerous copper alloys. Several cases of pitting corrosion of heat exchanger tubes were noticed to be made up of copper-nickel, specifically in marine environments. Many of these failures were mainly because of the biogenic sulfide produced by SRB. Copper–nickel alloys are much susceptible to microbial corrosion by SRBgenerated sulfides. Since 1980s, a distinctive type of localized corrosion was observed in copper pipes as reported by Campbell and coworkers (Campbell et al. 1993). The phenomenon was first reported in Britain, Germany, Sweden, and in the Middle East. In many of these cases a gelatinous film of microbial origin was present and was mainly made up of polysaccharides. The occurrence of this type of copper corrosion was shown to be associated with the existence of biofilms comprising of extracellular polymeric products secreted from aerobic heterotrophic bacteria, chiefly members of the genera Pseudomonas, Sphingomonas, or Acidovorax (Critchlay et al. 2004).

2.6.2 Carbon Steel Carbon steel was reported to be susceptible to anaerobic microbial corrosion induced by SRB (El-Gendy et al. 2016). A bio-electrochemical explanation of the biocorrosion in carbon steel in an anaerobic environment could be summarized as demonstrated by Videla (1988). The produced biogenic sulfides cause breaking down in carbon steel passivity which is likewise that of the abiotic sulfides. Additionally, presence of sulfide ion in neutral media results in formation of weak protective film of mackinawite; hence the damage which occurs in the anodic passive film is considered the first phase of corrosion. Therefore, the role of SRB can be either indirect via the release of aggressive species such as sulfides, hydrogen sulfide or bisulfides or other intermediate metabolic compounds such as thiosulphates and polythionates.

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2.6.3 Stainless Steel Stainless steels are widely used for the manufacture of nuclear power plants in fresh and sea water environments. It has been demonstrated that IOB, MOB and manganese depositing bacteria possess the potential to corrode stainless steels. Corrosion occurs as pits and it usually arises in regions adjacent to weldments. Moreover, SRB have been found to be able to corrode stainless steels, super stainless steels such as duplex steels and molybdenum steels.

2.6.4 Aluminium-Based and Nickel-Based Alloys Protective oxide films present on aluminum and its alloys could be disrupted and destroyed through microorganisms. Aluminum and 2024 and 7075 alloys used in aircraft and fuel storage tanks are susceptible to microbially influenced corrosion. Production of water-soluble organic/inorganic acids by bacteria and fungi can lead to pitting and intergranular corrosion in aluminum alloys. Aluminum magnesium (5000 series) alloys used in marine applications undergo pitting, intergranular corrosion, exfoliation, and stress corrosion induced by biofouling. Aircraft fuel tanks and sea water infrastructures made up of aluminum and its alloys are attacked by microorganisms such as Pseudomonas, Leptothrix, SRB, and fungi. The fungus, Cladosporium resinae grow on petroleum products, kerosene, or paraffins and utilize them as sole carbon sources, developing pinkish brown colonies. Fuel tanks especially in ground aircrafts are seriously contaminated by fungal and bacterial growth. For example, the following microorganisms were isolated from an aircraft tank sludge, namely, Pseudomonas aeroginosa, Aerobacter aerogenes, Clostridium sp., Bacillus sp., Desulfovibrio sp., Fusarium sp., Aspergillus sp., Cladosporium sp., and Penicillium sp. Pitting potentials of aluminum alloys could be lowered by microbial adhesion and interaction with organic acids generated by fungi.

2.6.5 Titanium-Based Alloys Titanium and its alloys are known for their outstanding excellent mechanical strength and high chemical stability (Yan et al. 2018). Besides, titanium is characterized by its light weight, thus it is very suitable in constructing materials for seawater related engineering applications. For instance, it has been used in marine industry (e.g. fasteners), offshore petro-chemical industry (e.g. hydrocarbon extraction devices), desalination plants (e.g. heat exchangers) and seawater-cooling power plants (e.g. cooling systems) (Wake et al. 2006). Although titanium is highly corrosion resistant; it is prone to biofouling. Biofilms comprising of SRBs and APB generate differential aeration cells which cause pitting of titanium and its alloys (Rao et al. 2005).

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Moreover, titanium-based alloys in marine environments are susceptible to biofilm formation by MOB and IOB as well as SRBs. Zhang et al. (2015) investigated the resistance behavior of both 304 stainless steel and titanium upon exposure to Paecilomyces variotii and Aspergillus niger in a high humidity atmospheric environment for periods of 28 days and 60 days. Scanning Kelvin Probe (SKP) and stereomicroscopy were used to analyze the corrosion behavior. It was found that the presence of fungi decreased the corrosion resistance of both 304 stainless steel and titanium. Moreover, titanium was more resistant than 304 stainless steel to corrosion because of the poor adherence of fungi to the surface of titanium.

2.7 Analytical Techniques and Tools Used for the Assessment of Microbial Corrosion Microbial corrosion is a very complex process. Modern analytical methods and techniques are now available to assess and study biocorrosion including;

2.7.1 Microbiological Assays In oil and gas industries, the most probable number (MPN) is the most preferred technique for microbial growth assessment (Skovhus et al. 2017). MPN is one of the most popular culturing techniques with different media composition and is used to detect microorganisms causing microbial corrosion. It is not costly and well employed in industry. One of the drawbacks of this method is the incubation time which may take from 24 h to few weeks depending on the species and the initial concentration of the tested sample. Additionally, several reports demonstrated that the planktonic population may be unrelated to the corrosion process that may take place at the surface (Dall’ Agnol et al. 2014). Still certain disadvantages concerning the microbiological techniques such as MPN hinder their lone use. Among which, the misleading results that might be obtained for mixed culture samples (Amann et al. 1995). Another major weakness point of MPN is its low accuracy as it mainly measures cell counts in order of magnitude. Other microbiological techniques include; flow cytometry which attracted attention in studying biocide efficacy in oil fields (Tidwell et al. 2015). Furthermore, to distinguish between bacterial cells during enumeration, immuno-fluorescent dyes are usually utilized (Douterelo et al. 2014). Biochemical techniques are extremely supportive tools for determining the metabolic activity of microorganisms associated with microbial corrosion. Biochemical tests involve deoxyribonucleic acid (DNA) analysis, cytochromes, cell wall proteins and constituents, photo-pigments, adenosine triphosphate (ATP), coenzymes F420 and NADH2 (Wang and Ivanov 2010). ATP measurement is an important tool to estimate the overall metabolic activity of

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microorganisms (Jia et al. 2019). ATP measurement greatly aids in providing information concerning microbial consortia as it helps to estimate the total live biomass in a sample (Douterelo et al. 2014). Additionally, metabolites can be used to determine microbial growth activity, among which is sulfate. It is worth noting that sulfate is the terminal electron acceptor for ideal SRB growth. By evaluating sulfide production, biocide efficacy can be tracked for SRB treatment (Jia et al. 2019). Assays like enzyme linked immunosorbent assay (ELIZA), adenosine 5 -phosphosulfate (APS) reductase, ATP and hydrogenase as well as Microscopic examination are among the employed microbiological techniques as well.

2.7.2 Electrochemical Assays Electrochemical techniques offer data from inside the oil field and results can be taken from day one and permanently as long as they are not corrupted. They can be used not only for studying microbial corrosion behavior, but also for biocide assessment (Jia et al. 2019). Electrochemical methods include: Open circuit potential (OCP) which is an easy technique to assess corrosion, Tafel polarization, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), electrochemical noise, scanning vibrating electrode technique and Linear polarization resistance (LPR) (Dall’ Agnol et al. 2014). It is important to emphasize that electrochemical techniques requisite specialized expertise so as to interpret the resultant data and also acquire good knowledge of the system to be capable of choosing the right set-up for each specific condition that may occur. Nonetheless, OCP and electrochemical noise are easy and safe to set in the field. Other techniques include pit depth and weight loss but unfortunately they take several days and even longer time to obtain the measurements’ results. LPR is a non-destructive technique and it is usually employed for corrosion studies of materials. It is an appropriate technique that provides near-real corrosion data, hence making it useful to be applied in oil fields. This technique depends on scanning in a linear direct current (DC) potential in a narrow range as ±10 mV or as small as ±5 mV, as performed in OCP. Then, the polarization resistance (Rp) is calculated based on potentiostat software. Rp is indirectly proportional to corrosion rate (Jia et al. 2019). As conducted by Jia et al. (2017c), biocide treatment with 100 ppm of four D-amino acids labeled as D-met, D-tyr, D-trp, and D-leu labeled were mixed to enhance the efficiency of 100 ppm Tetrakis hydroxymethyl phosphonium sulfate (THPS). The mixture was tested against a biofilm consortium on carbon steel type C1018. As demonstrated by Jia et al. (2017c), the polarization resistance (Rp) of the control (not treated) was less than that of the treated one. This meant that severe corrosion occurred in the untreated part. Transient Rp measurements help to indicate whether the used biocide is effective or when the effect does no longer take place. EIS is another technique used to study microbial corrosion. This technique depends on an alternating current potential with 5–10 mV amplitude and is applied over a large frequency range approximately10 MHz to 100 kHz. Microbial corrosion

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caused by Desulfotomaculum nigrificans on Q235 carbon steel was reported to be inhibited by benzalkonium chloride (BKC) within 21 days of incubation (Liu et al. 2017). EIS was used to observe the corrosion progress during incubation with and without BKC. EIS results were found to be in agreement with weight loss results and surface analysis images. Potentiodynamic polarization measurements apply a DC voltage in the range of plus and minus of several hundreds of mV to examine the corrosion behavior of a system. Anodic and cathodic Tafel slopes βa and βc values are measured. Corrosion current density (icorr ) obtained from the Tafel analysis is used to calculate corrosion rate. In a study performed by Jia et al. (2017d), 100 ppm of D-amino acids (D-met, D-tyr, D-trp, and D-leu) labeled as D-mix were used to enhance the efficiency of 60 ppm of alkyldimethylbenzylammonium chloride (ADBAC) against a field biofilm consortium on C1018 carbon steel. The icorr of the combination of 60 ppm ADBAC + 100 ppm D-mix was found to be lower than that of 60 ppm of ADBAC alone confirming biocide enhancement by the D-mix. It should be noted that potentiodynamic polarization may cause disruption to examined biofilms. Thus, it should be used with limitations.

2.7.3 Surface Analysis Assays Microscopes are conventional techniques used to study corrosion and can be beneficial for biocorrosion studies. Usually microscopic analysis requires low quantities of the tested sample. One more important advantage is that it distinguishes between viable cells from the dead ones. For instance, scanning electron microscopy can be coupled with energy dispersive X-ray analysis (SEM-EDX) to perform semiquantitative elemental analysis. Other surface analytical techniques involve XPS, time of flight-secondary ions mass spectrometry (ToF-SIMS), XRD, environmental scanning electron microscopy (ESEM), atomic force microscopy (AFM), confocal laser scanning microscopy (CLSM), microautoradiograghy (MAR). All of these techniques are employed for the elemental, chemical, and phase characterization of the target surface. Each one possesses distinct advantages and sample requirements. According to Liu et al. (2018), SEM is a basic microscope employed in observing biofilm structure and in determining the generated corrosion products. SEM provides high-resolution images that clearly describe different cell shapes in a certain mixed biofilm consortium (Jia et al. 2017a). SEM can clarify the efficacy of biofilm treatment but it definitely cannot distinguish between live and dead cells (Jia et al. 2017b). Biofilm on a metal surface requires fixation via a strong biocide first. Then, dehydrated using alcohol and followed by drying using CO2 in a specific critical point dryer (Jia et al. 2017b). Eventually, the non-conductive biofilm is then coated with thin platinum or gold films. Usher et al. (2014) demonstrated that hydrated samples can be studied via both environmental SEM and cryo-SEM, particularly those samples containing extracellular polymeric substances (EPS) as they might be degraded using the conventional SEM.

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CLSM is extensively used in microbial corrosion investigations in the last few years as reported by Xu et al. (2017a). To study biofilms, they are stained with dyes with different excitation wavelengths prior to examination. Under CLSM, live cells occur as green dots while dead cells appear as red dots when stained with the Live/Dead® BacLightT Bacterial Viability Kit L7012 (Life Technologies, Grand Island, NY, USA (Jia et al. 2019). Another important function of CLSM is that it is able to measure biofilm’s thickness. The obtained images are observed in three dimensional (3D) or two dimensional (2D) forms. Certain image analysis software for instance Image J software can be used to count the live and dead cells in 3D images (Xia et al. 2015). CLSM can demonstrate whether the dead cells are only at the top layer of a biofilm or in deeper places, therefore giving a hint concerning biocide treatment efficacy (Tidwell et al. 2015). Transmission electron microscope (TEM) provides very high-resolution images for biofilm structures and elemental analysis (Narenkumar et al. 2018). Biofilm samples need to be incorporated in epoxy and cut in cross-sections. AFM examines the surface topography via a microprobe (Jia et al. 2019).

2.7.4 Molecular Microbiological Assays Molecular microbiological methods (MMMs) are the new strategy employed recently to assess microbial corrosion. They involve; polymerase chain reaction (PCR), quantitative PCR (qPCR), denaturating gradient agro gel electrophoresis (DGGE), DNA microarray, fluorescent in-situ hybridization (FISH), sequencing and mass spectrometry (MS). MMMs make the identification of the most abundant species in any sample easier. They depend on using ribosomal genes (16S rDNA or 23S rDNA) or even functional genes that are responsible for important reactions (as apsA of the APS reductase enzyme) or pathways related to biocorrosion. Moreover, they also ease the assessment of the metabolic activities by studying the RNA or expressed proteins (Suflita et al. 2012).

2.7.5 Other Spectroscopic Assays Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and electron paramagnetic resonance (EPR) are other analytical techniques that are less employed in microbial corrosion detection. It should be kept in mind that sample collection and transference are essential for good analysis and fair results as certain tests require samples to be kept cold and/or even in an anoxic environment. This is required in order to avoid the oxidation of some chemical compounds that may exist either at the surface or at the bulk medium.

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2.8 Use of Biocides to Combat Biofouling Microorganisms are usually widespread in oil and gas production systems, frequently posing challenges to the integrity of pipelines and vessels. Microbial contamination in oil and gas facilities result in membrane, pipeline and vessel fouling in addition to production of biogenic harmful H2 S. Even though, there is a massive advancement in different science disciplines such as engineering, metallurgy, biology and chemistry, microbially influenced corrosion remains to be a worldwide problem in many industries and represents a serious challenge to the oil and gas facilities (Keasler et al. 2017). Reservoir souring represents another common problem caused by microorganisms. This problem occurs due to the proliferation of sulfur reducing microbes in formation water. Usually, water is injected to help to maintain reservoir pressure during secondary recovery. Though, this problem is predominantly troublesome in offshore systems where sulfate-rich seawater is injected, this problem also takes place in onshore fields in which produced water is mixed with fresh water right before injection. Because of the diversity of microbes which are capable of reducing sulfur, reservoir souring can be a major problem once these organisms are existed underground. Controlling microbial populations in reservoirs is often hard. Additionally, production of gases such as H2 S may lead to severe corrosion as a result of H2 S stress cracking beside the incidence of severe health and environment issues. Biocides are broadly used to control bacteria for many centuries ago, and are usually incorporated within a variety of products such as cosmetics, disinfectant formulations, pesticides, preservatives and antiseptics (Paulus 2012). Hence, biocides are referred to as active substances and preparations that possess an inhibiting effect on harmful bacteria. Biocides are chemicals that are used to disinfect, sterilize, and kill microorganisms. The extent of biocide effect is highly dependent on contact duration with the target microbes and the concentration of the chemical being applied. At low concentrations, most biocides provoke a biostatic effect, in which microbial growth is retarded but not inhibited and once the biocide is removed from the system, bacteria will regrow. Besides, some biocides when used at low doses they become a source of nutrition and may encourage bacterial growth. In oil field facilities, biocides can be injected either permanently or occasionally in batches. The latter is frequently the most common action. Biocides in oil field are divided based on the mechanism of action. Generally, non-oxidizing biocides act on both microbial cell membrane and cell wall, while oxidizing biocides act through series of oxidative reactions with cellular components. Narenkumar et al. (2019) investigated the biocorrosion behavior of Bacillus thuringiensis EN2 and B. oleronius EN9 on copper metal CW024A (Cu) in cooling water system (1% chloride). Corrosion was evaluated using weight loss measurements, EIS and surface analysis techniques. The presence of bacteria resulted in high corrosion rates of approximately 0.021 mm/y and 0.032 mm/y for EN2 and EN9, respectively than the control sample (0.004 mm/y). While, the addition of 2-mercaptopyridine (2-MCP) along with the two tested bacteria (EN2 and EN9) resulted in biofilm inhibition and a decrease in corrosion rate was

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noticed which reached 0.004 mm/y. More pits were revealed in presence of EN2 and EN9 as demonstrated by atomic force microscope (AFM).

2.8.1 Oxidizing Biocides 2.8.1.1

Hypochlorite (ClO− )

Hypochlorite is an unstable compound in its pure form thus it is usually handled in its liquid form. It is extensively used as an antimicrobial in water treatment (Gray 2014). It is a strong oxidizing compound than chlorine dioxide (ClO2 ). Hypochlorite tends to be consumed much more mainly when water contains high concentrations of reduced compounds.

2.8.1.2

Peracetic Acid (PAA)

Peracetic acid or peracids or peroxyacids are formulated through the reaction between hydrogen peroxide and short chains of organic acids such as acetic acid (Kitis 2004). In 1980s, PAA was first registered as an antimicrobial agent in the United States, and since then its application has been increased. It is widely applied in different fields including; food processing, hospitals, agriculture, facilities and industrial water systems. Recently, PAA has been used in oil fields as an alternative to hypochlorite and ClO2 . PAA degradation results in release of non-toxic constituents as it disintegrates into hydrogen peroxide and acetic acid, which will in turn convert into water, carbon dioxide and oxygen. Hence, they can be easily dissolved in water.

2.8.1.3

Chlorine Dioxide (ClO2 )

Chlorine dioxide is a non-charged chlorine compound. It is usually produced either as a gas or saturated in water. ClO2 is highly soluble in water and that explains why it is widely used as a bleaching agent and as an effective antimicrobial agent (Omran et al. 2013). Nonetheless, solubility decreases intensively with increases in temperature. It is important not to exceed ClO2 concentration above 30 volume percent as this may lead to severe explosions and the release of oxygen and chlorine. Consequently, all aspects of safety must be taken into account during ClO2 preparation to avoid any risks. Hence, because of such safety concerns and regulations, ClO2 is not widely applied in petroleum industries.

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2.8.2 Non-oxidizing Biocides Glutaraldehyde, quaternary ammonium compounds (quats), Tetrakis hydroxymethyl phosphonium sulfate (THPS) and 2, 2-dibromo-3-nitrilopropionamide (DBNPA) are among the most widely used non-oxidizing biocides (Omran et al. 2013). Other biocides that are used in fewer levels are 2-bromo-2-nitropropane-1, 3-diol (bronopol) and acrolein. It is worth noting that the effectiveness of most biocides is greatly influenced by water chemistry, salinity, temperature, oxygen content, and incompatibility with other chemicals.

2.8.2.1

Glutaraldehyde

Glutaraldehyde is an aldehyde organic compound which owns a particular high attraction towards proteins, reacting particularly with amide, amine and thiol groups. That explains its use as a fixing agent in laboratory procedures. Glutaraldehyde is less toxic but more expensive than formaldehyde. It is mostly used in countries where restricted regulations prevent the use of formaldehyde. It is highly soluble in water and it displays a high efficacy as an antimicrobial agent at high temperature (i.e. above 50°C), this is because of its thermal stability. Generally, glutaraldehyde works well with most other chemicals such as corrosion and scale inhibitors but still interference may occur with certain chemicals including; ammonia, primary amines and bisulfite oxygen scavengers (Jordan et al. 1993; Omran et al. 2013). However, changes in field application (e.g., staggering applications or injection in different locations in the system) can be done to mitigate potential compatibility problems. Additionally, certain studies showed its limited effect in penetrating and controlling microbial biofilms as reported by Stewart et al. (1998).

2.8.2.2

Tetrakis Hydroxymethyl Phosphonium Sulfate (THPS)

THPS is a commonly applied biocide in petroleum fields. It has the capability to control microbial growth in addition to chelating iron from iron sulfide scales (Campbell 2017). It is classified as a broad-spectrum biocide and it exhibits a dual mechanism for controlling SRB by either targeting particular amino acids on the cell membrane and by closing the sulfidogenic reduction pathway. Consequently, THPS is often nominated for the management of systems contaminated with SRB. Compared with glutaraldehyde, THPS shows higher thermal stability to approximately 160°C (320F). Also, interference occurs with other chemicals such as ammonium and bisulfite oxygen scavengers. Furthermore, limitations were reported in dealing with biofilms. It is worth mentioning that high concentrations of THPS may cause severe corrosion.

2.8 Use of Biocides to Combat Biofouling

2.8.2.3

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2, 2-Dibromo-3-Nitrilopropionamide (DBNPA)

DBNPA is a bromine-based compound which mitigates microbes very quickly. But unfortunately, DBNPA is rapidly decomposed into numerous byproducts like bromide ions, ammonia, dibromoacetic acid and dibromoacetonitrile (Campbell 2017). DBNPA is extensively used in seawater injection systems, mostly for membrane cleaning. It is also vital to mention that H2 S reacts with DBNPA, thus it may not be the best biocide to be chosen to deal with systems with biofilms as this may result in decreasing its efficacy as a biocide.

2.8.2.4

Quaternary Ammonium Compounds (Quats)

Quats are characterized by owning surfactant properties and that candidates them to be incorporated with corrosion inhibitors. Quats are positively charged nitrogen ions with aryl or alkyl groups. Quats are broadly used as antimicrobials and surfactants in several industries. As a biocide in petroleum fields, quats provide excellent control over microbial biofilms. They are usually applied in association with other biocides such as glutaraldehyde and THPS to support rapid control of microbial biomass. Nevertheless, because of their surface filming characteristics, quats may not be the first to select to be applied in systems with high levels of mineral deposits. In addition, their surfactant properties may disrupt oil and water separation through emulsification leading to foam formation.

2.9 Recent Research Towards Green Biocides 2.9.1 Extracts of Plant Biomaterials as Biocides Although several chemical inhibitors such as ethylene glycol, formaldehyde, sodium molybdate, glutaraldehyde, and quaternary ammonium salts have a great potential to effectively limit microbial activity and control biofilm formation. However, environmental concerns and regulations regarding the application of such chemical biocides retard their application in industries (Narenkumar et al. 2017, 2018). Recently, natural biocides/inhibitors derived from plant materials and agro-industrial waste extracts have received considerable attention (Omran et al. 2013; El-Gendy et al. 2016). The performance of marine infrastructures as well as equipment submerged in marine environment is very much vulnerable to the accumulation of macrofouling organisms such as barnacles, mussels, clams and hydroids (Omran et al. 2013). Such marine fouling organisms possess a larval or pseudo larval form that is released into water and through mobility in flow rates and currents they become distributed away from their place of origin (Lyons et al. 1988). At this point, they reach the adult stage in pipelines and subsequently cause clogging problems. Brachidontes, Modiolus,

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Mytilus, Perna, Dreissena, and Corbicula are among the most predominant macrobiofoulants genera. In a study performed by Omran et al. (2013), three natural water extracts of non-edible domestic wastes were evaluated for their biocidal activity against planktonic SRB i.e. non-halotolerant Desulfovibrio sapovorans (ATCC 33892), halophilic Desulfovibrio halophilus (ATCC 51179) and three SRB mixed cultures; SRB1, SRB2 and SRB3 as well as Brachidontes variabilis as an example of macro-biofouling organism. The three natural extracts were the water extract of waste bitter water of Egyptian lupine (Lupinus termis) seeds and the hot water extracts of mandarin (Citrus reticulum) and orange (Citrus sinensis) peels. Lupanine was the major component existed in Egyptian lupine waste bitter water extract. The chemical composition of each extract (natural biocide) was detected and identified using gas chromatography/mass spectroscopy (GC/MS) (Figs. 2.3, 2.4 and 2.5) (Omran et al. 2013). Seventeen compounds were detected in the hot water extract of orange peels. The following five compounds represented the highest peaks and they were: Itaconic acid anhydride; 5-dihydroxy-6-methyl-4H-pyran-4-one (DDMP); 2, 4-dihydroxy-2, 5-dimethyl-3(2H)-furan-3-one; 2, 3-dihydro-3 and 2, 3-dihydro-benzofuran and 2-methoxy-4-vinylphenol (4-vinyl guaiacol). Additionally, Other twelve minor compounds were detected: 1,2-cyclopentanedione; glutaric acid anhydride; 3,5dihydroxy-2-methyl, 4H-pyran-4-one; methyl methane thiosulphinate (MMTSO); 2-(3,4-dimethoxyphenyl)-6-methyl-3,4-chromanediol; nhexadecanoic acid; 5hydroxymethylfurfural (HMF);13-heptadecyn-1-ol; phenol, 2,2 -methylenebis (6-tert-butyl-4-ethyl); eugenol; androst-4-ene-3,17-dione, 12-[(trimethylsilyl)oxy]-, bis(Omethyloxime) and 5,5 -dimethoxy-3,3 -dimethyl-2,2 -binaphthalene-1,1 ,4,4 tetrone. Twenty compounds were detected in the hot water extract of mandarin peels. The following eight compounds represent the major constituents: d-Limonene; 2,4-dihydroxy-2,5-dimethyl-3(2H)-furan-3-one; 2,3-dihydro-3,5-dihydroxy-6 methyl-4H-pyran-4-one (DDMP); 3,5-dihydroxy-2-methyl-4H-pyran-4-one; 5hydroxymethylfurfural (HMF); 2-methoxy-4-vinylphenol (4-vinyl guaiacol); n-hexadecanoic acid and 5-methyl-2-furancarboxaldehyde. Moreover, twelve other minor chemical components were identified and they were: glutaric acid anhydride; S-methyl methanethiosulphinate (MMTS); benzoic acid; N,N bis-benzoyloxy-heptanediamide; methyl methane thiosulphinate (MMTSO); 1propanone, 1-(5-methyl-2-furanyl); 2-methoxy-5-(1-propenyl) phenol (isoeugenol); tetradecanoic acid (myristic acid); pentadecanoic acid; Z-11, hexadecenoic acid; 2-(3,4-dimethoxyphenyl)-5,6,7-trimethoxy-4Hchromen-4-one and 5,5 -dimethoxy3,3 -dimethyl-2,2 -binaphthalene-1,1 ,4,4 -tetrone. It was observed that the biocidal activity of the three tested water extracts was lower against the halophilic Desulfovibrio halophilus American type culture collection (ATCC) 51179 and the high salinity mixed culture SRB3 than the results recorded against the non-halotolerant Desulfovibrio sapovorans (ATCC 33892) and the low salinity mixed cultures SRB1 and SRB2 as revealed by the MPN technique. Authors assumed that halophiles possess strategies that permit them not only to survive osmotic stress, but also to withstand high salt concentrations. This is partially due to the formation of compatible solutes that permit them to balance their osmotic pressure (Omran et al.

2.9 Recent Research Towards Green Biocides

2, 4-Dihydroxy-2, 5-dimethyl-3(2H) furan-3-one

5-Hydroxymethylfurfural (HMF)

77

Glutaric acid anhydride

2, 3-Dihydro-3, 5-dihydroxy6methyl- 4H- pyran-4-one (DDMP)

Methylmethanethiosulfinate (MMTS)

3, 5-Dihydroxy-2-methyl, 4H-pyran4-one

2-Methoxy- Vinylphenol

n-Hexadecanoic acid

Fig. 2.3 Chemical structures of main common components of orange and mandarin peels hot water extracts

2013). This might explain their high resistance to biocides, as they are considered extremophile microorganisms which can survive under severe conditions. Furthermore, the three tested extracts displayed a good biocidal activity against Brachidontes variabilis and they exhibited less toxic effects towards non-target sea organisms including amphipodes, isopodes and decapodes when compared with chemical biocides. The capability of ginger (Zingiber officinale) water extract to act as a green biocide to control microbial corrosion caused by Bacillus thuringiensis EN2 on mild steel

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Eugenol

2, 5-Furandione, dihydro-3methylene

2-(3, 4-Dimethoxyphenyl)-6-methyl-3, 4chromanediol

1, 2- Cyclopentanedione

2, 3-Dihydro- benzofuran

Androst-4-ene-3, 17-dione, 12[(trimethylsilyl)oxy]-, bis (O-methyloxime)

13-Heptadecyn-1-ol

Fig. 2.4 Chemical structures of the main components of hot water extract of orange peels

1010 in a cooling water system was investigated by Narenkumar et al. (2017). Polarization and weight loss measurements, surface analysis, XRD, Fourier transform infrared spectroscopy (FTIR) were employed to determine the biocorrosion behavior under various incubation periods up to 4 weeks. It was observed that EN2 formed a thick biofilm on mild steel surface at the end of the incubation period and the weight loss reached 993 mg at the fourth week while the weight loss at the initial immersion period reached 194 ± 2 mg. A reduction in weight loss took place after the addition of Z. officinale water extract. The corrosion rate was reduced to about 41 ± 2 mg. GC/MS analysis assured the adsorption of Z. officinale active component (i.e. b-turmerone) on mild steel surface which aided in the formation of a protective layer to trigger biofilm formation. The optimum concentration was 20 ppm and was

2.9 Recent Research Towards Green Biocides

D-limonene

S-Methylmethanethiosulphinate (MMTSO)

Z-11, Hexadecenoic acid

Benzoic acid

2-Methoxy-5-(1-propenyl) phenol

Pentadecanoic acid

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5-Methyl-2furancarboxaldehyde

1- Propanone- 1- (5methyl-2- furanyl)

2-(3, 4-Dimethoxyphenyl)-5, 6, 7trimethoxy-

Tetradecanoic acid

N, N'-Bis-benzoyloxyheptanediamide

Fig. 2.5 Chemical structures of the main components of hot water extract of mandarin peels

found to achieve 80% of corrosion inhibition efficiency. Less corrosion products were produced in presence of Z. officinale as indicated by XRD. Parthipan et al. (2018) investigated the efficiency of garlic extract (GAE) as a green biocidal inhibitor to control microbial corrosion of stainless steel 316 and carbon steel API 5LX in the presence of Streptomyces parvus B7 and Bacillus subtilis A1. To determine the antibacterial activity of the GAE, agar well diffusion assay was employed. Results revealed that 100 ppm of GAE represented the minimum inhibitory concentration for inhibiting bacterial growth. Severe microbial corrosion occurred to both metals in presence of each bacterial strain A1, B7 alone and by their mixed consortium. It was shown that GAE had the potential to inhibit corrosion in presence and absence of bacteria. The inhibition efficiency percentage (IE %) for the abiotic system was about 81 ± 3% and 75 ± 3%, but in the presence of the mixed bacterial consortium (biotic system) the IE% was 72 ± 3% and 69 ± 3% for carbon steel and stainless steel 316, respectively. GC/MS of GAE indicated that GAE is sulphur rich and played

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a significant role in the inhibition of corrosion and microbial corrosion. Among the sulphur compounds that were found; diallyl disulphide, trisulfide, di-2-Propenyl, di-n-decylsulfone, 2-furancarboxaldehyde and 5-(hydroxymethyl). This was the first report to show that garlic extract can act as a green corrosion inhibitor as well as a biocide to control biocorrosion in hypersaline corrosive environment containing biofouling causing microorganisms. Stainless steel type 304L is frequently used in many industrial applications because of its resistance against corrosion. A protective film made up of chromium oxyhydroxide usually covers that type of steel and confers its high resistance. Nonetheless, in aggressive corrosive environments, 304L SS becomes susceptible to corrosion (Yuan and Pehkonen 2009). Pseudomonas and Bacillus species are aerobic bacteria which can accelerate corrosion rate by allowing the disruption of the passive films (Morales et al. 1993). Among the predominant species of Pseudomonas is P. aeruginosa which is a Gram negative aerobic bacterium and it is largely distributed in marine environment. P. aeruginosa has the potential to form biofilms on metal and alloy surfaces and to speed up their corrosion rates (Jia et al. 2017e; Xu et al. 2017b). According to Pedersen et al. (1988), Pseudomonas sp. are able to secrete organic acids which facilitate the disruption of passive films and consequently accelerate the corrosion rate. In a study performed by Lekbach et al. (2018), the efficacy of ethanolic extract of Cistus ladanifer to mitigate corrosion of 304L stainless steel (SS) in presence of P. aeruginosa was assessed via surface analysis techniques as well as electrochemical measurements. C. ladanifer is an aromatic shrub belonging to the Cistaceae family. It is commonly known to possess antimicrobial characteristics (Barros et al. 2013). The obtained findings showed that P. aeruginosa formed biofilms on the surface of 304L SS coupon and accelerated the corrosion rate resulting in formation of pitting corrosion with a maximum pit depth of 19.4 μm. Upon treatment with C. ladanifer extract, the growth of planktonic cells of P. aeruginosa was inhibited and the biofilm formation decreased. The biocorrosion rate was highly decreased as well. High-pressure liquid chromatography coupled with quadrupole time-offlight mass spectrometry (HPLC-Q-TOF-MS) was employed to identify and characterize the structural components of the plant extract. Sixteen phenolic and flavonoid compounds, tannins, phenolic acids, ellagic acid and derivatives, ellagitannin, and flavnol were identified. Many of these components are reported to own antimicrobial properties. Such components aided in the excellent anti-corrosion and anti-biofilm performance of C. ladanifer extract. Seeking an environmentally friendly and a safe natural compound that could protect against microbial corrosion, ethanolic extract of Salvia officinalis was selected for study by Lekbach and co-workers (Lekbach et al. 2019) S. officinalis belongs to Lamiaceae family. It is well known to be widely used in preparation of cosmetic formulations, medicine, food flavoring materials and insecticides (Kamatou et al. 2008). Previous research papers reported the abundance of phenolic compounds in S. officinalis plant, thus making it a great option to be tested for microbial corrosion mitigation (Zimmermann et al. 2011; Martins et al. 2014). Results revealed the presence of some antimicrobial and anti-corrosion compounds within the extract. The S. officinalis extract was found to be extremely effectibe in inhibiting biofilm

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formation and hindering mature biofilms. HPLC-Q-TOF-MS results demonstrated that most compounds existed within the extract belonged to oxylipins and phenolic families. Electrochemical results designated that P. aeruginosa accelerated microbial corrosion of 304L stainless steel, while the extract exerted an inhibition effect against microbial corrosion with an IE% of 97.5 ± 1.5%. This was credited to the formation of a protective layer by the adsorption of the extract components on 304L stainless steel surface. Results obtained from confocal laser scanning microscopy (CLSM) and electrochemical studies confirmed the protection of the coupon surfaces against pitting corrosion.

2.9.2 Micro- and Macro-Algae and Seaweeds As the process of biofouling does not only take place in man-made structures but also the implications of such problem extend to marine organisms (Dahms and Dobretsov 2017). Wahl et al. (2012) reported that most marine organisms do not suffer from marine biofouling. So, it can be concluded that such organisms possess certain antifouling strategies. By reaching the strategies which these marine organisms follow to protect themselves, it will be helpful to improve the present anti-fouling methodologies. Among the two most reported anti-fouling mechanisms; surface microstructures and surface wettability (Wahl et al. 2012). Additionally, several secondary metabolites are execreted by marine organisms which help in repelling or diminishing of biofouling causing species (Qian et al. 2009). Amazingly, it was found that certain microorganisms present on the surface of marine sponges, algae and corals help to monitor the colonization of hosts by the fouling causing organisms (Dobretsov et al. 2006; Wahl et al. 2012). Such species depend on different biological, chemical and physical strategies to mitigate biofouling (Dobretsov et al. 2013). Macroalgae belong to multicellular polyphyletic group which contains photosynthetic eukaryotic organisms (Lee 2008) Macroalgae are categorized into three main categories including; green macroalgae (division Chlorophyta), brown macroalgae (division Phaeophyta) and red macroalgae (division Rhodophyta) based on the genealogy of the existed plastids (Lee 2008). Some researchers include prokaryotic blue green algae (phylum Cyanobacteria). Marine macroalgae are usually existed in quite different types of water such as in polar, temporal, and tropical water bodies (Lee 2008). According to a study performed by Bhadury and Wright (2004), huge biomasses of marine macroalgae are wasted and only very few species are used in cosmetics, human food, fertilizers, biofuel and as sources of natural products.

2.9.2.1

Green Macroalgae (Chlorophyta)

Different anti-fouling compounds have been extracted from chlorophyta algae such as the genera of Ulva like Ulva rigida (Chapman et al. 2014), Ulva pertusa (Yingying et al. 2015), Ulva reticulate and Ulva lactuca (Prabhakaran et al. 2012), Codium

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such as Codium fragile (Águila-Ramírez et al. 2012), Caulerpa such as Caulerpa prolifera (Smyrniotopoulos et al. 2003), Caulerpa racemosa (Batista et al. 2014) and Chlorococcum such as Chlorococcum humicola (Bhagavathy et al. 2011). The nature of the extracted compounds ranges from alkaloid phenolic acids to organic extracts, polar and non-polar extracts. Prabhakaran et al. (2012) performed a study to screen and evaluate the biocidal potential of various seaweed extracts including; Sargassum wightii, Ulva reticulate and Halimeda macroloba, sea grasses such as Halodule pinifolia and Cymodocea serullata as well as mangrove plants like Rhizophora apiculata, Rhizophora mucronata and Avicennia marina against some marine fouling bacteria. The tested species of seaweeds, seagrasses and mangrove samples were collected, washed thoroughly, air dried and fine powdered and then were extracted using solvents such as ethanol and methanol. The active fractions of the extracts were eluted with the ethanol and analyzed via FTIR. The biofouling bacteria were isolated by scrapping a biofilm grown on PVC sheet from a marine environment. Among ten isolated strains, four isolates were selected for this study and they were Flavobacterium sp., Pseudomonas sp., Bacillus sp. and Cytophaga sp. The biocidal potential of Avicennia marina was recorded to limit the growth of Flavobacterium sp. (16 mm) and Bacillus sp. (20 mm). Moreover, the extracts of Rhizophora mucronata limited the growth of Flavobacterium sp. (18 mm) and Bacillus sp. (18 mm). Interestingly mangrove plant ‘extract displayed the highest biocidal activity against the primary biofilm forming bacteria than both of seaweeds and seagrasses. The inhibition activity was largely dependent on the existed major functional groups including; hydroxyl, amino, carbonyl and phosphoryl functionalities, NH2 (amide I and II), aliphatic (fatty acids) of the prepared extract. Hence, the study gives an insight into using such natural sources to inhibit biofouling.

2.9.2.2

Brown Macroalgae (Phaeophyta)

Different genera of brown algae have been investigated including; Sargassum such as Sargassum muticum (Plouguerné et al. 2010; Silkina et al. 2012), S. thunbergii (Li et al. 2013), S. horneri (Cho 2013), S. furcatum (Batista et al. 2014) and S. vulgare (Carvalho et al. 2016). Many of these algal alcoholic extracts were proved to exhibit antibacterial (including anti-quorum sensing), anti-diatom, antialgal and anti-larval effects. Examples of the anti-fouling compounds extracted from brown macroalgae: (a) sesquiterpenoid (-)-gleenol from T. atomaria; (b) sn-3-O(geranylgeranyl) glycerol from Taonia atomaria and Dyctiota sp.; (c) dimethylsulphopropionate from Fucus vesiculosus and (d) monocyclic meroditerpenoid from Cystoseira tamariscifolia. Prabhakaran et al. (2012) reported that the ethanolic extract of the seaweed Sargassum wightii exhibited high bactericidal activity against Bacillus sp. and Flavobacterium sp. which was like the extracts of the green algae Halimeda macroloba and Ulva reticulata. The anti-fungal activity of Fucus vesiculosus was studied by Lachnit et al. (2010a, b) and Saha and Wahl (2013). Two identified compounds were isolated from F. vesiculosus namely; proline and dimethylsulphopropionate (DMSP). Schwartz et al. (2017) demonstrated that extracts of Sargassum

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muticum exhibited a high biocidal activity against the growth of bacteria, diatoms and the settlement of Bugula neritina larvae than the native Sargassum species.

2.9.2.3

Red Macroalgae (Rhodophyta)

Several genera of red macroalgae such as Asparagopsis spp. and Laurencia spp. were found to exert antimicrobial activity specifically antibacterial, anti-diatom, antispore and anti-larval effects. Certain compounds were found to be deposited on the surface of Laurencia translucida mainly hexadecanoic acid, docosane, and cholesterol trimethylsilyl ether (Paradas et al. 2016). Al-Lihaibi et al. (2015) managed to identify certain components namely; 2, 10-dibromo-3-chloro-7-chamigrene and 12-hydroxyisolaurene from Laurencia obtuse. These compounds prevented the settlement of the barnacle Balanus amphitrite at a concentration three-fold less than the copper sulfate. In a study performed by Cen-Pacheco et al. (2015), certain chemical constituents were isolated and identified namely; 28-hydroxysaiyacenols B and A, saiyacenols B and C in addition to dehydrothyrsiferol. All compounds were efficient only against diatoms Navicula cf. salinicola and Cylindrotheca sp., while 28-hydroxysaiyacenols B and A prevented the germination of Gayralia oxysperma spores. It is worth mentioning that surface of the marine macroalgae is usually covered with several species of bacteria, fungi and microalgae. They are usually referred to as “epibionts”. Additionally, the composition of such epibionts varies according to the algal parts as well as the surrounding environmental conditions (Saha and Wahl 2013). Da Gama et al. (2014) reported that in some cases, some of these epibionts penetrate the thalli of macroalgae. Numerous investigations revealed that epibionts accompanying algae have the capacity to produce anti-fouling compounds and aid in defending their hosts (Holmstrøm and Kjelleberg 1999; Burgess et al. 2003; De Oliveira et al. 2012; Satheesh et al. 2016). Dobretsov and Qian (2002) and Harder et al. (2004) demonstrated that Vibrio sp. isolated from the green algae Ulva reticulata produced an anti-fouling compound. Another investigation performed by Kanagasabhapathy et al. (2009) demonstrated that different quorum sensing (QS) inhibitory compounds were produced from the bacteria which were existed on the surface of the brown algae Colpomenia sinuosa. Batista et al. (2014) isolated the attached diatoms and surface attached bacteria via ethanol treatment. Their obtained data pointed out that microorganisms living on the surface of some algae might be responsible for producing QS inhibitory molecules. Since marine algae produce different classes of biologically active metabolites, these metabolites are exploited in synthesizing commercial products for instance antibiotics, cytotoxic agents, anti-inflammatory, immunosuppressive and cosmetic products (Dahms and Dobretsov 2017). Isolation of such bioactive compounds can also be used in developing environmentally-friendly anti-fouling paints. Such substances belong to classes of amides, fatty acids, lipopeptides, steroids, alkaloids, lactones, pyrroles and terpenoids. Interestingly, algal secondary metabolites can be produced commercially via metabolic and genetic engineering techniques.

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Macroalgae represent a large multicellular group of photosynthetic eukaryotic organisms (Lee 2008). As reported by Dahms and Dobretsov (2017), several metabolites have been isolated and identified from brown algae with anti-fouling potential. Among these substances; (a) sn-3-O-(geranylgeranyl) glycerol isolated from Taonia atomaria and Dyctiota sp., sesquiterpenoid (-)-gleenol isolated from T. atomaria; monocyclic meroditerpenoid isolated from Cystoseira tamariscifolia; dimethylsulphopropionate from Fucus vesiculosus; 1-(3, 5 dihydroxyphenoxy)-7 (2, 4, 6-trihydroxyphenoxy)-2, 4, 9-trihydroxydibenzo-1, 4-dioxin; and 6, 6 bieckol. Additionally, several researchers investigated anti-fouling compounds in Sargassum spp, amongest; phlorotannins, galactoglycerolipids, stigmasta-5, 22-E-, 28-triene3β, 24α-diol, and chromanols (Plouguerné et al. 2010; Li et al. 2013; Cho 2013; Nakajima et al. 2016). A bio-inspired anti-fouling mechanism of macroalgae was investigated by Chapman et al. (2014). Saccharina latissima (sugar kelp) and Fucus guiryi (Guiry’s wrack) are usually existed in several areas such as Irish shores in Dublin, Ireland. The tested macroalgae were chosen because they are resistant to biofouling during high and low fouling seasons. Furthermore, a pre-extracted brominated furanone was incorporated within the matrix (0.05 μg/ml). The brominated furanone was extracted from Ulva rigida. The matrix that was composed of replicated macroalgae samples along with the brominated furanone compound and then they were tested for their anti-fouling activity. Results demonstrated that furanone-doped materials with replicated surface topography prevented biofouling dominance. Paradas et al. (2016) reported that several genera such as Laurencia spp. and Asparagopsis spp. (belong to red algae), possessed antibacterial, anti-diatom, anti-larval, anti-fouling effects as well as exerting an inhibiting effect on quorum sensing process. Among the identified anti-fouling compounds in red algae; 2,10-dibromo-3-chloro-7-chamigrene from Laurencia obtusa; Omaezallene from Laurencia sp.; 12-hydroxyisolaurene from Laurencia obtuse; Dehydrothyrsiferol; Saiyacenols B; Saiyacenols C; 28-hydroxysaiyacenol A from L. viridis and 28-hydroxysaiyacenol B from Laurencia viridis (Dahms and Dobretsov 2017). Oktaviani et al. (2019) investigated the potential antibacterial activity that could be exhibited by two seaweeds Chaetomorpha antennina and Turbinaria ornata and against 14 isolates of fouling bacteria symbolled as (F1–F14). Extract of both seaweeds was performed using hexane, methanol and ethyl acetate. Phytochemical analysis was carried out for both seaweeds. It was found that C. anteninna extract possessed more phytochemicals such as phenols, steroids, flavonoids, triterpenoids, saponin and alkaloids. On the other hand, T. ornata extract contained only saponin, phenol, steroid and alkaloids. F5, F6, F7, F8, F10, F11, F12, F13 and F14 bacteria were not affected by the tested seaweed extracts. C. antennina extract posed a better biocidal effect than T. ornate extract. The diameter of inhibition zone was 6 and 2 mm for C. antennina and T. ornata extract, respectively at a concentration of 10 μl/disk.

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2.9.3 Inhibition of Quorum Sensing to Combat Biofouling As demonstrated by Rocha-Estrada et al. (2010) and Grandclément et al. (2016), quorum sensing (QS) is a mechanism used by microorganisms to facilitate their communication. This mechanism harmonizes their behavior for instance motility, sporulation, biofilm formation; resistance towards biocides and bioluminescence (Jia et al. 2019). QS mainly depends on concentration of signal molecules and microbial consortium (Bhargava et al. 2010). The three most studied QS systems are N-acyl homoserine lactone (AHL) based signaling system which appears in Gram-negative bacteria and luxS-encoded autoinducer 2 (AI-2) QS system which occurs in both Gram-positive and Gram-negative bacteria (Kalia 2013). In addition to oligopeptide based QS system which appears in Gram-positive bacteria. As reported by Christiaen et al. (2014), quorum sensing inhibition (QSI) is an effective route to monitor biofilm formation. QSI retards QS via different mechanisms (Lade et al. 2014) and include; • controlling the synthesis of QS molecules by inhibiting or reducing the activity of the gene responsible for synthesizing such molecules, • degradation of signal molecule, • modifying the binding of signal molecules to receptor sites, and • blocking receptor sites with antagonistic molecules. Marine macroalgae possess the capacity to enhance, prevent, or compromise QS signaling molecules in bacteria (Saurav et al. 2017). Still, there is no clear evidence whether the real biosynthetic origin of QS inhibitors in macroalgae, comes from the algae themselves or from the bacteria associated with them or by both routes (Goecke et al. 2010). In most of cases, the mechanisms of QS inhibition by algal metabolites are not clear and need to be studied in more details. Borchard et al. (2001) demonstrated that hypobromous acid interferes with bacterial QS signaling and genes. Hypobromous acid was produced by the brown algae Laminaria digitata. Kanagasabhapathy et al. (2009) reported that the bacteria present on the surface of the green algae Ulva sp. and Colpomenia sinuosa had the capacity to inhibit QS and subsequently inhibited biofouling. It was found that this kind of algae secret furanones which inhibit AHL bacterial signals. Dobretso et al. (2011) revealed that the brown algae Spatoglossum sp. produced dulcitol which acted as a QS inhibitor. This isolated compound resulted in compromising luminescence production in E. coli-based reporters in presence of AHL signals. Jha et al. (2013) extracted 2dodecanoyloxyethanesulfonate from the red algae Asparagopis taxiformis and the isolated compound possessed the potential to inhibit QS of Serratia liquefaciens MG44 and Chromobacterium violaceum CV026. Batista and co-workers (2014) revealed that the QS of the bacterium C. violaceum CV017 was inhibited by 91% of polar (methanol/water) extracts of the red algae Asparagopis taxiformis (Batista et al. 2014). In a study performed by Carvalho et al. (2016) green, red and brown macroalgae isolated from the Brazilian coast caused QS inhibition of C. violaceum CV017. Saurav et al. (2017) introduced the first report for the isolation of a QS inhibitory compound and it was isolated from the marine red macroalgae Delisea

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pulchra. According to Dahms and Dobretsov (2017), algae polar extracts showed considerable antibacterial potential against biofilm forming bacteria. Interestingly, the minimum inhibitory concentrations (MICs) of the non-polar extracts were found to be 10 to 1000-fold more efficiency. As reported by Kalia and Purohit (2011), the enzymatic degradation of AHL is the most studied QSI strategy. Various naturally synthesized inhibitors were reported to disturb QS mechanisms. Bacteria, fungi, animals, plants and marine organisms are among the natural sources that are employed to inhibit QS signaling molecules (Kalia 2013; Tang and Zhang 2014). Many naturally occurring constituents such as ajoene from garlic and iberin from horseradish proved to possess QSI effect against P. aeruginosa (Jakobsen et al. 2012). Moreover, vanillin was tested as a natural inhibitor against QS of P. aeroginosa as demonstrated by Choo et al. (2006). Paczkowski et al. (2017) reported the ability of naturally occurring plant constituents to inhibit QS such as coumarins, tannins, phenolics, alkaloids, quinines, terpenoids and saponins. Nevertheless, most of the natural QS inhibitors are generated in very small portions and may exert toxicity. And still, cost is another disadvantage of this strategy for inhibiting industrial biofilms (Jia et al. 2019).

2.9.4 Biofouling Inhibition by Microorganisms An interesting research area is the use of microorganisms to inhibit other corrosion causing microorganisms. Such action can be attained by nitrate reducing bacteria and bacteriophages.

2.9.4.1

Microbial Corrosion Inhibition by Nitrate-Reducing Bacteria (NRB)

A suggested solution to overcome the dramatic effect of SRB is via nitrate injection which enhances the growth of heterotrophic nitrate reducing bacteria (hNRB) as well as sulfide-oxidizing nitrate reducing bacteria (SO-NRB). Both are generally referred to as “nitrate reducing bacteria” (NRB). As reported by Grigoryan et al. (2008), when SRB existed in a microcosm containing mixtures of butyrate, propionate and acetate, it was observed that SRB oxidized propionate and butyrate then acetate. Nevertheless, presence of hNRB aids in utilizing all three compounds simultaneously. Thus, a competition takes place between SRB and NRB in which hNRB will overcome SRB (Thauer et al. 1977). SO-NRB are autotrophic bacteria and no competition takes place with SRB. In fact, SO-NRB reduce nitrate to nitrite, nitrous oxide, nitric oxide, and nitrogen (Hubert and Voordouw 2007). The generated nitrite is toxic to SRB as it can inhibit the synthesis of dissimilatory sulfite reductase (Dsr). Dsr is the enzyme which catalyzes the reduction of sulfite to sulfide. Furthermore, SRB can be eliminated by the effect of nitrous oxide. This might take place as nitrous oxide increases the redox potential to a level where strict anaerobic bacteria such

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as SRB cannot survive within (Jenneman et al. 1986). Schwermer et al. (2008) performed a study to evaluate the efficiency of nitrate treatment on the integrity of bacterial biofilms in a seawater injection system. It was found that nitrate pierced throughout the entire biofilm and was chiefly transformed into nitrite. Nonetheless, the study target was to mitigate microbially influenced pitting corrosion by inhibition of SRB, it was found that pitting corrosion was not affected. On the other hand, uniform corrosion was greatly inhibited. Authors attributed this action as nitrite usually causes pitting corrosion. According to Videla and Herrera (2009), nitrite is an anodic inhibitor and inadequate concentration of nitrite might result in pitting corrosion. Hence, it is usually recommended that monitoring of nitrite is vital for effective application of corrosion control by NRB. Corrosion control using NRB is an attractive option for industry as it is an environmentally friendly methodology that can substitute biocides. Bodtker et al. (2008) demonstrated the efficacy of long term treatment with nitrate on corrosion control in comparison with biocide treatment in Veslefrikk and Gullfaks oil fields. It was noticed that biocide treatment stimulated SRB activity and increased the corrosion rate. Conversely, nitrate treatment reduced the activity of SRB in both fields and increased the number of NRB. It was observed that corrosion at the Gullfaks field was reduced up to 40% whereas, no significant decrease took place in Veslefrikk oil field (Zarasvand and Rai 2014).

2.9.4.2

Microbial Corrosion Inhibition by Bacteriophage

Using bacteriophages as a new methodology to inhibit corrosion attracted lots of interest worldwide. Bacteriophages are type of viruses that are able to infect bacterial cells only. They depend mainly upon the host cell’s replication mechanism to produce multiple copies and further infect other bacterial hosts. Destiny of bacteriophage differs after infecting the bacterial cell host. Some phages go through a lytic cycle and others may undergo a lysogenic cycle. In a lytic life cycle, host cells become lysed and infect more bacteria, while in a lysogenic cycle, phages remain in a dormant state referred to as “prophage” and replicate within the host cell, until a lytic cycle is induced by either a physical or chemical method (Zarasvand and Rai 2014). An advantage of using phage over biocides is itself replication capability. Eydal et al. (2009) managed to isolate lytic phages to inhibit Desulfovibrio aespoeensis. To search for the bacterial host cells that were susceptible to the isolated phage, six different species of Desulfovibrio and ten SRB strains were isolated. It was noticed that D. aespoeensis was the only host susceptible to the isolated lytic phage. Sillankorva et al. (2010) exposed the phage fIBB-PF7A to dual species biofilm containing P. fluorescens and Staphylococcus lentus. The phage fIBB-PF7A infected P. fluorescens only, and partially disrupted the biofilm structure releasing nonsusceptible cells of S. lentus from biofilm to the planktonic phase. Hence, switching the biofilm condition of bacterial cells from sessile to planktonic states improves the efficacy of the used biocide. As biocides are more potent towards planktonic bacteria rather than sessile forms. Identification of factors affecting the phage behavior can be used for successful inhibition of corrosion causing bacteria. Walshe et al. (2010)

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studied the effect of different factors such as pH, dissolved organic matter, ionic strength and flow rate on the transport of MS2 type bacteriophages. It was observed that high flow rate helped the transport of phages; while high ionic strength and low pH increased viral adsorption in aquifer environments that hindered phage transport. Phage diffusion in biofilm was also affected by the growth phase of the host. Hu et al. (2012) realized that active live cells increase the diffusion of phages within biofilm because of high rates of phage proliferation, while dead cells prolong phage diffusion. Moreover, bacterial capsule is another parameter that hinders phage diffusion. Lu and Collins (2007) reported that engineered T7 bacteriophage had the potential to release biofilm degrading enzyme referred to as “DspB” intracellularly. The released enzyme aided in the reduction of biofilm bacterial cells. Pedramfar et al. (2017) isolated corrosion causing bacterium. Samples were collected from a petroleum pipeline in Gandomkar petroleum station in Chaharmahal and Bakhtiari, Iran. The rusted pipe samples were cultured in a selective culture medium i.e. brain heart infusion (BHI) broth medium. The isolated bacteria were identified via molecular identification. The isolated corrosion causing bacterium was identified as Stenotrophomonas maltophilia strain PBM-IAUF-2 and was deposited in GenBank with accession number of KU145278.1. Bacteriophages were isolated via whole plate titration methods. The morphological structure was observed via TEM. The isolated bacteriophage belongs to Siphoviridae family of phages. The growth curve of S. maltophilia strain PBM-IAUF-2 indicated the effectiveness of the tested bacteriophage in controlling bacterial population. Effect of phages reached the maximum between 8 and 14 h of incubation. Due to the shortage in fresh water supplies, urgent strategies are required such as water reuse as well as water desalination (Ma et al. 2018). Recent techniques have evolved regarding water purification. Ultrafiltration (UF) is a membrane technique which depends on low pressure which helps in removing microorganisms, colloids, and organic compounds from water. UF does not require any extra use of chemicals during filtration which make UF more advantageous rather than its counterparts i.e. advanced oxidation, coagulation, disinfection, etc. (Bonnélye et al. 2008). Nevertheless, as with other membrane techniques, UF is subjected to irreversible fouling which is caused by microorganism propagation (Gutman et al. 2014). Chlorine is among the chemical cleaning reagents employed to mitigate biofouling in commercial membranes processes is chlorine. But unfortunately polymeric membrane materials are very susceptible to oxidative damage caused by chlorine. Thus, in order to prevent biofouling, there is an urgent need to incorporate functional materials within the membrane matrix to reduce sorption of organic constituents as well as bacteria (Ma et al. 2018). Different types of NPs and polymeric materials with anti-fouling characteristics have been applied during the construction of anti-fouling membranes such as polysulfobetaine (Rahaman et al. 2014; Ma et al. 2015), polyethylene glycol (Chen et al. 2011), silica NPs (Liang et al. 2013), perfluorooctanoate (Kwon et al. 2015) and polydimethylsiloxane (Gao et al. 2015), and biocidal agents e.g. quaternary ammonium (Ye et al. 2015), metal NPs, graphene oxide (Perreault et al. 2014, 2016). Recently, certain biological materials can be used as anti-biofouling components during membrane fabrication such as peptides and enzymes (Kim et al. 2011;

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Yeroslavsky et al. 2015) due to their superior properties such as low cost, antimicrobial properties as well as low toxicity to humans. Bacteriophages also seem to be an interesting option as they occur naturally in marine and soil environments. Ma et al. (2018) investigated the potential use of T4 bacteriophage to monitor biofouling during membrane ultrafiltration (UF) against Escherichia coli. The tested phage was immobilized on the membrane surface to inhibit propagation of E. coli. Minimization of 36% of E. coli growth was observed after 6 h of filtration for the T4-functionalized membrane. Interestingly, surface modification of the membrane with O2 plasma treatment led to an increase in the number of bound phage and therefore resulted in enhancement of the biofouling resistance of the membrane. By applying different concentrations of phages, bacterial growth was delayed, controlled and mitigated. The resultant data assured that bacteriophage aided in resisting biofouling in an eco-friendly manner.

2.9.4.3

Other Reported Studies

Due to the extreme need for using safe, environmentally friendly and natural materials as corrosion inhibitors and biocides instead of the conventional toxic chemicals, the use of bacteria and their extracellular polymeric substances (EPS) gained lots of interest. As conducted by Pedersen and Hermansson (1989, 1991) and Jayaraman et al. (1997a, b), bacteria and their EPS aid in corrosion inhibition, most probably because of biofilm formation and oxygen elimination that otherwise if existed would oxidize the metals. According to the study introduced by Jenneman et al. (1997), Thiobacillus denitrificans had the capability to significantly inhibit the growth of SRB with the addition of monosodium phosphate and ammonium nitrate to the system under study. According to Wang et al. (2004), growth of SRB biofilms could be inhibited by the biological denitrification of T. denitrificans via utilization of corrosive sulfide. Thus, T. denitrificans could retard the growth of SRB induced corrosion to some extent without killing. Moradi et al. (2015) and coworkers investigated the corrosion inhibitive effect by Vibrio neocaledonicus sp. and the produced EPS. Marine V. neocaledonicus sp. KJ841877 was isolated from marine sludge samples that were collected from the Eastern Sea. Results revealed that the high inhibition efficiency against corrosion of carbon steel was achieved by the creation of an inhibitory layer that covered the whole surface of the metal. The main composition of this inhibitory layer was Fe-EPS complex as revealed by XPS. Based on EIS results, corrosion resistance of carbon steel was increased by more than 60-folds in presence of this bacterium. Additionally, potentiodynamic polarization measurements showed that corrosion current density (icorr ) decreased in samples exposed to V. neocaledonicus sp. KJ841877. Field emission scanning electron microscope (FESEM) was used to observe the microstructure of carbon steel surface and the formed inhibitive layer. In presence of V. neocaledonicus sp., an intact film layer extensively covered the metal surface after 6 h and

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became thicker with time. The obtained result is considered as the highest corrosion inhibitory effect reported for bacteria. Moreover, it was almost comparable with industrial coatings such as electroless Ni. In 1963, Bdellovibrio bacteriovorus was discovered by Stolp and Starr (1963). It is a Gram negative predatory bacterium which has the ability to attack and feed on other bacteria (Monnappa et al. 2014). B. bacteriovorus life cycle is divided into two stages involving; attack phase (AP) and growth phase (GP). AP cells swim rapidly to search for prey with the help of a single polar flagellum; while GP cells consume the prey during their growth and reproduction (Karunker et al. 2013). Monnappa et al. (2014) reported that B. bacteriovorus can penetrate deeply into prey biofilms and destroy them. Accordingly, attention should be paid for using such predators to control SRB growth via determination of the optical density at 600 nm (OD600 ) as well as sulfate concentration in medium. Electrochemical analysis and weight loss measurements were conducted to evaluate the anti-corrosion effect on X70 pipeline steel. It was found that B. bacteriovorus inhibited the growth of SRB in culture medium which was indicated by the decrease of OD600 value and increase in sulfate concentration. Additionally, corrosion rate of X70 pipeline steel was reduced from 19.17 to 3.75 mg/dm2 day in presence of B. bacteriovorus. Inhibition of B. bacteriovorus was further indicated by the negative shift of corrosion potential of the X70 pipeline steel electrodes. In a study performed by Qiu et al. (2016), it was proved that Bdellovibrio bacteriovorus had a corrosion inhibition effect by controlling microbial corrosion of X70 steel upon exposure to SRB. Inhibition of SRB was assessed by the decrease in values of both sulfate concentration and optical density. Electrochemical analysis including tafel polarization curves, EIS and weight loss measurements were used to determine the corrosion inhibitive effect. It was found that corrosion rate declined from 19.17 to 3.75 mg/dm2 day. While, corrosion potential shifted towards the negative direction. This is considered the first report concerning the ability of B. bacteriovorus to inhibit microbial corrosion caused by SRB. According to Suma et al. (2019), a novel bacterial mediated system for corrosion inhibition of mild steel was applied by using Pseudomonas putida RSS biofilm. The corrosion rate of mild steel was found to decrease by 28 folds when compared with control. Formation of iron-extracellular polymeric substance (Fe-EPS) was the reason behind the development of a strong and stable coating layer. It was noticed that the established biofilm remained adhered on mild steel surface and hence it conferred further protection. Electrochemical results proved inhibition of corrosion for 12 months of treatment with insignificant corrosion rate of approximately 3.01 × 10−2 mmpy.

2.10 Use of Polymer Coatings to Combat Biocorrosion Lately, within the last few years, a huge development in the fabrication of robustly bonded, uniform and antibacterial polymer coatings on metallic substrates has been attained (Yang et al. 2015). As previously discussed, great efforts have been directed

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towards the use of biocides to control and mitigate microbial corrosion. However, using polymers to provide protection against biocorrosion has attracted the attention of several researchers. Polymers commonly used to prevent and control biocorrosion are basically categorized into one of the following three categories: (i) traditional polymers combined with biocides, (ii) antibacterial polymers containing quaternary ammonium compounds, and (iii) conductive polymers. Table 2.3 represents a comparison between the three types of polymers.

2.11 Conclusions Petroleum industries suffer from severe problem represented in biofouling including both micro- and macro-biofouling. With no doubt, presence of microorganisms in oil and gas facilities causes problems which are extremely costly. These problems range from reservoir souring, pipeline failure, corrosion, foam formation, etc. Microbial corrosion has been reported to occur in oil and gas treating facilities such as refineries, gas-fractioning plants, tanks, wells and petroleum pipeline systems. It is believed that microbial corrosion is one of the most damaging mechanisms to pipeline materials which occurs due to the accumulation of microbial communities like bacteria, fungi, microalgae, etc. Macrobiofouling results from the deposition and growth of macroorganisms such as barnacles and mussels. It is an old serious problem in industries which threatens human health and wealth. The undesirable effects of biofouling on petroleum pipelines, offshore platforms and engineered structures such as ships resulted in large drawbacks to the petroleum sector in terms of a notable increase in the consumption of manpower, fuel, materials and high economic cost. The economic costs and social consequences include: decrease in the efficiency and service life of machines due to the formation of corrosion products over the machinery leading to plant shut down, product (oil and gas) contamination and/or loss of products due to corrosion, and release of toxic corrosion products that have severe health effects. Seawater is widely used in oil and gas industries for cooling purposes, fire-fighting, oil-field water injection and desalination plants. Oil-field seawater is a suitable medium for microorganisms as it contains a high sulfate concentration (~20 mM) and other nutritional requirements which are needed for microbial growth. It is commonly known that the most destructive corrosion is frequently noticed in oxic-anoxic environments where the aerobic and anaerobic microorganisms exist. Different types of microorganisms are involved in aerobic microbial corrosion including; sulfur oxidizing bacteria, metal oxidizing bacteria and slime producing bacteria. Whilst, different types of microorganisms are responsible for anaerobic microbial corrosion including; sulphate reducing bacteria, iron reducing bacteria and nitrate reducing bacteria. There are different approaches through which microbial and macrobial corrosion can be inhibited. The applications of biocides are the most practical strategy for biofouling mitigation. Majority of these biocides are embedded within self-polishing coatings, controlled depletion paints and metal embedded polyacrylicresins to tackle biofouling. However, the consequences of the

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Table 2.3 Different types of polymers used to combat biocorrosion, examples, advantages and disadvantages Categories of Examples polymers used for biocorrosion inhibition

Advantages

Disadvantages

Traditional polymers incorporated within biocides

Polyurethane, fluorinated compounds, epoxy resins, polyimides, silicone, coal-tar epoxy, and polyvinyl chloride

Polyurethane: impermeability, good adhesion and abrasion resistance, flexibility, and biocompatibility Silicones: Good potential for corrosion protection

Can be degraded by microorganisms, thus leads loss in corrosion resistance (Ramezanzadeh et al. 2015), however chemical incorporation of antibacterial agents into polyurethane resins, resulted in a significant reduction in the percentage of microorganisms, and their antibacterial activity remained unchanged over time due to non-occurrence of volatilizing and leaching of the antibacterial agents (Grover et al. 2016)

Antibacterial polymers containing quaternary ammonium moieties

Quaternary ammonium compounds (QUATS)

Can be used as biocides and corrosion inhibitors against corrosion of steel and iron. This take place by attacking the plasmic membrane of cells which leads to lipid dissolution and release of intracellular components (Qi et al. 2017)

Exert un satisfactory results on sessile macroorganisms within biofilms (Guo et al. 2018)

Conductive polymers

Polypyrrole (PPY), polyaniline (PANI), and polythiophene (PBT)

Environmental stability, high conductivity, and unique redox mechanisms, play a role as barriers and inhibitors, protection of anodic dissolution, and mediation of oxygen reduction (Shi et al. 2015), widely employed as anticorrosion coatings for aluminum, mild steel, stainless steels, copper, and its alloys

Poor adhesion on the substrate surfaces, lack of chemical stability (Lv et al. 2014)

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chemical based biocides are so intense that most of the marine regulatory bodies like the international maritime organization, biocidal product regulation (EU 528/2012) etc., have banned their use. Hence, intensive studies have been carried out to explore green anti-biofouling agents like the use of extracts of plant biomaterials, micro- and macro- algae and seaweeds and by the usage of microorganisms to counter the effect of biofouling causing microorganisms.

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Chapter 3

Emphasis on the Devastating Impacts of Microbial Biofilms in Oil and Gas Facilities

Abstract Both natural and man-made surfaces are vulnerable to colonization by microorganisms which form a slimy layer in which high amounts of microbial metabolites are embedded inside. When microbial consortia become embedded within a matrix of exopolysaccharides this usually describes the condition of biofilms. Microbes inhabiting such matrix get different benefits such as abundance of water and nutrients, improvement in gene transfer; and protection against harsh environmental conditions such as presence of toxins, chemicals, disinfectants, antibiotics and desiccation. Biofilms cause severe adverse effects in different fields including; medical, industrial, marine, oil, gas and drinking water disciplines. This chapter focuses on the effect of biofilms particularly in oil and gas industries. It reviews the different aspects concerning biofilm structure, developmental stages, techniques that are usually employed for the characterization of biofilms and the produced exopolysaccharides. Furthermore, it gives a spot upon the possible preventative strategies that could inhibit biofilm formation and the different surface factors that usually aid in the microbial adherence to surfaces. Keywords Microbial biofilms · Composition · Stages · Extracellular polymeric substances · Economic impact

3.1 Introduction Approximately more than 90% of the total existed aquatic bacteria are usually attached to interfaces, for instance surface microlayers and to sediment/water interface (Rao 2015). Biofilm is defined as “a consortium of biotic elements like bacteria, cyanobacteria, and algae adhered to a substratum via the production of extracellular polymeric matrix which has the potential to entrap soluble and particulate matters, immobilizes extracellular enzymes, and acts as a reservoir for nutrients and different elements” (Rao 2015). According to Zobell and Allen (1935) and Zobell (1938, 1939), bacteria were found to be the main cause behind biofilm formation in ships. The composition of biofilms varies dramatically. Biofilms cause severe problems in several fields including healthcare industry (Floyd et al. 2017), water treatment and © Springer Nature Switzerland AG 2020 B. A. Omran and M. O. Abdel-Salam, A New Era for Microbial Corrosion Mitigation Using Nanotechnology, Advances in Material Research and Technology, https://doi.org/10.1007/978-3-030-49532-9_3

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marine industries (Chapman et al. 2010, 2013, 2014; Gangadoo et al. 2016), fresh water systems (Chapman and Regan 2011), sensor windows (Chapman and Regan 2012), implant industries (Gangadoo and Chapman 2015) and oil and gas facilities (Liduino et al. 2019; Li et al. 2020). Elbourne et al. (2019a, b) demonstrated that biofilm formation is a dynamic process. First, biochemical conditioning of the substrate takes place. This conditioning step facilitates the settlement of free living microorganisms on the surface which contains chemically active constituents that act as a foodstuff. Afterwards, microorganisms move through either by the impact of the hydrodynamic flow or via the action of organelles such as flagella, fimbriae, curli or pilli as well as their outer membrane proteins (Elbourne et al. 2019a, b). Such organelles help bacteria to interact with the surface. These physical bacterial properties along with the natural flow enable bacterial cells to overcome the repulsive forces in the surrounding environment. Besides, establishment of biofilms is greatly influenced by the nature of the substrate (i.e. charge, hydrophilicity, hydrophobicity, etc.). Once the bacterial adherence is initiated, the attached bacterial cells begin to produce extracellular polymeric substances (EPS) (Elbourne et al. 2019a, b). The attached cells start to secrete eicosapentaenoic acid and start communication via a process referred to as quorum sensing (QS). Then, as bacterial cells start to replicate, the secreted EPS accumulate on the surface where three-dimensional structure referred to as “the mature biofilm” becomes established. Subsequently, the severe aspect of microbial corrosion is represented in biofilm formation. Biofilms are comprised of different constituents such as adsorbed and absorbed matters, organic solutes, metallic ions and inorganic particles. The development of a microbial biofilm is more favorable to microorganisms rather than the planktonic growth. Biofilms help in creating differential zones and gradients such as differential aeration, differential acidification and ion concentration regions. Moreover, the most important reason why microbes assimilate into biofilms is to establish different strategies to withstand unstable and severe environmental conditions. When the environmental conditions become harsh and unfavorable, a distinctive biological stress response is prompted leading to biofilm formation. In most natural environments, microbial adhesion to surfaces is the predominant lifestyle for microorganisms. This is because biofilms offer desirable micro-environment where the cells will not be affected by the stress of external forces and shear stress. It is worth noting that, biofilms are also sometimes vital to microorganisms in order to provide protection against antimicrobials, toxins, predators, desiccation, ultraviolet (UV) radiation and other biological stress factors (Lories et al. 2020). Besides, biofilms help in increasing the phenotypic diversity to microbial populations, enhance nutrient access and abundance, endorse a supportive metabolism and gene transfer. Nonetheless, growth in a biofilm also has few disadvantages like minimization of mass transfer.

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3.2 Biofilm Definition and Composition Biofilms have been referred to by more than one term such as periphyton and mycrophytobenthos. The term periphyton was first suggested by Behnin in 1924 and was used to designate organisms that grow attached to an artificial surface in water (Cooke 1956). Periphyton is defined as “a complex community which largely involves heterotrophic bacteria, photoautotrophic algae, fungi, protozoans, viruses, metazoans as well as organic and inorganic detritus attached to substrates”. This term is often used in freshwater and aquaculture pond systems. Contra wise, the term microphytobenthos is used in marine ecosystems to describe the photosynthetic microorganisms, such as cyanobacteria as well as eukaryotic algae which adhere to illuminated sediments (MacIntyre et al. 1996). The broader term “biofilm” is used for the general description of all of these criteria (Sanli et al. 2015). According to Vu et al. (2009), the term “biofilm” was first coined in 1978. Biofilm can be defined as “‘matrix-enclosed bacterial population adherent to each other and/or to surfaces or interfaces” (Costerton et al. 1995). To fully understand the concept of biofilm, it is essential to identify the states at which bacteria occur. The first condition is the planktonic or free living or freely swimming form. Bacteria favor this state when the nutrients are available in the surrounding bulk environment. Contrary, when the nutrients become not available and limited in the bulk solution and exist on surfaces, bacteria start to attach and adhere themselves to the surface and become sessile or motionless upon these surfaces. The so-called biofilm is made up of such sessile bacteria. A biofilm is a complex structure which is largely composed of water (95%), bacteria, extracellular polymeric substances (EPSs), enzymes, proteins, eDNA, lipids, corrosion products and metal ions. EPS involve the presence of different macromolecules which mediate initial cell attachment to the material surface and provide perfect conditions for extensive redox and enzymatic activities. These biopolymers can be categorized into two main types “tight” if they are strongly attached to the material surface by non-covalent interactions and “loose” if they are weekly bound to the surface (Beech and Gaylarde 1989). The produced EPS by the microorganisms perform more than one role including (i) trapping nutrients and toxic compounds, (ii) increasing the activity and stability of extracellular enzymes by buffering pH and salinity variations, (iii) quorum sensing, (iv) exchanging genetic information, (v) serving as physical anchor, and (vi) providing protection against predators (Decho and Gutierrez 2017). EPS do not consist only of polysaccharides, but also they are made up of proteins and in certain cases lipids, nucleic acids and other biopolymers (Flemming and Wingender 2001). Decho and Gutierrez (2017) demonstrated that most marine bacteria produce heteropolysaccharides with 3–4 different monosaccharides, such as pentoses, hexoses, uronic acids or amino sugars arranged in groups. The thermophilic bacterium Bacillus thermoantarcticus produces a sulfate heteropolysaccharide containing mannose and glucose, and a sulfate homopolysaccharide containing mannose as the major component (Manca et al. 1996). The EPS produced by the thermophilic strains Geobacillus tepidamans showed unusual feature such as stability

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at high temperatures (i.e. the purified EPS showed thermal degradation at 280°C) (Kambourova et al. 2009). It is worth mentioning that a study by Van der Merwe et al. (2009) revealed that the production of EPS per unit of biomass was greater in the colder zones of the ice cores, suggesting a cryoprotectant role of EPS for sea ice biota. Biofilms helped bacterial cells for billions of years from sever environmental conditions and allowed them to colonize almost every habitat on Earth. An attached bacterial cell gains benefits from the solid-liquid interface, particularly the nutrients adsorbed at the surface (De Carvalho 2018).

3.3 Developmental Stages of Biofilms Formation of biofilm may require few hours to few weeks in order to develop depending largely on substratum composition, the physical and the biological features of the surrounding environment (Wang 2011). The development of a biofilm is the consequence of succeeding physical, chemical and biological interactions that occur simultaneously. Biofilm formation is generally described in (Fig. 3.1). The first components that associate to the surface are not microorganisms but organic molecules, salts and solvated ions. These components are utilized by bacteria as nutrients, electron acceptors, enzymatic cofactors, trace elements, etc. They are transported from the bulk electrolyte to the metal surface where they become adsorbed and subsequently retained by the heterogeneous structure of the surface. Almost immediately after a clean surface comes into contact with water, a complex layer of organic and inorganic deposits is formed. These components form a conditioning layer that neutralizes the surface charge and reduces the surface free energy. Some planktonic (free living) cells are transported from the bulk electrolyte to the preconditioned surface (Dang and Lovell 2016). These pioneer cells become embedded within the boundary layer via electrostatic attraction and physical forces. A fraction of the transported cells becomes adsorbed onto the preconditioned surface for a definite time and later desorbs (reversible adsorption) (Furey et al. 2017). Desorption is mainly controlled by the shear stress caused by a flowing electrolyte; however, there are other physical, chemical and biological factors, that independently or collectively may influence the separation process such as the quorum sensing (QS) phenomenon which is cell to cell communication process. The microbial fraction that is able to remain adsorbed onto the surface constitute an irreversibly adsorbed film after a critical residence time. The cells that became irreversibly adsorbed start to develop and replicate using nutrients from both the electrolyte and the metallic surface. This leads to a progressive increase in the number of sessile cells and accordingly the biofilm thickness and density increase. A substantial production of extracellular polymeric matrix (EPM) promotes the biofilm cohesion. New cells (secondary colonizers) and organic and inorganic matters attach to the developed biofilm as it reaches a mature state. The secondary colonizers metabolize wastes from the primary colonizers and produce their own waste which other cells may use. QS regulates the concentration of cells in the biofilm and mediates desorption phenomena when critical cellular

Proteins

Lipids

Development

Nucleic acid

Stages of biofilm formation

Different bacterial species

Active biofilm

Colonization

Initial attachment by the Chemical and physical interactions

Fig. 3.1 Diagrammatic representation describes the cyclic stages for the formation of active biofilm. Cells initially attach to a surface via physical and chemical interactions to form cell monolayer. Afterwards, cells begin to proliferate in the monolayer to form an active biofilm and release the EPSs. At this point, the surface becomes preconditioned for further development of biofilms which is affected by several environmental conditions like mechanical and hydrodynamic stresses. Then, biofilms reach maturity and regain mobility and undergo chemotaxis. Biofilms detach and start spreading to another surface

Polysaccharides

Maturation

Biofilm detachment and dispersal

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concentrations are reached. External parts of a biofilm detach and return to the bulk electrolyte. The detached cells might reattach elsewhere to a new surface to develop a new biofilm or become incorporated in a previously established one. The cells that remain attached to the biofilm form multispecies consortia with highly complex architecture and heterogeneous structure. When the formation of biofilms takes place in oil and gas facilities, they cause severe losses to pipelines, pollution to the produced products and enhancement of metallic degradation processes (corrosion).

3.4 Estimated Economical Costs Due to Biofilm Formation in Oil and Gas Industries The costs behind biofilm formation to several industries are extensive. Fitridge et al. (2012) reported that in case of aquaculture, the estimated cost reached 1.5–3 billion USD $ per year. Ibrahim (2012) demonstrated that the estimated costs for biofilm formation in heat exchangers are 7.5% of the total maintenance cost. While in oil and gas facilities, microbial corrosion and biofilm cost approximately 20–30% of total corrosion costs (Skovhus et al. 2017a, b). Fernandes et al. (2016) reported that in case of maritime transport biofilm formation caused 1.6–4% of annual operational cost for a ship and 35–50% increase in fuel consumption. According to Maddah and Chogle (2017), biofilm formation caused high operational cleaning costs in water desalination systems.

3.5 Techniques Employed for Biofilm Characterization Progress in different microscopic technologies facilitated the characterization of biofilms to be easily investigated, interpreted, understood and visualized. Different microscopes are used, among which the confocal laser scanning microscopy, scanning electron microscopy and the cryo-electron microscopy.

3.5.1 Confocal Laser Scanning Microscopy (CLSM) CLSM is a microscopic technique which depends on using a range of fluorescent probes that aid in biofilm visualization. It has no destructive effect during the visualization of biofilms. It allows in-situ analysis of biofilm samples on substrates. Another advantage of CLSM is the ability to observe biofilms in either their fully hydrated or living states. It also validates the detection of the complexity and the heterogeneity

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of the studied biofilm. Different wavelengths are employed (458, 477, 488, 514 and 633 nm) to yield emission fingerprinting. Waller et al. (2018) developed biofilms in Petridishes and then the dishes with the established biofilm were submerged into a phosphate buffer saline (PBS) solution. Afterwards, the intact cells within the biofilm were stained with Syto9 to ease the imaging process. Optical images were taken from a number of locations to visualize the biofilm structure. Olson et al. (2018) visualized cultures of medically formed biofilm communities of Candida albicans and C. glabrata using CLSM.

3.5.2 Scanning Electron Microscopy (SEM) For many previous decades, scanning electron microscopy (SEM) was a standard technique to visualize and inspect biofilms. Usually, to visualize biofilms via SEM, biofilms are allowed to grow on substrates, chemically fixed, dehydrated, freeze fractured, critical point dried, and then sputter coated and analyzed. Recent methodologies in SEM rely on using focused ion beam (FIB) which demonstrates the structure of biofilms. Unfortunately, it has some disadvantages including; destruction of the sample with the appearance of amorphous layers within the sample, and it is a time consuming technique. Preferably, focus ion beam scanning electron microscopy (FIB-SEM) should be employed along with other techniques to provide comprehensive information concerning the studied sample.

3.5.3 Cryo-Electron Microscopy (EM) Cryo-EM provides high-resolution images for the targeted biofilm structural appearance. Modern cryo-EM employ new techniques such as electron cryotomography (ECT) and single particle analysis (SPA). But these techniques are closely linked to the sample size as large microbial cells become too thick to permit a meaningful analysis. To overcome such problem new techniques were invented such as soft X-ray tomography (SXT) and cryo-scanning transmission tomography (CSTET) as reported by Briegel and Uphoff (2018). Hrubanova et al. (2018) revealed that using high pressure freezing (HPF) allows fixation of hydrated samples. Henceforth, detailed information of the biofilm structure can be obtained. The conjunction of the HPF and freeze-fracture process upgraded EM-based imaging of bacterial biofilms as well as the associated EPS within the biofilm.

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3.5.4 Scanning Transmission X-Ray, Atomic Force, Soft X-Ray and Digital Time-Lapse Microscopy Scanning transmission X-ray microscopy (STXM) is used to study hydrated biofilms because of the capability of soft X-rays to pierce into water. STMX, CLSM and transmission electron microscope (TEM) are usually employed to determine the distribution of macromolecular constituents in a biofilm such as proteins, polysaccharides, nucleic acids and lipids as demonstrated by Lawrence et al. (2003). That aided in mapping the biofilm composition and structure. Additionally, atomic force microscopy (AFM) elucidates the topography of the biofilm surface and helps in analyzing the EPS of bacterial biofilms which exist on surfaces (Palmer and Sternberg 1999; Hansma et al. 2000). Soft X-ray microscopy is used to investigate the early steps of bacterial colonization (Gilbert et al. 1999). Moreover, digital time-lapse microscopy is used for in-situ purposes to investigate the growth and detachment of biofilms within flow cells (Stoodley et al. 2001). Eventually, the near-field scanning optical microscopy is employed to examine the structure and composition of bacteria that build up the biofilm.

3.5.5 Fourier Transform Infrared, Nuclear Magnetic Resonance and Raman Spectroscopy Fourier transform infrared (FTIR) spectroscopy is usually used in analyzing microbial aggregates on membrane surfaces (Ridgway et al. 1983; Suci et al. 2001). FTIR gives information concerning the chemical structure of the fouling layers as reported by Suci et al. (2001). Unfortunately, it does not provide data concerning biofilm thickness but it can differentiate between different types of fouling that took place on the same examined membrane (Schmid et al. 2003). Nuclear magnetic resonance (NMR) microscopy is employed to investigate industrial biofouling in reverse osmosis (RO) membranes. NMR microscopy gives quantitative measurements of RO membrane biofouling and the expected influence on mass transport and hydrodynamics in RO membranes. In a study performed by Cui et al. (2011), surface-enhanced Raman spectroscopy (SERS) facilitated the examination of fouling proteins on polyvinylidene fluoride (PDVF) membranes.

3.6 Characterization of EPS In order to be able to characterize the produced EPS, EPS must be well extracted from the biofilm and its components must be identified and quantified (Nguyen et al. 2012). A perfect EPS extraction method should not modify its properties or cause lysis of the viable cells (Nielsen and Jahn 1999). Techniques employed for EPS extraction are

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categorized into three categories: chemical and physical methods, and a combination of both methods. The traditional physical methods involve heating (Morgan et al. 1990), ion exchange (Frolund et al. 1996), centrifugation, dialysis, sonication and filtration (Comte et al. 2006). Chemical methods involve the employment of chemical agents for instance, formaldehyde, ethylenediamine tetraacetic acid (EDTA), ethanol and sodium hydroxide (Liu and Fang 2002). Comte et al. (2006) demonstrated that the yield of EPS from the physical methods is usually less than those produced by the chemical methods. Even though, the physically extracted EPS are less contaminated and free from reagents that cause less cell lysis. The combination of both methods is more efficient as a high yield can be attained (Nielsen and Jahn 1999). Other techniques include; FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), high performance size exclusion chromatography, high performance liquid chromatography (HPLC), gas chromatography-mass spectrometry (GC-MS), deoxyribonucleic acid (DNA) assays and proton nuclear magnetic resonance (NMR) can be also employed for the characterization of the secreted microbial EPS (Nguyen et al. 2012).

3.7 Multiple Roles of Biofilms in Microbial Corrosion The roles of biofilms in microbial corrosion depend mostly on their composition, structure and their physiological activities. All of these factors are based upon a combination of intrinsic factors such as the genotype of the attached cells and extrinsic factors that include the surrounding physico-chemical environment (Sutherland 2001). Generally, biofilms influence corrosion by accelerating its rate (Geesey and Bryers 2000). Biofilms can accelerate metal corrosion throughout the following criteria: • The creation of oxygen concentration or differential aeration cells through a patchy distribution of microbial colonies and their products. As a result, localized electrochemical corrosion cells are established (Hamilton 1995). An oxygen concentration gradient is usually created in the surface due to the consumption of oxygen by aerobes. Accordingly, deeper layers of the biofilm are turned into anaerobic niches, which serve as perfect habitats for the growth of sulphate reducing bacteria (SRB) (Flemming and Schaule 1996). • EPS, which constitute the main mass of biofilm underpin the maintenance of such heterogeneities and microenvironments. EPS also influence corrosion more directly by metal binding and/or retention of corrosion products. This process is referred to as the “chelation of metal ions” (Hamilton 2000). • Alteration of the corrosion inhibitor’s stability at the metal surface (Hamilton 1995). • Modification of the medium conductivity (Hamilton 1995). • Inhibition of biocide action (Hamilton 1995). • The aerobic and facultative heterotrophic species in the surface regions of the biofilm can create nutrient and physicochemical conditions necessary for the

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growth and activity of SRB at the base of the biofilm, where they can initiate microbial corrosion (Videla 1994). In order to mitigate reservoir souring in oil and gas facilities, nitrate injection can be applied as it endorses the growth of nitrate reducing bacteria (NRB) which can in turn inhibit the growth of SRB (Gieg et al. 2011). But unfortunately, NRB may be corrosive themselves if the injected nitrate is not totally utilized in the reservoir. Hence, both NRB and nitrate can eventually end up in oil transportation pipelines. Thus, this may lead to microbial corrosion attacks by NRB as iron oxidation along with nitrate reduction provides energy for respiration of NRB (Ghafari et al. 2008). Nijburg et al. (1998) reported that Bacillus licheniformis is a facultative anaerobe which has the ability to respire nitrate. Moreover, according to López et al. (2006) B. licheniformis is an abundant microbe that is extensively existed in oil field biofilms. In a study introduced by Xu et al. (2013), behavior of B. licheniformis as a nitrate reducer was investigated. It was found that B. licheniformis was a nitrate reducer corrosive strain to C1018 carbon steel under anoxic conditions. The recorded weight losses after 3 and 7 days were 0.24 and 0.89 mg/cm2 , respectively. Moreover, the measured pit depths in the immersed coupons were 13.5 μm and 14.5 μm for 3 and 7 days, respectively. The resultant data revealed that B. licheniformis caused aggressive pitting corrosion under anaerobic conditions. Cetin and Aksu (2013) investigated the corrosion behavior of low steel alloy in presence of Desulfovibrio caledoniensis. D. caledoniensis was isolated from an oilwater mixture that was sampled from production well in Batman, Turkey. The isolated strain was identified via ABI 3100 genetic analyzer (REFGEN laboratory, METU Ankara, Turkey). The SRB isolates utilized formate, butyrate or fumarate as carbon sources in presence of sulfate. D. caledoniensis is a Gram negative and non-spore forming bacterium. The cells are rounded rods, with an average size of 0.5 ± 0.1 μm to 3 ± 0.4 μm. Two layers of corrosion products with different composition were produced after incubating the isolated SRB strain for 1 month with the steel coupon. SEM micrographs of the steel coupon incubated with a culture medium containing D. caledoniensis confirmed the formation of corrosion products and distribution of cells throughout the coupon. Energy dispersive X-ray spectrum (EDS) analysis demonstrated that the upper layer was mainly composed of Fe (64.7%) and P (30.8%), in addition to other elements. While, the bottom layer was composed of Fe, P and S with a percentage of 86.1, 5.2 and 3.8%, respectively. Thus, there was an increase in the Fe and S contents and low P content at the bottom layer. Assessment of the influence of the isolated strain to the low steel alloy was demonstrated by electrochemical impedance spectroscopy (EIS) as well as Tafel exploration technique. The Tafel plots revealed a cathodic shift of corrosion potential and EIS measurements revealed the increase in corrosion rates with increasing the time of incubation. S32654 super austenitic stainless steel (SASS) is strongly resistant to corrosion. In a study conducted by Li et al. (2015), the influence of corrosive marine bacterium Pseudomonas aeruginosa was investigated in deep. The corrosion behavior was studied using electrochemical measurements such as linear polarization resistance (LPR) and EIS. It was found that corrosion rate of S325654 SASS was speeded up

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in presence of P. aeruginosa biofilm as demonstrated by the negative shift in the open circuit potential (EOCP ). Additionally, a decrease in polarization resistance and an increase in corrosion current density were observed in culture medium. The pit depth which resulted from the presence of P. aeruginosa reached 2.83 μm after 14 days of incubation. This was much deeper than that of the control which reached only 1.33 μm. XPS was used to detect the released corrosion products from the coupon upper surface layer. It showed the presence of certain elements including C, Mo, N, O, Cr, Na, Ni, Fe and Cl. The presence of Na and Cl elements on the surface was due to the use of seawater as a simulated culture medium. It was likely that the P. aeruginosa biofilm catalyzed the formation of CrO3 , which was detrimental to the passive film, resulting in microbial pitting corrosion. Moreover, high resolution Cr core-level spectrum was noticed and it was attributed to the presence of Cr, Cr2 O3 and CrO3 . Acceleration of corrosion was related to the formation of CrO3 which had a damaging effect on the passive film. Corrosion of X80 pipeline steel caused by Bacillus cereus was investigated by Wan et al. (2017) via electrochemical and surface techniques. Scanning electron microscopy assured the presence and adherence of a number of B. cereus cells to X80 steel. EIS showed that B. cereus had the capability to accelerate corrosion of X80 steel. Besides, surface analysis revealed that B. cereus could accelerate pitting corrosion in X80 steel. The deepest pit reached nearly 11.23 μm. U-shaped cracks and holes occurred after 60 days of immersion in presence of B. cereus. XPS data showed the presence of NH4+ on X80 steel surface. Thus, it was interpreted that B. cereus is a type of nitrate-reducing bacteria and that a nitrate reduction mechanism was responsible for X80 steel microbial corrosion. It is generally recognizable that the thickness and structure of SRB biofilm differs greatly within the different nutritional environments. In real fields, certain stress conditions may hinder the availability of consumable organics which are required for SRB metabolism. One of the most important reasons is the limited diffusion of organics from the bulk-fluid phase to the inside of biofilm (Matin et al. 1989). Nevertheless, as previously studied in many reports such as the ones introduced by Chen et al. (2015) and Xu et al. (2016a, b), SRB have the ability to survive on steel when there is deficiency in carbon sources. This takes place as elemental iron serve as an energy source, but this leads to pitting corrosion. Liu et al. (2018) investigated the effect of SRB biofilms on X80 pipeline steel in simulated CO2 -saturated oil field produced water. In the simulated oil field produced water, SRB cells were able to survive and grew. Growth of planktonic and sessile cells was noticed and reached counts of approximately 106 cells/ml and 106 cells/cm2 for planktonic and sessile cells, respectively after 21 days of immersion. Electrochemical measurements such as potentiodynamic polarization and EIS confirmed the increase in corrosion rate by SRB biofilm. XPS revealed the presence of EPS elements. SEM revealed the overlapping of the biofilm on X80 pipeline steel and the presence of corrosion products were detected by EDS. Li et al. (2019) studied the corrosion behavior of Brevibacterium halotolerans on X80 pipeline steel. X-ray diffraction (XRD) and XPS analysis revealed the existence of FeOOH, Fe2 O3 and FeSO4 as corrosion products produced by B. halotolerans. Electrochemical analysis (OCP, EIS and polarization curves) and measurements of pitting depths supported the adverse effect of B.

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halotolerans in accelerating pitting corrosion of X80 steel. Pitting corrosion might have been occurred because of the elemental oxidation of iron in X80 to get more electrons which are required for nitrate reduction underneath the biofilm. Moradi and coworkers (2019) presented an exciting study concerning the double effect of Psudoalteromonas piscicida biofilm on microbial corrosion of A36 CS. This was investigated in two different hydrodynamic circumstances; orbital shaking incubator and flat plate bioreactor. After two weeks of exposing A36 CS surface to P. piscicida biofilm, it was corroded in flat plate bioreactor and a large number of wide and deep cracks was noticed on the surface after biofilm removal. Contrary, the corrosion rate of A36 CS was reduced to its lowest value when A36 CS was exposed to P. piscicida in artificial seawater under the orbital shaking condition for 2 weeks. P. piscicida had an inhibitory influence after one week of exposure as evaluated by the electrochemical results. Additionally, the impedance value increased because of formation of protective oxide layer. Yet, when the biofilm was placed in the flat plate bioreactor it became heterogeneous. Decrease in corrosion resistance of A36 CS occurred because of the diffusion of Cl− ions. FESEM was employed to differentiate between the two studied cases. In the orbital shaking condition, homogenous biofilm with multilayers of bacteria cells covered the coupon surface after 21 days of incubation. While, in the flat plate bioreactor, mushroom-like biofilms were formed with different sizes and were distributed heterogeneously on the surface. Also, FTIR spectra showed different biofilm compositions in both hydrodynamic conditions. Eventually, the hydrodynamic conditions can significantly alter the biofilm physical nature, affect biofilm gene regulation, and result in diverse types of corrosion behavior. This study highlights the capability to control unfavorable biofilm structures by altering the hydrodynamic conditions.

3.8 Prevention of Biofilm Formation Because of the presence of many problems resulting from the microbial interaction with surface such as biofouling, disruption and efficiency loss, a number of strategies have been developed to avoid the bacterial attachment to surfaces and prevent the upcoming consequences of biofilm formation (Elbourne et al. 2019a, b). Among these strategies is the use of nanomaterials to prevent initial biofilm formation. Hasan et al. (2013) differentiated between two important terms i.e. anti-biofouling and bactericidal effect. Anti-biofouling usually refers to “the capability of a surface to minimize or repel the initial attachment of microbes” while the bactericidal surfaces refer to “the surfaces that possess a capacity to inactivate or kill microbial cells that comes in contact with the surface”. Conventionally, oxidizing and non-oxidizing biocides have been extensively used to inhibit and/or mitigate biocorrosion, for instance; bromine, chlorine, ozone, formaldehyde, glutaraldehyde and quaternary ammonium compounds (Guo et al. 2018). Yet, injecting these biocides has been found to be far from satisfactory. According to Costerton (1987), this is due to the fact that biocorrosion commonly

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occurs beneath the biofilms and sessile microorganisms within biofilms are extremely resistant to biocides than planktonic populations. Meanwhile, it is very predictable that microorganisms become more resistant by usage of a single biocide for long terms (Guo et al. 2018). Accordingly, this results in utilization of higher concentrations from the used biocide. Studies conducted by Franklin et al. (1991) and Neville et al. (1998) demonstrated that in some cases, high doses of biocides might lead to initiation and propagation of localized corrosion. Besides, negative impacts on the surrounding environments and upon human health might take place because of biocide inherent toxicity. They are also responsible for mortalities in non-targeted organisms. Another protection method that has been used is the cathodic protection. Cathodic protection revealed to effectively retard microbial corrosion of stainless steel induced by aerobic bacteria (Guezennec 1994). Whereas, it shows no influence on the activity of anaerobic bacteria like SRB. Besides, using biocides and cathodic protection are somehow costly for many industries. Henceforth, providing barriers as protective coatings between environment and various substrates are probably the best solution adapted by many industries to defeat microbial corrosion. Koch et al. (2002) ascribed that almost 89.5% of total costs is dedicated to the usage of protective coatings. Thereby, protective coatings have been extensively considered as an important methodology to protect constructions from biocorrosion since the 1980s, when the damage because of biocorrosion began to be extremely recognized. According to the previously mentioned steps of biofilm formation, possible anti-biofilm strategies may involve (i) inhibition of microbial adhesion and colonization to surfaces; (ii) interfering with the quorum signaling molecules that modulate the development of biofilms; and (iii) finally biofilm disaggregation (Francolini and Donelli 2010). Additionally, designing materials with anti-biofilm effect can take place either by physicochemical alteration of the material surface (anti-adhesive surface) or by using biocidal agents which bind to the material surface or released into the surrounding environment.

3.8.1 Incorporation of Antimicrobial Nanomaterials Nanomaterials such as nanoparticles (NPs) (Hajipour et al. 2012, Omran et al. 2018a, b), nano-rods (Kuo et al. 2009), nano-cubes (Alshareef et al. 2017), nano-dots (Aftab et al. 2019) and two-dimensional materials (Zhang et al. 2016; Sun et al. 2018) exert an outstanding antimicrobial potential against a broad spectrum of pathogenic bacteria (Omran et al. 2018a) and fungi (Anghel et al. 2013; Arciniegas-Grijalba et al. 2017). Several studies have been performed to highlight the role of nanomaterials that have biocidal activity which in turn can eradicate biofilm formation including; iron (III) oxide (Anghel et al. 2013), zinc oxide (Mahamunia et al. 2019), silver NPs (Omran et al. 2018b), copper NPs (Alshareef et al. 2017) and copper oxide NPs (Omran et al. 2019), calcium oxide NPs and titanium dioxide NPs (Dizaj et al. 2014). In case of biomedical implanted devices, nanomaterials are usually incorporated within a matrix composed of polymers or any immobilized surfaces to guarantee the

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antimicrobial effect to prevent biofilm formation. The main factor behind the high biocidal activity of nanomaterials is the large surface area to volume ratio. Yu et al. (2014) incorporated AgNPs into porous silica by using ethanol where the solvent (3-aminopropyl)-triethoxysilane (APTES) acted as a modifying agent, and ethylene glycol acted as the reducing agent. Qureshi et al. (2013) reported a method of a layer-by-layer coating made up of AgNPs on titanium orthopedic implant via APTES crosslinking with a layer of silane to form a self-assembled layer. Duraibabu et al. (2014) formulated a nanostructured hybrid coating formulation for the mitigation of mild steel corrosion and microbial prevention. The formulation was composed of tetra functional epoxy resin reinforced with ZnO NPs.

3.8.2 Polymer Coatings According to Elbourne et al. (2019a, b), polymers have been tested as antimicrobial surfaces. Such surface polymers act as either physical barrier which minimize microbial attachment, or exterminate pathogenic microorganisms during surface adsorption (Song and Jang 2014). This can be done via covalent and non-covalent tethering which occurs via atom radical transfer polymerization (ARTP) (Hasan et al. 2013). Commonly used polymers as biofilm formation inhibitors include chitosan (Goldberg et al. 1990), poly (β-lactam) (Tew et al. 2002), N-alkylated poly (ethyleneimines) (Lin et al. 2003), polyacrylate derivatives (Kenawy et al. 2007) and poly (vinyl-Nhexylpyridinium) (Yang et al. 2011). Such polymers cause disruption to microbial cells leading to cell death. It was found that there is a proportional correlation between biocidal activity of these polymers and their molecular interactions (Lin et al. 2009). Unluckily, some polymers lack biocompatibility thus limiting them in vivo application (Cheng et al. 2008). Therefore, different studies have been devoted for the synthesis of biocompatible polymer coatings (Li et al. 2011; Nederberg et al. 2011).

3.8.3 Naturally Occurring Antibacterial Surfaces and Their Biomimetic Counterparts Naturally occurring biomimetic antimicrobial nanostructured surfaces facilitates bacterial cells’ inactivation during their adhesion to surfaces by inducing membrane rupture of bacterial cells (Elbourne et al. 2017). Ivanova et al. (2012) reported the first study concerning the construction of surfaces for mechanical inactivation of P. aeruginosa ATCC 9027 cells. Theories presented by Pogodin et al. (2013) and Xue et al. (2015) supported the idea of presence of a mechano-responsive mechanism of cell rupture in which bacterial cell membrane was distorted and eventually ruptured. Several naturally occurring substances possess antibacterial surface architecture such as nano-spikes, -pillars, -cones, -wires and -spinules.

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3.8.4 Anti-adhesive Surfaces The primary initial adhesion of microorganisms to abiotic materials is the key factor for biofilm formation (Mao et al. 2011). This initial adhesion is influenced by different factors, some of these factors are concerned with the colonized surface such as surface free energy, surface electrostatic charge, roughness, hydrophobicity and other chemical properties (Chen et al. 2011; Villanueva et al. 2014). Generally, adhesion of microorganisms readily occurs when the surface is rough, hydrophobic and coated with conditioning films (Simões et al. 2010). While, the other factors which would affect surface adhesion are related to cell surface properties for instance the presence of extracellular appendages, cell to cell communication interactions in addition to secretion EPS (Mebert et al. 2016). Eventually, certain environmental factors can influence biofilm formation such as pH, nutrient availability and ionic forces (Garrett et al. 2008). Typically, bacterial adhesion to surfaces is studied via surface free energy, charge and wettability of the surface under study (Zhang et al. 2013).

3.8.4.1

Surface Free Energy

Surface free energy refers to “the excess of energy in surface atoms” (Dingreville et al. 2005). According to Callow and Fletcher (1994), surface free energy is “the energy that results from surface atoms, molecules and surface groups that are able to react with other atoms, molecules and groups, respectively”. There is a difference between the atoms of bulk materials and the atoms at a free surface. The latter mediates different amounts of energy than that of a bulk material. Measurement of the intermolecular or interfacial attractive forces can be tracked by the surface free energy (Zhao et al. 2005). Additionally, it is an indication to the degree to which water can be adsorbed on a surface. Two important terms are usually used to describe surfaces namely hydrophobicity (low wettability) and hydrophilicity (high wettability). Generally, it is found that hydrophobicity increases with a decrease in surface free energy (Callow and Fletcher 1994). Surface free energy greatly influences bacterial adhesion (Mebert et al. 2016). In a study performed by Baier and his colleague, it was proved that there is an optimum range of surface free energy for which adhesion is minimized. Baier and Meyer suggested the optimum value of surface free energy which aids in biofouling inhibtion is almost 2030 mJ/m2 (Baier and Meyer 1992). However, the main question is whether most organisms adhere better on hydrophobic or hydrophilic surfaces, yet it remains under investigation. Many research articles suggested that materials with low surface free energy are the ones that are capable of preventing bacterial adhesion. Pereni et al. (2006) concluded that substrates with low surface free energy prevented bacterial adhesion. Tsibouklis et al. (1999) prepared coatings from poly (methyl propenoxy fluoro alkyl siloxane) and poly (perfluoroacrylate) in glass slides with low surface energy and rigidity. It was observed that the coatings had the capacity to mitigate bacterial colonization on surfaces. It was suggested that surfaces with low

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surface free energy were more resistant to biofilm formation and were easy to clean due to the weak binding at the substratum liquid interface (Baier 1980).

3.8.4.2

Super Hydrophobic Surfaces

As reported by Zhang et al. (2013), super hydrophobicity facilitates the bacterial removal via minimizing the adhesion forces between them. Interestingly, super hydrophobic surface is somehow similar to the natural phenomenon of the lotusleaf or self-cleaning effect. Generally, water droplets on a lotus leaf can easily roll off when it is sided, thereby permitting the self-cleaning effect. On the other hand, in the rose petal effect, a high water contact angle is responsible for the super hydrophobicity of the surface and it generates a strong adhesion between the leaves and the water droplets (Nosonovsky and Bhushan 2012). Consequently, two main criteria determine the antimicrobial surface and they involve the presence of a very high water contact angle and a very low roll-off angle (Marmur 2004). Wettability is an important property of any material; it demonstrates information about chemical structure of the material as well as its surface topography (Genzer and Efimenko 2006). Material wettability is largely dependent on material structure. In reality, super hydrophobic surfaces cannot be tailored by surface chemistry alone (Lafuma and Quere 2011). Two unique hypotheses were proposed to expect the macroscopic contact angle of an aqueous droplet on a rough surface. These hypotheses are the Wenzel module Wenzel (1936) and the Cassie Baxter model (Cassie and Baxter 1944). The Wenzel model claims that the aqueous solution of a liquid wets the whole rough surface. This model is mainly dependent on the surface roughness and it is mainly dealing with sticky surfaces. Moreover, the surface properties increase with the magnification of surface roughness; a hydrophilic surface will become more hydrophilic and the hydrophobic surface will become more hydrophobic. This model does not involve the presence of air under a water droplet so it cannot be applied in the lotus leaf type surfaces (Crick et al. 2011). Contrary, according to the Cassie Baxter model the droplet incompletely wets the rough surface because of the trapped air within the microstructures. The model is dependent on the contact between the solid and liquid fraction. Thus, this module is more preferable to describe the interactions at the liquid solid interface in a slippery lotus effect (Crick et al. 2011). Crick et al. (2011) assumed that super hydrophobic surfaces applying Cassie Baxter wetting mechanism have the potential to prevent the attachment between bacterial cells on surfaces. The contact angle is measured via goniometer employing the sessile drop technique. This technique with the help of a camera and a software analysis measures the contact angle which is obtained from the image of a droplet deposited over a solid surface (Miller et al. 1996).

3.8 Prevention of Biofilm Formation

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Electrostatic Charge

The classical theory of colloid stability namely Derjaguin Landau Verwey Overbeek clarifies the process microbial adhesion to different interfaces. It is a qualitative model, but it also can calculate the changes in adhesion free energy (Hermansson 1999). Generally, bacterial surface adapts to the changes in environmental conditions (Chen et al. 2011). Among the environmental alterations that would result in changes in cell surface hydrophobicity; increased substrate flux (Van Der Mei et al. 1995), different salinities (Van Loosdrecht et al. 1987) as well as variations in environment pH (Villanueva et al. 2014). Microbial cell surfaces are usually negatively charged because of the presence of carboxylates, phosphates, etc. in their membranes (Chen et al. 2011). In order to get information about electrostatic interactions; it is essential to determine both of the point of zero charge (PZC) and the isoelectric point (IEP) (Claessens et al. 2006). Van der Wal et al. (1997) reported differences between PZC and IEP measurements in bacterial cell walls. Furthermore, Gelabert et al. (2004) demonstrated that PZC of diatom cells was several pH units greater than their IEP. Besides, many factors such as cell age and growth conditions would result in alterations in bacterial IEP (Harden and Harris 1953) and PZC (Haas 2004). Obviously, electrostatic interactions between the negatively charged microbial cell surface and another negatively charged surface is expected to be repulsive and diminish bacterial adhesion (Harimawan et al. 2011). Chen et al. (2010) demonstrated that zeolite coatings containing aluminum increased the density of charged groups on material surface, resulting in alteration in both the tested surface charge and hydrophobicity. It was found that adhesion of marine species Halomonas pacifica onto the zeolite coated metal surfaces in flowing environments resulted in reducing their initial attachment and thereby reduced biofilm formation.

3.8.4.4

Roughness

The first report made on the relation between surface roughness and bacterial adhesion was introduced in the early of 1980s as revealed by Jendresen et al. (1981). Roughness has been usually measured by using SEM however; this technique has certain limitations concerning its resolution as it lacks a precise determination of an object height (Bonetto et al. 2006). Contrary, AFM is much preferred as it can reach sub nanometric resolution (Miller et al. 1996). Moreover, it has the ability to quantify the adhesion forces between both bacteria and abiotic surfaces with a high precision and resolution (Razatos et al. 1998). It is obvious that surface roughness affects bacterial adhesion (Rodriguez et al. 2008). Generally, bacteria are able to attach themselves easily to pits and crevices where they can be shielded against the undesirable environmental conditions and shear forces. Different factors affect the bacterial attachment to rough surfaces (Scheuerman et al. 1998). Several studies investigated the role of surface roughness on bacterial attachment. For instance, adhesion of S. aureus on rough stainless steel surface was higher compared with smooth surfaces (Mebert et al. 2016). Additionally, Hou et al. (2011) reported that

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E. coli preferred the attachment and biofilm formation rough surfaces. Contrary, some authors revealed that influence of roughness was negligible as reported by Woodling and Moraru (2005) who demonstrated that bacteria can also colonize electropolished stainless steel surfaces. Moreover, the adherence of Pseudomonas sp., Candida lipolytica, and Listeria monocytogenes to stainless steel surface was not influenced by surface roughness (Hilbert et al. 2003). Other researchers such as Cao and coworkers (2006) studied the bacterial adhesion in modified silicone in addition to silanes such as hyaluronan, heparin, fluoroalkylsilane and self-assembled octadecyltrichlorosilane (Cao et al. 2006). Authors concluded that roughness might exert minor effect on bacterial adhesion. Thus, strong arguments on the effect of surface roughness and its relation to bacterial attachment still remains. Different fabrication techniques have been proposed to synthesize random nano rough surfaces including; chemical etching, reactive ion etching, controlled polymer coatings and anodic oxidation (Ivanova et al. 2013). Such techniques have been used to identify whether surface roughness influence bacterial adhesion or not. Nano phase materials possess high surface area and increased number of surface grain boundaries. Nano phase materials have more influence on cellular responses than the other conventional materials. Matching with the previous findings, the number of attached bacteria that belong to different taxa i.e. E. coli, S. aureus and P. aeruginosa considerably increased onto glass surfaces with reduced nanoscale roughness (i.e. decreasing surface roughness was attained by chemical etching) (Mitik-Dineva et al. 2008a, b, 2009). Additionally, the incorporation of nitrogen or silicon diamonds like carbon films reduced surface roughness. It was found that surface roughness was remarkably reduced with the increase in nitrogen content in diamond like carbon films. Liu et al (2008) demonstrated that adhesion of P. aeruginosa was minimized with the decrease in surface roughness. Nano rough titanium surfaces prepared via electron beam evaporation resulted in decreasing the attachment of Staphylococcus epidermidis, S. aureus and P. aeruginosa when compared with conventional (nano smooth) titanium with the same surface chemistry structure (Puckett et al. 2010). Moreover, in a study conducted by Durmus et al. (2012) it was observed that attachment of S. aureus to nano rough polyvinylchloride (PVC) surfaces prepared from lipase was less than the conventional PVC surfaces. Recent studies performed by Rizzello et al. (2011, 2012) revealed that cells of E. coli could not adhere to gold nano rough surfaces prepared by wet chemistry. As mentioned earlier, surface roughness is affected by wettability. Nano rough hydrophobic surfaces were found to delay bacterial adhesion when compared with hydrophilic substrates. For instance, attachment of P. aeruginosa on ethanol treated PVC was found to be delayed in comparison with the unmodified PVC (Loo et al. 2012).

3.9 Conclusions In oil and gas facilities, biofilms are established as a consquence of metal immersion in aqueous environments. Generally, the first stage in biofilm establishment takes

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place by the formation of a thin conditioning film. This film is nearly 20–80 nm thick and is composed of the deposited inorganic ions and highly reactive molecular mass organic compounds. This initial conditioning film possesses the potential to amend the electrostatic charges and wettability of the metal surface which facilitates its further colonization by biofilm forming microorganisms. Within a very short time i.e. minutes to several hours, microbial growth takes place and extracellular polymeric substances are secreted which results in biofilm development. The developed biofilm is a dynamic system. Microorganisms affect corrosion by changing the electrochemical parameters at the metal/solution interface. Such alterations result in different impacts like the induction of localized corrosion. Traditional strategies for biofilm prevention are chemically-based; however, the recent understanding of the fouling mechanisms enabled the usage of biotechnological approaches as effective alternatives for biofouling control.

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Chapter 4

Corrosion and Biofouling Mitigation Using Nanotechnology

Abstract Almost every oil and gas facilities and underwater equipment infrastructures are prone to the overwhelming effects of corrosion and biofouling. Nonetheless, the achieved advancement in the science of corrosion and biofouling control, both problems continue to pose major concerns to several facilities worldwide. Nanotechnology is an immensely growing field due to its miscellaneous applications in our daily life. Nanotechnology have revolutionized the scientific world by the creation of new techniques products and methodologies. Nano-scaled materials possess extraordinary features than their micro-scaled counterparts. Henceforth, widespread efforts are being directed towards promotion of the effective usage of nanomaterials to control/mitigate corrosion and biofouling. This chapter highlights a spot on the history of the science of nanotechnology, the different types of produced nanomaterials and the different synthetic approaches. Moreover, this chapter emphasizes the role played by nanomaterials to protect oil and gas constructions from corrosion and biofouling. Studies revealing investigations upon the employment of different nanomaterials in paints, coatings and as corrosion inhibitors will be reviewed in details. Keywords Biofouling mitigation · Corrosion control · Nanotechnology · Nanomaterials · Petroleum facilities

4.1 Introduction History and origin of nanotechnology began with Richard Feynman’s historic lecture in 1959 at the California Institute of Technology entitled “there is plenty of room at the bottom” in which he outlined the idea of building objects from the bottom-up. The term nanotechnology was first introduced by Professor Norio Taniguchi in Tokyo Science University (Khandel and Vishwavidyalaya 2016; El-Gendy and Omran 2019). This brilliant suggestion did not gain much attraction until the mid-1980s, when Eric Drexler published “Engines of Creation: The Comming Era of Nanotechnology” in 1986 which aided in understanding the potentiality of nanotechnology

© Springer Nature Switzerland AG 2020 B. A. Omran and M. O. Abdel-Salam, A New Era for Microbial Corrosion Mitigation Using Nanotechnology, Advances in Material Research and Technology, https://doi.org/10.1007/978-3-030-49532-9_4

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(Morais et al. 2014). Nanotechnology has become one of the most important technologies in all areas of science particularly modern materials science (Visweswara and Hua 2015). The term nano originates from the Greek word “nanos” which means “dwarf” in Greek (El-Gendy and Omran 2019). Nanotechnology is defined as “the creation and exploitation of materials which exist at the nanoscale level up to 100 nm in size” (Vasile 2019). Nanotechnology manipulates materials whose structures possess specific innovative and enhanced chemical, biological and physical functionalities. Nanotechnology has undergone a tremendous rise in the last few decades (Mo et al. 2014). It is a multidisciplinary scientific branch combining physics, chemistry, biology, electrical engineering, biophysics and material science altogether. According to the European Commission (EC) in October 2011, nanomaterials have been defined as “natural, incidental or manufactured particles either in an unbound state or as aggregations in which dimensions are in the size range of 1–100 nm” (EC 2011). Nanoparticles are viewed as the fundamental building blocks of nanotechnology. They are atomic or molecular aggregates (Yadav et al. 2017). They exhibit new or improved properties. The unique properties of nanoscale materials have given rise to tremendous research activities directed towards NPs fabrication, characterization and applications (Schröfel et al. 2014). NPs have characteristic physical, chemical, electronic, electrical, mechanical, magnetic, thermal, dielectric, optical and biological properties (Zhou et al. 2015). The large surface to volume ratio of NPs compared to their bulk materials makes them attractive candidates for many applications (Palomo and Filice 2016). A huge investment in nanotechnology is obviously observed through the increased interest in nanotechnology-related research and development (R&D). According to the National Nanotechnology Initiative (NNI), NNI has alone received approximately $27 billion in 2018 as a proposed budget for the year 2019 (National Nanotechnology Initiative 2018). Additionally, Massachusetts Institute of Technology (MIT) has invested a huge budget of about $350 million for the state-of-the-art nanoscale research centre called “MIT. nano” (Chandler 2014). Another example is NanoMech, which is a leading company in nano-manufacturing, has received approximately $10 million investments from Saudi Aramco Energy Ventures (SAEV). Vast research Revolution of nanotechnology had a major progress in oil and gas industries (Alsaba et al. 2020). This chapter introduces the state-of-the-art investigations concerned with corrosion inhibtion and biofouling mitigation using nanotechnogy-based methodolgies.

4.2 Metal Nanoparticles 4.2.1 Zero Valent Iron Nanoparticles (ZVI) NPs There are many forms of zero valent iron (ZVI) NPs including; uncapped, surfacemodified and bimetallic (ZVI) NPs (Hsueh et al. 2017). The advantages of using iron

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nanoparticles compared with micrometre scaled particles is their higher efficiency and reactivity in degradation reactions, due to high surface area, mobility and filtration efficiency (Wang et al. 2016). Being nano-sized, particles remain in suspensions for long time, thereby facilitating their various applications (Zhou et al. 2015). Iron nanoparticles have received considerable attention for their potential application in groundwater treatment and site remediation. Recent studies demonstrated the effect of (ZVI) NPs in the remediation of halogenated organic contaminants and heavy metals (Bhatti et al. 2020). This is mainly because (ZVI) NPs possess a large active surface area which serve as strong and effective reductants.

4.2.2 Gold Nanoparticles (AuNPs) Gold nanoparticles (AuNPs) are among the most important metallic NPs. AuNPs have become the focus of intensive research. The surface of AuNPs is notably appropriate to function as a stable and non-toxic platform on which therapeutic compounds can be delivered (Rajan et al. 2017). As a result, AuNPs have wide spread applications in different disciplines such as catalysis, biochemical sensors, photothermal therapy, drug delivery and tissue/tumor imaging (Rajan et al. 2017; El-Gendy and Omran 2019). AuNPs can detect deoxyribonucleic acid (DNA) with high sensitivity and selectivity (Kumar et al. 2011). Gold nano-rods are employed to detect cancer stem cells and they are beneficial for cancer diagnosis and in identification of different classes of bacteria (Tomar and Garg 2013). Antibacterial activity of AuNPs is extensively reported against both Gram negative bacteria (Pseudomonas aeruginosa and Escherichia coli) and Gram positive bacteria (Staphylococcus aureus) (Amini et al. 2018). The antimicrobial potential of AuNPs is strongly linked to the particle size as high antimicrobial activity is achieved when the particle size is much reduced as reported by Xie et al. (2018). Xie and colleagues observed the high antibacterial effect of Au nanoclusters on both Gram positive and Gram negative bacteria when the size reached 2 nm. The small size enabled AuNPs to interact better and to promote their uptake by bacterial cells. Moreover, the conjugation of AuNPs with antibiotics such as streptomycin, ampicillin and kanamycin resulted in a marvellous bactericidal activity compared with antibiotics alone. This was evaluated on the following strains E. coli DH5α, Micrococcus luteus and S. aureus as demonstrated by Gupta et al. (2019). Silvero et al. (2018) reported a single-step reaction for the preparation of kanamycin-capped AuNPs (Kan-AuNPs). The prepared KanAuNPs expressed a high toxicity towards Vero 76 cell line while the antibacterial assay showed broad spectrum activity of Kan-AuNPs against Kanamycin resistant bacteria such as Enterobacter aerogenes (ATCC 13048), Staphylococcus epidermidis (ATCC 12228), Streptococcus bovis (ATCC 9809), Pseudomonas aeruginosa PA01 and P. aeruginosa UNC-D (Baptista et al. 2018). Furthermore, according to Ahmad et al. (2013), AuNPs exhibited admirable size dependent anti-fungal activity against Candida isolates particularly for 7 nm sized AuNPs.

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4.2.3 Silver Nanoparticles (AgNPs) Many centuries ago, silver was used as an antiseptic agent (Lansdown 2006), particularly in drinking water disinfection before being consumed (El-Gendy and Omran 2019). Silver-based salts were used to disinfect drinking water prior to consumption (Chou et al. 2005). The ability of silver ions to bind to cellular components is the reason behind its lethal effect on microbial cells (Kim et al. 2007). Yet, some bacteria managed to resist the antimicrobial effect of silver ions. AgNPs are undoubtedly the most widely used NPs among all as they are being used in textile industries, water treatment, sunscreen lotions (Rai et al. 2009), biomedicine (prosthetics bone, and surgical instruments), fashion (clothes and footwear production), beauty industry (conditioners, cosmetics and toothpaste) and as antimicrobial agents (for the treatment of wounds and infections) (Durán et al. 2016). AgNPs are one of the most promising products in industries applying nanotechnology. The development of consistent processes for the synthesis of AgNPs is an important aspect of current nanotechnology research (Nasiriboroumand et al. 2018). AgNPs proved to be promising because of their high antimicrobial efficiency against bacteria, viruses, fungi and other eukaryotic microorganisms (Sadeghi et al. 2015; Golubeva et al. 2017; El-Gendy and Omran 2019). The biocidal activity of AgNPs exceeds that of the bulk silver, mainly because of the high surface area. According to Elbourne et al. (2019), AgNPs proved to express high antibacterial potential against a number of Gram positive bacteria (Staphylococcus aureus, Bacillus subtilis and Staphylococcus epidermidis) and Gram negative bacteria (Pseudomonas aeruginosa and Escherichia coli). Besides, AgNPs proved to be efficient against antibiotic-resistant bacterial strains such as vancomycin-resistant Staphylococcus aureus (VRSA), methicillinresistant Staphylococcus aureus (MRSA), ampicillin-resistant Escherichia coli and erythromycin-resistant Streptococcus pyogenes. Likewise, AgNPs were reported to possess antimicrobial action against some fungi. It was reported that AgNPs with a size of 12.5 nm inhibited the growth of both Candida spp. (Panácek et al. 2009) as well as Trichosporo nasahii (Xia et al. 2016). Yet, the overall activity towards fungi is less than that of bacterial strains (Omran et al. 2018; Elbourne et al. 2019). Several mechanisms have been suggested for the biocidal effect of AgNPs including; leaching of Ag+ ions which are commonly known to have toxic effects on bacterial cells. Furthermore, AgNPs binds to bacterial cell walls and leads to membrane leakage (Elbourne et al. 2019).

4.2.4 Cobalt Nanoparticles (CoNPs) Cobalt (Co)-based nanoparticles reside among the most promising nanomaterials for technological applications like; information storage devices, magnetic fluids and catalysts because of their good electro-activity and cost effectiveness (Chekin et al.

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2016). Cobalt nanoparticles (CoNPs) display a wide range of interesting size dependent structural, electrical, magnetic and catalytic properties. In particular, because of their large surface area, CoNPs possess high chemical reactivity which makes them suitable for catalysis (Balela 2008). Cobalt is also among the nanomaterials which exert an antimicrobial potential (Omran et al. 2019).

4.2.5 Copper Nanoparticles (CuNPs) Copper nanoparticles (CuNPs) are widely used in different commercial applications such as antimicrobial agent, catalyst, gas sensor, electronics, batteries, heat transfer fluids, etc. (Kasana et al. 2017).

4.3 Carbon Based Nanomaterials (NMs) Carbon based NMs are used in a variety of applications including; optics, electronics and biomedicine. Carbon based nanomaterials involve:

4.3.1 Fullerenes Fullerenes are molecules of 60 atoms of carbon (C60 ). Fullerenes and their derivatives are very insoluble in bio-fluids (Da Ros et al. 2001). Their insolubility limits their application in medical fields. However, they attracted the attention of many scientists for their role in inhibiting the human immunodeficiency virus (HIV), DNA photo cleavage, neuro-protection and apoptosis (Wilson et al. 2000).

4.3.2 Carbon Nanotubes (CNTs) Carbon nanotubes (CNTs) are single-walled (SWCNTs), double-walled (DWCNTs) and multi-walled (MWCNTs) particles. They are cylindrical-shaped carbon particles with a diameter of 1–10 nm with a length of a few micrometers (Fujisawa et al. 2016). They are flexible and have been used not only in the manufacturing industries (i.e. aircrafts, sports equipment, etc.) but also as electron field emitters, nanoprobes in atomic force microscopy and microelectrodes in electrochemical reactions. They are currently being investigated as potential hydrogen storage devices. CNTs have undoubtedly been one of the most promising nanomaterials for diverse applications in mechanics, electronics, materials science, sensors, energy harvesting devices and much more (Fujisawa et al. 2016).

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4.4 Metal Oxide Nanoparticles 4.4.1 Cobalt Oxide NPs Cobalt has two readily available oxidation states, Co2+ and Co3+ , meanwhile, cobalt oxides exist in three main structures. The simplest one is cobalt (II) oxide (CoO) which has a rock salt structure (Donaldson and Beyersmann 2000). The second main structure is cobalt (II, III) oxide (Co3 O4 ) (Patnaik 2002). While, the third composition is the cobalt (III) structure (Co2 O3 ) (Petitto et al. 2008). Cobalt oxide nanomaterials possess desirable optical, magnetic and electrochemical properties and have been used as super capacitors in energy storage devices, electro-chromic sensors and in lithium rechargeable batteries (Raman et al. 2016). Moreover, Co3 O4 NPs were employed as adsorbent for the removal of dyes from aqueous solutions (Shahabuddin et al. 2016). Cobalt oxide complexes were traditionally used as dying agents in ceramic and glass production; they adapt different colours depending on the metal ion binding together with the cobalt oxide.

4.4.2 Iron Oxide Nanoparticles (IO) NPs The three most common forms of iron oxides in nature are magnetite (Fe3 O4 ), maghematite (γ-Fe2 O3 ) and hematite (α-Fe2 O3 ) (Ali et al. 2017). Iron Oxide (IO) is a ferromagnetic material with high magnetic moment density and it is naturally present in high concentrations in the environment. (IO) NPs in the size range under 20 nm exhibit an inimitable form of magnetism, i.e. super magnetism (Nochehdehi et al. 2017). Due to their low toxicity, super-paramagnetic properties, high surface area to volume ratio, and simple separation methodology, magnetic iron oxide (Fe3 O4 and γ-Fe2 O3 ) NPs have attracted much attention particularly in biomedical applications for protein immobilization such as diagnostic magnetic resonance imaging (MRI), thermal therapy and drug delivery (Hasany et al. 2012).

4.4.3 Zinc Oxide Nanoparticles (ZnO NPs) Properties of zinc oxide (ZnO NPs) were widely investigated due to their potential applications in electronic devices (Laiho et al. 2008), chemical sensors and solar cells (Yong-Zhe et al. 2009), antimicrobials (Vijayakumar et al. 2018), water remediation technologies (Dimapilis et al. 2018) and also in sunscreens and cosmetics because of their ability to block ultraviolet rays (UV) (A/B) (Ju-Nam and Lead 2008). ZnO NPs are II–VI semiconductors with wide band gap energy nearly 3.3 eV, and high excitation energy of approximately 60 eV. Thus, it can tolerate large electric fields, high temperature and high power operations (Bai et al. 2015). These properties make

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it highly applicable in solar cells, photo catalysis and chemical sensors (Ul Haq et al. 2017). ZnO NPs proved to exhibit a wide range of antimicrobial potential against different microorganisms. According to Elbourne et al. (2019), 19.82 nm sized ZnO NPs were found to inhibit growth of methicillin sensitive S. aureus (MSSA), MRSA and methicillin-resistant S. epidermidis (MRSE) strains. Furthermore, ZnO NPs exhibited antimicrobial activity against food pathogenic bacteria such as Klebsiella pneumonia (Reddy et al. 2014), Listeria monocytogenes, Escherichia coli and Salmonella enteritidis (Jin et al. 2009). Antimicrobial action of ZnO NPs is suggested to take place either via disrupting the outer cell membrane thus affecting cell integrity or by prompting the generation of reactive oxygen species (ROS) which initiates cell oxidation and consequently cell death. ZnO NPs exhibited antimicrobial potential towards the pathogenic yeast C. albicans at a concentration of 0.1 mg/ml (Lipovsky et al. 2011). Besides, Erythricium salmonicolor was found to be inhibited by ZnO NPs as demonstrated by Arciniegas-Grijalba et al. (2017).

4.4.4 Titanium Oxide NPs (TiO2 NPs) Titanium dioxide (TiO2 ) NPs received much attention for application in the fields of photocatalysis and photocells due to its stability and low cost (Cruz-González et al. 2020). TiO2 NPs can also be used in energy storage devices (Wang et al. 2007), paints and coatings (Wildeson et al. 2008), cosmetics, skin products, sunscreens (Huang et al. 2006) and waste water treatment (Goutam et al. 2018).

4.4.5 Cerium Oxide Nanoparticles (CeO2 ) NPs CeO2 NPs have received much attention in nanotechnology due to their useful applications as catalysts, fuel cells and antioxidants in biological systems (Charbgoo et al. 2017). Recently, CeO2 NPs have emerged as fascinating materials in biological fields such as in bio-analysis, biomedicine and drug delivery (Kaittanis et al. 2012).

4.5 Nanoparticle Synthesis Approaches To date, there are numerous techniques for synthesizing nanomaterials. However, nanomaterials (NMs) can be generated through two main approaches, i.e., “topdown” and “bottom-up” approaches (Birnbaum and Pique 2011) as illustrated in Fig. 4.1.

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Top to bottom

Mechanical/ Ball milling Chemical etching Thermal/laser ablation Sputtering

Toxic Synthesis of NPs

Chemical/Electroch emical precipitation Vapor deposition Atomic/molecular condensation Sol-gel process Spray pyrolysis Laser pyrolysis Aerosol pyrolysis

Bottom to up

Green Synthesis Microbes (Bacteria, yeast, fungi, actinomycetes) Algae Plant extracts & fruit peels

Non toxic

Fig. 4.1 Different synthesis approaches of nanoparticles

4.5.1 Top-Down Approach It is the approach which starts with the material of interest and then undergoes size reduction via physical and chemical processes to produce NPs i.e. breaking down the bulk material into smaller and smaller dimensions. In the top-down approach, a block of a bulk material is whittled or sculptured to get the nano-sized particles. The topdown approaches involve attrition or milling, lithography, etc. The main disadvantage

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of the top-down approach is the design of imperfect surface structure. The produced nanomaterials by attrition have a somehow broad size distribution. Additionally, the prepared nanomaterials might contain some impurities (Balasooriya et al. 2017).

4.5.2 Bottom-Up Approach It is the approach in which NPs are built from atoms, molecules and smaller particles/monomers (Balasooriya et al. 2017). In the bottom-up approach, the individual atoms and molecules are placed or self-assembled precisely where they are needed. The molecular or atomic building blocks fit together to produce NPs. Bottom-up approaches are more favourable and popular in the synthesis of NPs and many preparation techniques of bottom-up approach have been developed. Decreasing the dimension of NPs has a pronounced effect on the physical properties that significantly differ from the bulk material. These physical properties are caused by their large surface atom, surface energy, spatial confinement and reduced imperfections. Usually, NPs are produced by either physical or chemical methodologies (Heera and Shanmugam 2015). Additionally, biological methods have been recently employed to avoid some disadvantages associated with the physical and chemical synthetic methods (Fig. 4.2). Figure 4.3 illustrates a schematic presentation for the synthesis methodologies of NPs.

4.6 Applications of Nanotechnology Science in Gas and Oil Industries With the increased attention towards nanomaterials and their novel use in different industries involving but not restricted to food, biomedical, electronics, materials, etc., the application of nanotechnology in oil and gas industries is a subject which attracts intense investigations by major oil companies (Alsaba et al. 2020). This is reflected through the enormous funds that are invested on the research and development, with respect to nanotechnology. Lately, nanotechnology has been extensively investigated for different applications in oil and gas facilities such as drilling fluids, cementing and enhanced oil recovery.

4.6.1 Application of Nanotechnology in Drilling and Hydraulic Fracturing of Fluids Drilling fluids are responsible for the transportation of drilled cuttings during a drilling operation from the wellbore to the surface. Likewise, hydraulic fracturing

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Synthesis of Nanoparticles

Conventional methods

Biological methods

Bacteria Chemical methods

Physical methods Fungi

Self-assembly

Selflithography

High energy ball milling

Yeast

Algae Plasma processing

Lithography Plants

Chemical vapor deposition

Gas condensation

Physical vapor

deposition

Mechanical method

Sol-gel processing

Fig. 4.2 Different synthetic methods of nanoparticles

fluids are used to carry the proppants (solid structures mainly sand, treated sand or man-made ceramic components) to the fractured zone of a reservoir. Additionally, they aid in performing a successful fracturing process. Several researchers investigated the development of these two fluids by the help of nanotechnology. Amanullah et al. (2011) reported that incorporation of nanomaterials in smart fluids will result in the formation of tight and thin mud cake. Additionally, it helps to enhance the filtration and rheological characteristics of these fluids. Nowadays, numerous fluids employed in oil industry involve the presence of macro and micro sized particles; therefore, unavoidable damage might take place. Amanullah et al. (2011) successfully prepared different water based nano-fluids with three commercial available NPs at a concentration 0.5 part per billion (ppb). The addition of a regular viscosifier and a tri-functional additive ensured the stability of the NPs in the dispersing phase in addition to enhancement of the filtration properties of the nano-fluid. Moreover,

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Fig. 4.3 Schematic representation of chemical synthesis of nanoparticles

in order to assure the stability of the nano-fluid, a rational viscometer was used to measure the nano-fluid’s gel strength and its viscous characteristics. These measurements were determined at different time intervals, at zero time, instantly after fluid preparation and at 18, 48 and 72 h. The closeness of the resultant data proved that the nano-fluid was stable, and had the capacity to fulfil the needed requirements for field applications. The prepared nano-fluid exhibited better viscous features in comparison with bentonite mud. Also, it displayed stable gel strength. Furthermore, the mud cakes generated by the nano-fluid were thin and tightly packed and were less than 1 mm in thickness. Crews and Huang (2010) reported that the use of NPs with surfactant in brine that has internal breaker resulted in facilitating the removal of polymer residues from hydraulic fracture. Hurnaus and Plank (2015) demonstrated that the use of NPs in crosslinking of fracturing fluid improved the viscosity.

4.6.2 Formulation of Nano-Emulsions for Cement Spacers via Nanotechnology Sometimes it is vital to substitute one fluid system with another one during drilling thus; spacers are usually sited in between the fluid systems throughout the displacement process. Van Zanten and Ezzat (2010) demonstrated that oil based mud (OBM) needs to be detached by spacers when displacing cement in order to prevent contamination. Data introduced by Maserati et al. (2010) showed that cement spacers made up of nano-emulsions can efficiently clean OBM from wellbore surface during cementing procedures in addition to reversing the wettability of this surface. Nano emulsions are characterized by good stability and high surface areas. Maserati et al.

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(2010) prepared nano-emulsions by a two-step process. The process involved presence of water, 10% aromatic solvent concentration and surfactant. These novel cement spacers are usually referred to as “nano-spacers”. They are prepared by the addition of weighting agents to nanoemulsions and by commercial gelling. The efficacy of the prepared nano-spacers was compared with that of commercial spacers that are commonly used in the field. Metallic grid test showed enhancement in mud removal performance with a percentage of 95%. Likewise, the wettability revealed that the nanospacers reverted oil-wet surfaces to water-wet ones completely. The resultant contact water angle exhibited a drastic decrease in contact angle from 70 to approximately zero.

4.6.3 Application of Nanotechnology in Operations’ Logging During drilling of wells, information concerning reservoir fluid, lithology and rock properties should be comprehensively collected in details. Logging refers to “the process of gathering such data”. Singh and Bhat (2006) introduced an innovative idea namely “nanologging”. This idea depends on the possible use of nanorobots in logging applications in petroleum industries. Nanorobotics implicates the use of robots that are micrometer in diameter and equipped with constituents that are nanometer in size. Nanorobotics introduce information concerning the precise time needed for drilling as they are extremely small and have the ability to get very close to the formation. Hence, there will be a great minimization in rig hours as well as the logging costs. The nanorobot will contain nanosensors to collect information, nanomotor as a drive mechanism, shield made up of carbon alloys to provide down hole protection, microprocessors to control data from surface computer, and electro-magnetic transmitter for data transfer to the surface through electromagnetic waves. Furthermore, nanorobot can be translocated via mud circulation system. Still, certain challenges and risks were revealed such as the negligence or incompetence of personnel dealing with nanorobots in addition to malfunctioning because of unexpected machine-machine interactions. Further research and progress in nanotechnology will aid in overcoming these challenges.

4.6.4 Control of Formation Fines During Production via Nanotechnology Production rate may be reduced because of the transference of formation fines near wellbore regions leading to pore blocking. Such particles are usually smaller than 37 mm (Tiffin et al. 1998) and they lead to damage in production pump and mesh screen erosion. Huang et al. (2008) demonstrated that NPs can coat proppant surfaces during fracturing process because of the high surface forces and the van der Waals

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electrostatic forces. A fracturing process can be treated by the addition of 1 g of NPs per 1000 g of proppant in slurry form to the surfactant fracturing fluid and then mixed with the proppants. Then, the fracturing fluid is broken and the mixture is discharged in an acrylic tube that contains a 100 mesh screen at the bottom.

4.6.5 Hydrocarbon Detection Using Nanotechnology Berlin et al. (2011) reported the use of engineered NPs for the detection of hydrocarbons in oil-field rock. Hence, the NPs in this case are referred to as “nanoreporters”. A hydrophobic cargo was prepared in aqueous solution along with engineered NPs and synthetic seawater and then conveyed through different reservoir rock samples. This cargo 2, 20, 5, 5’-tetrachlorobiphenyl, was loosed when the carrier fluid faced hydrocarbons. The cargo was one of the congeners of polychlorinated biphenyl (PCB). Yu et al. (2010) conducted the synthesis of dolomite and sandstone via hydrophilic carbon clusters (HCCs) NPs which were then surface treated with polyethylene glycol (PEG). Yet, further improvement was needed and hence the surface treatment material was substituted with polyvinyl alcohol (PVA). Moreover, minimizing aggregation of NPs was crucial and thus oxidized carbon black (OCB) substituted HCCs which in turn led to better results.

4.6.6 Enhanced Oil Recovery Applications A number of researchers have directed their research towards improving enhanced oil recovery (EOR). This occurred because of the fact that two-thirds of oil is left behind after the primary and secondary recovery (Bai 2008). Recent investigations have applied NPs to enhance EOR techniques. The main objective of these investigations is to study the effect of nanoparticles in improving oil recovery. For instance, aluminium oxide NPs reduced oil viscosity (Hogeweg et al. 2018), titanium dioxide NPs improved the stability of water that is injected for EOR applications (Ding et al. 2018), graphene oxide reduced oil viscosity (Elshawaf 2018), silicon dioxide improved foam stability and increased sweep efficiency (Ajulibe et al. 2018; Ibrahim and Nasr-El-Din 2018). In spite of the fact that NPs might enhance some of the previously mentioned parameters, it could also exert a negative effect on some other parameters. Hogeweg et al. (2018) demonstrated that zinc oxide tends to form large particles leading to difficulties in injection. Addition of NPs to brine or ethanol may result in poor recovery compared to brine or ethanol alone. Settling issues and injection blockage have also been described previously by Ding et al. (2018).

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4.6.7 Application of Nanotechnology in Corrosion and Biofouling Inhibition Because of the lethal consequences of corrosion and the metallic destruction that takes place in gas and oil facilities, many researchers focused their studies on using nanotechnology for corrosion mitigation (Murugesan et al. 2014). Atta et al. (2013) fabricated AgNPs via the reduction of silver nitrate (AgNO3 ) along with trisodium citrate in an aqueous solution and in the presence of polyethylene glycol thiols and poly (vinyl pyrrolidone) as stabilizing agents. The characteristics of the prepared AgNPs were studied by transmission electron microscope (TEM) and dynamic light scattering (DLS). Ultraviolet-visible (UV/Vis) absorption spectrum was used to study the effect of HCl on the stability of the dispersed AgNPs. Polarization techniques and electrochemical impedance spectroscopy (EIS) were employed to study the corrosion inhibition efficiency of the polyethylene glycol thiol and the self-assembled monolayers of AgNPs. Polarization curves designated that the coated silver polyethylene glycol thiols acted as mixed type inhibitors. The data of corrosion inhibition efficiency estimated by polarization measurements were in good agreement with those obtained by EIS measurements. Atta et al. (2014) performed a study in which AgNPs were synthesized by the reduction of AgNO3 with p-chloroaniline in the presence of polyoxyethylene maleate 4-nonyl-2 propylene-phenol as a stabilizer. The size of the prepared AgNPs was less than 10 nm. The synthesized AgNPs were incorporated to prepare a hybrid polymer using a semi-batch solution polymerization method in the presence of N-isopropylacrylamide (NIPAm), 2-acrylamido- 2-methylpropane sulfonic acid (AMPS), N, N-methylenebisacrylamide (MBA) and potassium persulfate (KPS). The prepared AgNPs and hybrid polymer were characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and TEM. Electrochemical measurements such as polarization measurements and EIS evaluated the corrosion inhibition efficiency of the AgNPs and hybrid polymer against steel corrosion in the presence of HCl solution. It was revealed that AgNPs and the hybrid polymer acted as a mixed type-inhibitor and the corrosion inhibition efficiency percentage increased with increasing inhibitor concentration. Mild steel has been extensively utilized because its cost effectiveness in several fields such as mining, marine infrastructure, petroleum production and chemical processing (Duraibabu et al. 2014). Unfortunately, the chief drawback in using mild steel is its limited resistance against corrosion. Several advantages of epoxy resin made it a suitable candidate as a coating material for the protection of steel as well as submerged structures among which is the amazing salt-water resistance, good insulating features, and the strong adhesion capability to different materials (Galliano and Landolt 2002). Two common mechanisms usually take place to reduce metallic corrosion by epoxy coatings either by acting as a physical barrier film to repel deleterious corrosive species or by serving as a reservoir for corrosion inhibitors to prevent the attack by aggressive species (Duraibabu et al. 2014). Still, epoxy coatings are susceptible to damage by wear and surface abrasion (Wetzel et al. 2003). Such disadvantages resulted in localized defects in the consumed coating and damage

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to its mechanical strength as well as its appearance. Therefore, nanoscale inorganic filler particles can be dispersed within the epoxy resin matrix to produce an epoxy nanocomposite coating. Increasing the incorporation of NPs into epoxy resins offers a chance to increase the durability and integrity of coatings as these nano-sized particles fill the cavities in the used coating (Lam and Lau 2006). In addition, NPs incorporated within epoxy coatings provide excellent barrier properties for protection against corrosion (Lamaka et al. 2007). Recently, epoxy antimicrobial coatings gained lots of interest as they provide surfaces with the required protection against corrosion causing microorganisms. Therefore, the development of epoxy nano-structured coatings with antimicrobial properties is essential. The tetraglycidyl 1, 4-bis (4-amine-phenoxy) benzene (TGBAPB) epoxy resin matrix was functionalized with (F-ZnO) and non-functionalized (N-ZnO) to develop distinct modified functional epoxy nanohybrid coatings. TGBAPB was synthesized via 1, 4-Bis (4nitrophenoxy) benzene (BNPB). While, the nano sized ZnO NPs was prepared by homogeneous precipitation technique and then by calcination. The formation of ZnO NPs was confirmed via FTIR and TEM. Additionally, ZnO NPs were amine functionalized by grafting 3-aminopropyltriethoxysilane (APTES) as coupling agent. The FTIR spectra showed that silane coupling agent bonded to ZnONPs surface enhanced the dispersibility as well as compatibility with TGBAPB epoxy matrix. EIS was used to detect the influence of surface functionalization of ZnONPs towards corrosion resistance. Data indicated that the coating film had a good corrosion resistance. Furthermore, the antimicrobial test indicated that functionalized ZnO NPsTGBAPB coating exhibited strong antimicrobial activity against Escherichia coli. Thus, the TGBAPB-F-ZnO coating is recommended as a corrosion inhibitor and a biocide to control microbial corrosion. Yee et al. (2014) successfully synthesized Ag-polymer nanocomposite (Ag-PNC) via an ion-exchange and reduction processes. The prepared nanocomposite exhibited a promising anti-micro-biofouling effect by interfering with biofilm formation and consequently caused inhibition of macro-biofouling. Dowex microspheres provided a supporting matrix for the immobilization step in addition to acting as a template for AgNPs on the polymer surface. The borohydride reduction technique was used to load over 60 wt% AgNPs. Scanning electron microscope (SEM) images demonstrated the identical distribution of AgNPs with a diameter ranging between 20 and 60 nm on the microbead surface, while UV/Vis analysis showed the characteristic surface plasmon resonance (SPR) peak of the prepared AgNPs from 406 to 422 nm. Interestingly, thermal stability of the prepared nanocomposite was improved by the addition of AgNPs, with significant degradation at 460°C compared with 300°C for the copolymer microbead alone. Moreover, the glass transition temperature of Ag-PNCs increased from 130°C to 323°C. The polymeric microbead served as a physicochemical anchor to Ag ions to attach to and successively formed a stable matrix which aided in controlling the agglomeration and growth of AgNPs. Furthermore, the synthesized Ag-PNC material was found to effectively inhibit biofilm formation by the marine fouling bacterium Halomonas pacifica (ATCC 27122). H. pacifica is a Gram negative bacterium and was obtained from the American Type

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Culture Collection and was cultured in Zobell Marine Broth 2216. Besides, a biocompatibility analysis with human keratinocytes and human lung fibroblast exhibited no changes in cell morphology, thus causing no significant toxicity to human cells. Besides, a toxicity study for the effect of Ag-PNC against non-target marine microalgae Isochrysis sp. and D. tertiolecta displayed no morphological changes. Therefore, Ag-PNC is strongly suggested as a promising anti-microfouling agent. Maia et al. (2015) investigated two compounds with well-known biocidal effect i.e. the antifouling agent 4, 5-dichloro-2-octyl-4-isothiazolin-3- one (DCOIT) and 2 mercaptobenzothiazole (MBT), in two states i.e. free and encapsulated forms. These two compounds were successfully encapsulated in silica nanocapsules and the resultant materials were characterized via SEM, thermogravimetric analysis (TGA) and adsorption/desorption isotherms. Assessment of the antibacterial activity of silica nanocapsules loaded with biocides was done using the real-time monitoring of the bacterium (recombinant bioluminescent strain of E. coli). Results showed inactivation of the tested bacterial strain as a result for the release of the biocides from silica nanocapsules. The prepared nanomaterials showed high potential to be incorporated within an anti-fouling coating. Christopher et al. (2016) prepared ZnO NPs via ultrasonication method. The fabricated ZnO NPs were dispersed with polyurethane nanocomposite and then they were modified with two biopolymer compounds (i.e. lignosulfonate and sodium alginate). The coating was fully characterized using SEM, high resolution transmission electron microscope (HRTEM) and XRD. Potentiodynamic polarization and EIS were employed to investigate the influence of incorporating modified ZnO NPs on the polyurethane coated steel. Results showed that increasing the percentage of surface modified ZnO NPs in polyurethane coating did not only promote their dispersion however, it improved the corrosion resistance of the nanocomposite coating. Still, further research is required to improve the interfacial interactions between nanofillers and polyurethane to ease the process of coatings in industry. According to Shirehjini et al. (2016), paints rich with zinc particles should be closely in contact with each other in order to reach satisfied cathodic protection. Therefore, pigment volume concentration should be in order with that of critical pigment volume concentration. Otherwise, the electrical contact will not be enough and accordingly the metal will not be completely protected (Kakaei et al. 2013). In the past, efforts were made to improve the protectiveness of zinc rich paints by controlling zinc content, particle size and shape of zinc metal (Park and Shon 2015). Several pigments such as micaceous iron oxide and lamellar Zn and Al pigments were employed (Arman et al. 2013). According to Schaefer and Miszczyk (2013), carbon nanotubes and zinc NPs were used to improve the protective features of zinc rich coating. Therefore, a study performed by Shirehjini et al. (2016) investigated the effect of addition of clay NPs to zinc rich coating and evaluated its effect on cathodic protection. OCP measurements assured the outstanding efficacy of this coating when clay content was 1 wt%. EIS results revealed that the addition of 1 wt% clay NPs resulted in high protection against corrosion because of clay dispersion within the coating. Contrary, the addition of more than 1 wt% clay nanoparticles reduced the long term protection due to decrease in intercalation of clay.

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Kang et al. (1998) demonstrated that polyaniline exhibits various chemical structures that are dependent on both potential and pH. Polyaniline chemical structures involve; leucoemeraldine, emeraldine and pernigraniline bases as well as leucoemeraldine and emeraldine salts. Multiple research articles studied the anticorrosive effect of polyaniline against mild steel (Wessling 1997), copper (Özyılmaz et al. 2005), stainless steel (Zhong et al. 2006), iron (Sathiyanarayanan et al. 2007), and aluminium and aluminium alloys (Gupta et al. 2013). Graphene is a two dimensional monolayer of sp2 bonded carbon, which is characterized by superior features such as high mechanical, thermal, electrical and optical properties (Novoselov et al. 2005). According to Jafari et al. (2016), graphene is now one of the most competing materials with excellent anti-corrosion features because of its chemical structure, outstanding thermal and chemical stability, significant flexibility and impermeability to molecules. Chang et al. (2012) demonstrated the successful use of polymer/graphene composites for inhibiting steel corrosion. This was due to its great effectiveness as a barrier to prevent the passage of both water and oxygen. Yu et al. (2014) successfully managed to prepare well-discreted polystyrene/modified graphene oxide composite to provide protection against corrosion. The as-prepared composite exerted excellent anti-corrosion effect in comparison with polystyrene alone. In a study presented by Jafari et al. (2016), polyaniline-graphene nanocomposite (PANI/G) was used as a coating to protect copper from corrosion. Jafari and co-workers managed to successfully electrodeposit PANI/G nanocomposite on Cu by cyclic voltammetry technique in a sulphuric acid medium. The prepared nanocomposite was characterized using FTIR, UV/Vis, XRD, and TGA. SEM analysis demonstrated the morphology of PANI/G nanocomposite as Cu was fully coated with the prepared composite and graphene NPs were homogeneously covered by polyaniline film deposits. It is worth noting that PANI/G nanocomposite remained integrated with no imperfections after being immersed in 5000 ppm NaCl solution for 120 min. The coating effectiveness against corrosion was evaluated by potentiodynamic polarization and EIS studies. The coating prepared from PANI/G nanocomposite exhibited excellent corrosion resistance in aggressive corrosive environments. The results revealed that the use of polyaniline with graphene NPs aided in the establishment of a protective layer therefore shifted the corrosion potential of the metal substrate to low values and decreased the corrosion rate. In addition, the corrosion inhibition efficiency reached 98% as indicated by the electrochemical measurements. As mentioned earlier, has been reported to be a two-dimensional material that is made up of hexagonal sp2 hybridized carbon network (Soldano et al. 2010), while graphene oxide (GO) is a chemically modified graphene with functional groups such as hydroxyl, epoxy and carboxyl groups (Li and Liu 2010). GO sheets were reported to be used as building block materials for the fabrication of new composites (Pasricha et al. 2009). De Faria et al. (2017a, b) investigated the preparation, characterization and antibacterial potential of a nanocomposite composed of GO sheets decorated with AgNPs (GO-Ag). The GO-Ag nanocomposite was prepared in presence of AgNO3 and sodium citrate. The physicochemical properties were characterized via UV/Vis spectroscopy, TGA, XRD, Raman spectroscopy and TEM. The approximate size of AgNPs which were deposited on the GO surface was 7.5 nm. For perfect

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nucleation and growth of AgNPs, oxidation debris fragments were found to be vital. The antibacterial potential of both GO and GO-Ag nanocomposite against Pseudomonas aeruginosa was investigated using the standard plate counting technique. No antibacterial activity was detected by GO over the tested concentration range. Alternatively, the GO-Ag nanocomposite expressed high biocidal activity with a minimum inhibitory concentration ranging from 2.5 to 5.0 g/ml. Moreover, the antibiofilm activity against the sessile cells of P. aeruginosa adhered on stainless steel surface was investigated. It was found that GO-Ag nanocomposite exerted a 100% inhibition rate against the adhered cells after being exposed to GO-Ag nanocomposite for one hour. This is considered the first research work that has reported the capability of GO-Ag nanocomposites to inhibit the growth of microbially adhered cells and to mitigate biofilm formation. Therefore, it can be used as an antibacterial coating material to avoid biofilm development. Khowdiary et al. (2017) prepared cationic quaternary ammonium polymers enclosing different molecular weights of non-ionic polyethylene glycol chains via polyethylene terephthalate glycolyzed polymer. Likewise, 24–35 nm sized AgNPs were prepared using trisodium citrate as a reductant. UV/Vis spectra revealed the loading of AgNPs on the cationic surfactants. TEM results showed the stability and assembling of the AgNPs on the cationic polymers. The assembled AgNPs along with the prepared cationic polymers were tested for their biocidal activity against sulphate reducing bacteria (SRB) e.g. Desulfomonas pigra using the serial dilution most probable number (MPN) method. Antimicrobial assay demonstrated that the prepared cationic surfactants exhibited good biocidal activity against the tested SRB strain. The reason behind the antimicrobial action of the synthesized quaternary cationic polymers might be due to the adsorption of cationic compounds on the cellular membrane and to the disturbance and deregulation of biological reactions within the cells. The adsorption of the prepared cationic quaternary compounds on the cell membrane is due to its high surface activity as well as its amphipathic properties. The adsorbed molecules penetrated the cell membrane and interfered with the existed enzymes, proteins and DNA, leading to disturbance to the cellular biological reactions. The tested compounds showed low biocidal effect against D. pigra at low concentrations of 100 and 200 part per million (ppm). By increasing the concentration to 400 ppm, the effectiveness of the compounds increased and the count of the bacterial cells decreased extensively. In a study performed by Al-Naamani et al. (2017), it was proved that chitosan/ZnO nanocomposite could serve as a successful coating to prevent biofouling and settlement of biofoulers such as bacteria, fungi, benthic diatoms, macro-algae and larvae. A procedure has been developed to prepare effective and novel coatings to prevent biofouling. Surface morphology was characterized via field emission scanning electron microscope (FESEM) and structural analysis was identified via EDX both demonstrated successful interaction between chitosan and ZnO NPs. Decrease in hydrophilicity, solubility and swelling properties aided in improving the wettability of the coating surface. Growth inhibition of the marine fouling bacterium Pseudoalteromonas nigrifaciens and the fouling diatom Navicula incerta was achieved. Thus, it can be concluded that the incorporation of ZnO NPs with chitosan as a

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coating material is a promising methodology to mitigate the development of marine biofoulers on wetted surfaces. As previously mentioned when pipelines, ship hulls, oil platforms and ocean sensors are submerged in marine environments they become vulnerable to biofouling. Although there are extremely effective anti-fouling coating compounds such as tributyltin (TBT). However, since 1960s, TBT was proved to exert detrimental toxicological effects on non-target sea organisms. This led to a global banning on using it since 2008 by the International Maritime Organization (Qian et al. 2009). Accordingly, discovery of new anti-fouling strategies which are eco-friendly and effective in combating biofouling was urgently required. Yee et al. (2017) developed a green and an innovative methodology to produce high stable and dispersed nanotubular silverTiO2 materials. This was constructed by a hydrothermal reduction of AgNPs in conjunction with the citrate method on TiO2 nanotubes. Structural and surface characteristics were studied via UV/Vis, EDX, XRD, TEM and FESEM. UV/Vis spectrophotometer showed a reduction of the TiO2 band gap and a shift took place towards the visible spectrum due to the combination of Ag and TiO2 . Electron microscopy assured the successful synthesis and uniform distribution of the prepared nanocomposite. Diameter of AgNPs ranged between 32 and 103 nm (SEM imaging). XRD showed the presence of face centred cubic (fcc) Ag and TiO2 only, thus confirmed the purity of the prepared samples. The effectiveness of the biofilm inhibition was directly related to the size of AgNPs. The addition of very low concentrations of Ag enhanced the anti-fouling property of pure TiO2 to exert an extremely effective anti-fouling effect. Meethal et al. (2018) successfully managed to prepare polyaniline zinc oxide hybrid nanocomposite (PNZ) in water medium. The polymer matrix was made up of emeraldine salt of polyaniline. The prepared hybrid of PNZ attained emeraldine base form. Preparation of emeraldine base was confirmed by transmission and optical analyses. A mixture of metal oxide—polymer semiconductor hybrid was fabricated via sol gel precipitation technique. ZnO nanostructures were templated with the previously prepared hybrid of PNZ. XRD, FTIR and FESEM were employed to study and characterize the structural, optical and morphological structures of the prepared hybrid. The anti-corrosion performance of ZnO polyaniline hybrid nanocomposite was studied using potentiodynamic polarization measurements as well as EIS. Measurements showed that PNZ showed high impedance value hence, it displayed a better anti-corrosion performance. Synthesis and fabrication of colloidal spheres of polymer/inorganic compound hybrids are considered one of the most exciting research fields in the last two decades. They are elastic, rigid, heat resistant to inorganic materials in addition to being highly stimuli-responsive with superior photoelectric properties. Therefore, they can be tremendously employed in functional coatings, synthesis of composites, biomedical and photoelectric materials (Bollhorst et al. 2017). Pan et al. (2018) synthesized raspberry like poly ethyl methacrylate (PEMA)/SiO2 colloidal spheres which were grafted by a hydrophilic diblock copolymer poly (2-methacryloyloxyethyl phosphorylcholine-b-3-(trimethoxysilyl) propyl methacrylate) (poly(MPC-b-MPS)) on the SiO2 nanoparticles via the reaction of silanol groups of SiO2 with the

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methoxyl groups of MPS. The prepared copolymer-grafted hybrid sphere-based coatings displayed anti-biofouling performance as well as self-repairing capability. Sarkar et al. (2018) conducted a study in which nanohybrid geopolymer zinc oxidesilica based (GMZnO-Si) was investigated for its potential to anti-biodeteriorate cement materials. Rod shaped zinc oxide nano-rods (ZnO NRs) were synthesized and spherical silica NPs were decorated around the surface of ZnO NRs. Characterization of the fabricated ZnO-SiO2 composite was done by using different techniques such as FTIR, XRD, FESEM, EDS, TEM, and X-ray photoelectron spectroscopy (XPS). Mechanical properties of GMZnO-Si were found to be much higher than that of control samples. Tests of rapid chloride ion penetration, water absorption and sulphate resistance were performed to determine the durability of the prepared nanohybird. E. coli, S. aureus and A. niger were used as bacterial and fungal models for inspecting the antimicrobial effects of GMSi and GMZnO-Si. It was noticed that presence of ZnO nano rods in sufficient amounts within the prepared composite inhibited the growth of the tested microbial strains. Surfactants are organic compounds which have the affinity to inhibit or minimize steel corrosion at low concentrations in corrosive environments (Abd-Elaal et al. 2018). Surfactant chemical structure plays the chief role in corrosion inhibition. Presence of functional groups such as carbonyl and hydroxyl groups, ethylene oxide, benzene ring, oxygen and nitrogen atoms beside the presence of hydrophobic chains are the main reasons behind their adsorption capability on steel surface (Mobin et al. 2016). Besides, surfactants play an important role as self-assembling as well as capping agents which help in controlling shape and size and conferring stability to the prepared nanoparticles (Huang et al. 2017). In a study performed by Abd-Elaal et al. (2018), three non-ionic surfactants derived from hydroxyphenyl propionic acid were synthesized and labelled as HTOPD, HTOPT and HTOPH. The three synthesized surfactants showed a high potential to stabilize AgNPs. Synthesis of the prepared silver nanohybird was characterized using TEM, UV/Vis spectroscopy and dynamic light scattering (DLS). The surface tension data were determined to study the impact of AgNPs. The long carbon tail of HTOPH surfactant offered the highest stabilization and the lowest agglomeration with the successful preparation of small sized AgNPs. Nanohybird AgNPs capped and stabilized with HTOPD, HTOPT and HTOPH exhibited low critical micelle concentration (CMC) compared with the non-ionic surfactants alone. Additionally, it was found that the ability of the prepared nanohybrid system to aggregate in micelles was higher in comparison with surfactant. This was confirmed by the change in values of free energy adsorption as well as micellization. The synthesized HTOPD, HTOPT and HTOPH non-ionic surfactants displayed a perfect corrosion inhibition efficiency against steel corrosion in 0.5 M HCl. The resultant data indicated that the inhibition efficiency was directly proportional to the length of the hydrophobic chains of the prepared surfactants. The surfactant HTOPH exerted the maximum inhibition efficiency at all tested temperatures. The tafel polarization curves indicated that the three surfactants acted as mixed type inhibitors and they obeyed Langmuir adsorption isotherm. The produced AgNPs enhanced the antimicrobial potential of the non-ionic surfactants against Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa, Escherichia coli, Candida albicans and

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Aspergillus niger. It was noticed that the silver nanohybrid system with HTOPD non-ionic surfactant was the most efficient type in mitigating the growth of the tested fungi and bacteria. Rasheeda et al. (2019) studied the biocidal activity of interlinked chitosan-ZnO NPs at 10% initial ZnO loading (CZNC-10) against SRB in simulated injected seawater on S150 carbon steel. It was found that 250 μg/ml of CZNC-10 was the optimum concentration for SRB inhibition. The biofilm and corrosion products with and without CZNC-10 were characterized by XPS. XPS showed that the corrosion products were mainly iron sulphides and iron oxides, while there were significant decrease in presence of CZNC-10. It was apparently observed that CZNC-10 reduced biocorrosion by inhibiting SRB growth and via the establishment of a more protective layer on the carbon steel surface to prevent any upcoming bacterial attacks. Additionally, the structural appearance of the biofilm formed by SRB on carbon steel was studied at different time intervals (i.e. after 4, 7 and 28 days) in absence and presence of CZNC-10. During the first days of incubation, it was observed that SRB were mainly rod shaped bacteria. After 4 days of incubation in SRB media, the bacterial cells started to metabolize and produce small quantities of extracellular polymeric substances (EPS) through which bacteria adhered to the metal surface (Chen et al. 2014). Thus, carbon steel coupons were vulnerable to bacterial adhesion and subsequent biofilm formation (Chen et al. 2017). After 4 days of SRB incubation with carbon steel coupons, a layer of biofilm appeared on the coupon surface. An obvious damage of the bacterial cells was in presence of CZNC-10. The bacterial damage was proposed to be due to the biocidal effect of CZNC-10 against SRB. After 7 days of incubation in SRB media, SRB cells were still observed either individually or in small clusters on the coupon surface. However, by elongating the incubation time till 28 days in presence of CZNC-10, both coupons exposed to SRB in presence and absence of CZNC-10 showed somehow the same morphology. Uneven deposits due to the produced corrosion products were observed. Moreover, the profilometry analysis showed less corrosion damage on the coupon surface treated with CZNC-10. EIS showed an approximate increase in charge transfer resistance (Rct) of about 3.2 and 2.8 on carbon steel coupon after 21 and 28 days of incubation in presence of CZNC-10. Totally, the study confirmed that the CZNC-10 can be used as an effective and eco-friendly corrosion inhibitor and as a biocide against SRB in an attempt to mitigate microbially influenced corrosion. The cost effectiveness and high stress strength made carbon steel one of the most used pipeline material in oil production and transportation (Sun et al. 2016; Xiang et al. 2017). However, carbon steel is enormously vulnerable to corrosion in a CO2 -containing environment (Xiang et al. 2017). CO2 is a corrosive agent which dissolves in water and produces carbonic acid which causes early breaking down of pipelines, leading to worldwide catastrophes because of electrochemical corrosion (Elgaddafi et al. 2015; Laumb et al. 2017). Unfortunately, most of the water generated in oil and gas fields is rich with CO2 (Wei et al. 2016). Currently, plenty of CO2 corrosion inhibitors such as Schiff bases, imidazoline derivatives and quaternary ammonium salts have been formulated (Zuo et al. 2017). Though, synthesis of such organic compounds is complex and requires high energy, therefore there was a

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need to employ green chemistry to overcome such problems. Carbon dots (CDs) are known to be novel fluorescent nanomaterials which are characterized by their high and stable fluorescence, low toxic effects and biocompatibility. In a study performed by Cen et al. (2019), N, S-CDs were synthesized via the hydrothermal method using hypotoxic aminosalicylic acid and thiourea. They were tested for their ability to act as corrosion inhibitors. N, S-CDs were characterized by UV/Vis spectrophotometer, XRD, FTIR, Raman, TEM, photoluminescence spectroscopy and elemental analyzer. The inhibition effect of N, S-CDs was investigated using EIS, potentiodynamic polarization and weight loss measurements. Surface characterization of carbon steel was carried out using SEM along with EDS, XPS, atomic force microscopy (AFM) and contact angle measurement. Results revealed that N, S-CDs can effectively protect carbon steel from corrosion and the inhibition efficiency increased with the increase in the concentration of N, S-CDs reaching 93% at 50 mg/l. Even at a low concentration such as 10 mg/l N, S-CDs, the corrosion current density reduced from 1.472 × 10−4 A·cm−2 in the blank condition to 2.99 × 10−5 A·cm−2 after 12 h of immersion time. The existed functional groups on N, S-CDs aided in its adsorption on carbon steel and formation of a hydrophobic layer on the metal surface with a thickness of approximately 40 nm. Sharifi et al. (2019) synthesized a corrosion inhibitor via the chemical addition of nitrogen, sulfur and phosphorous atoms to graphene oxide nanostructure (NSP-GO) to evaluate its anti-corrosive effect of mild steel in a saline medium with 3.5 wt% NaCl. It incredibly increased the anti-corrosive performance of two synthesized water-soluble polymeric compounds i.e. urea formaldehyde (UF) and melamine formaldehyde (MF). The corrosion current density for both MF and UF polymers shifted from 30.2 μAcm2 to 2.7 μAcm2 and 3.2 μAcm2 , respectively at a concentration of 500 ppm. Meanwhile, with the addition of NSP-GO, the corrosion current density fell to almost zero. Data obtained from potentiodynamic polarization measurements and EIS revealed that the inhibition efficiency reached 100%. This high level of protection occurred due to the high surface decoration covering ability of graphene oxide nanosheets with heteroatoms. The SEM images showed a reduction in the number of pits and a decrease in the severity of the damage by using the prepared composite polymeric compounds. It was suggested that the heteroatoms that decorated GO nanosheets acted like anchors to fix the GO sheets towards the metal surface and thus helped MF and UF polymers to form film protectors. One of the most employed techniques to inhibit, manage and minimize the detrimental effects of corrosion is coating (Abdeen et al. 2019). Coating has the advantage of being applied internally or externally within wide range of temperatures (Singh et al. 2014). However, using coatings is somehow costly, but they are more feasible in a long run and on large-scale applications. They guarantee massive savings concerning safety, repair costs and maintenance of equipment (Samimiã and Zarinabadi 2011). Generally, protection introduced by coatings takes place either via passivation (Van Velson and Flannery 2016) or active protection (Saji 2012). As demonstrated by Mingming et al. (2006), passive protection is achieved only when coatings form a physical barrier of oxides between the desired surface and the surrounding environment. While, active protection takes place by the addition of inhibitors to aggressive environments to avoid or reduce corrosion effects (Dariva

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and Galio 2014). Electroless nickel-phosphorous (Ni-P) coatings are characterized by their outstanding resistance towards wear and corrosion which make them suitable candidates in various industries (Liu and Zhao 2011). Nowadays, the addition of NPs within Ni-P matrix coatings highly upgrades their properties and result in entirely new characteristics to the coating performance (Aal et al. 2008). Liu and Zhao (2011) demonstrated the incorporation of polytetrafluoroethylene (PTFE) and TiO2 within Ni-P matrix to aid in preparing highly effective nanocomposites with corrosion resistance capability. Furthermore, Liu and Zhao (2011) demonstrated that Ni-P-PTFE nanocomposite coatings possessed good antibacterial activity compared with Ni-P coatings alone. Aal et al. (2008) prepared Ni-P-TiO2 nanocomposite coatings with different concentrations of TiO2 NPs via electroless technique. Novakovic et al. (2006) demonstrated that corrosion resistance and hardness was greatly improved by the incorporation of TiO2 NPs into Ni-P coatings. Moreover, Chen et al. (2010) demonstrated that the addition of TiO2 NPs to Ni-P coatings significantly resulted in an increase in the microhardness of the prepared coating. The biocidal potential of TiO2 NPs was first reported in 1985 by Matsunaga et al. (1985). The micro-biocidal action of TiO2 NPs was investigated in details by Huang et al. (2000) and Wang et al. (2000). It was suggested that TiO2 NPs produce strong oxidizing power upon exposure to illumination with UV light with wavelengths less than 385 nm. The first oxidative disruption occurs on the cell wall via interaction with TiO2 NPs. Afterwards; the further oxidative damage occurs in the cytoplasmic membrane and results in cell death and lysis (Huang et al. 2000; Wang et al. 2000). In a study performed by Kikuchi et al. (1997), TiO2 films exhibited an antibacterial effect upon coating on several materials for instance tiles, glass and stainless steel after being exposed to weak ultraviolet light. It was found that the number of viable cells of Escherichia coli was significantly minimized on the illuminated TiO2 film. Moreover, Li and Logan (2005) demonstrated that bacterial attachment on TiO2 coated surfaces was majorly decreased after exposure to UV light. It was also observed that the water contact angle on TiO2 -coated surfaces reduced from 59° to 5° after exposure to UV light. In a study introduced by Yu et al. (2003), water contact angle of TiO2 films on stainless steel was found to decrease from 45–50° to 10–18° after exposure to UV light. Additionally, the prepared TiO2 films displayed amazing antibacterial efficiency against Bacillus pumilus. Allion et al. (2007) observed that bacterial adhesion was significantly decreased after the exposure to UV irradiation as the water contact angle on TiO2 films reduced from 100° to 5°. Besides, the TiO2 films minimized bacterial adhesion up to 80%. The above studies indicated that ultraviolet illumination of TiO2 surfaces could produce a high or even super-hydrophilic surface. Marciano et al. (2009) investigated the addition TiO2 into diamond like carbon coating (DLC) and revealed that the antibacterial potential of DLC-TiO2 coating increased with the increase in TiO2 content in the coating. In a study performed by Zhao et al. (2013), different concentrations of TiO2 were incorporated with Ni-P matrix and were plated on stainless steel 316L substrate via electroless deposition technique. The biocidal effect of the coating was evaluated against different types of bacterial strains including; the freshwater bacterium Pseudomonas fluorescens and two marine bacteria Vibrio alginolyticus 2171 and Cobetia marina 4741 which are

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mainly responsible for biofouling on the surface of ships hulls, heat exchangers and pipelines, etc. The addition of TiO2 NPs into the Ni-P matrix took the advantages of both constituents (i.e. Ni-P alloy and TiO2 ) like high corrosion and wear resistance as well as the antibacterial characteristics. The obtained data revealed that the Ni-PTiO2 coatings minimized the bacterial adhesion of three tested biofouling bacterial strains up to 75% and 70%, respectively when compared with stainless steel and Ni-P coating alone. It was noticed that electron donor surface energy of the Ni-P TiO2 coating reached high levels by the incorporation of TiO2 NPs after exposure to UV irradiation. Therefore, the number of adhered bacteria was reduced with the increase in electron donor surface energy of the coating. Hence, Ni-P-T TiO2 coatings are considered promising candidates with a great potential for reducing biofouling in pipelines, heat exchangers and ship hulls. Sano et al. (2017) conducted experiments to assess biofilm inhibitory effect of silane coating dispersed with copper and silver nanopowder. SEM, EDX, optical microscopy and Raman spectroscopy were used to observe and detect the biofilm depositions. Moreover, focused ion beam (FIB) processing was used to observe threedimensional structures of the specimens. It was noted that biofouling was inhibited by the effect of copper nano-powder that was dispersed into silane-based resin, keeping in mind the fact that the resin coating alone did not exhibit any ability to suppress biofouling. This might be interpreted because of the antibacterial properties of copper NPs. Surprisingly, it was observed that the powder of AgNPs dispersed in the same silane-based resin did not suppress biofouling, although silver is known to exert antimicrobial effects as copper. Upgrading the performance of polymer coatings via the incorporation of nanomaterials is a trial conducted by many researchers to mitigate corrosion and microbial growth in oil fields. One of these trials was the study presented by Kumar et al. (2018). In this study, CuO/TiO2 nanocomposite was used as nanofiller for epoxy coatings to protect steel surface against rusting and bacterial growth. Oxalate method was employed to prepare a novel TiO2 -CuO nanocomposite. The structural characteristics and morphological features were characterized using XRD, EDX, Raman spectroscopy and electron microscopic analyses. Results of electrochemical measurements conducted in 3.5% NaCl solution assured the corrosionprotective properties of epoxy coatings along with the prepared TiO2 -CuO nanocomposites compared with the pure epoxy coating alone. The prepared composite exhibited a strong antibacterial action against the Gram-negative bacterium Escherichia coli. Because oil and gas pipelines are operated under severe chemical, physical and mechanical conditions, which sometimes cause catastrophic failures, Nickelphosphorous (Ni-P) coatings are excellent candidates to protect oil and gas pipelines from corrosion. Ni-P coatings are advantageous because they have superior corrosion resistance properties in addition to high hardness. However, electroless Ni-P coatings suffer from low toughness, which limited their use. MacLean et al. (2019) demonstrated a novel incorporation of nanosized particles of NiTi alloy within the coating which resulted in improving its performance. MacLean and co-workers managed to plate API X100 pipe steel with the novel Ni-P-nano-NiTi composite coating. Scratch

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tests were performed to evaluate the influence of NiTi NPs on wear damage. Indentation tests were done to evaluate the crack modes of the coating as well as the dent resistance. The incorporation of nanosized Ni-P matrix resulted in toughening of the used coating. Iron oxide (Fe2 O3 ) NPs are known to have versatile applications in different fields including; gas sensors, catalysis, solar energy, biomedicine as well as their magnificent magnetic properties (Jeyasubramanian et al. 2016). Based on all of these diverse applications, Jeyasubramanian and his colleagues (2019) prepared (Fe2 O3 ) NPs which were dispersed in alkyd resin via the high energy ball-milling technique. The chemical structure of the synthesized nano iron oxide impregnated alkyd coating (NIAC) was examined by spectroscopic analysis. FESEM revealed the surface morphology of the prepared (Fe2 O3 ) NPs as agglomerated particles with a size of 23 nm. FTIR analysis supported the strong bonds and the uniform distribution of (Fe2 O3 ) NPs with the alkyd resin matrix. The anti-corrosive properties of NIAC were studied using weight loss technique, potentiodynamic polarization measurements as well as EIS in 3.5% NaCl solution. It was revealed that iron dissolution from steel was suppressed and prevented by NIAC coating. Titanium dioxide is a promising ceramic material with distinctive physical and chemical features including self-cleaning (Giolando 2016), ultra violet (UV) protection (Chen and Mao 2007), large refractive index (Giolando 2016), photocatalytic activity (Lorencik et al. 2016) and high abrasive and corrosion resistance (Shen et al. 2005a, b). Titanium oxides can be implemented in different fields for instance sensing, photovoltaics, electrochromics, self-sterilising and self-cleaning construction materials, etc. (Abdeen et al. 2019). According to Shen et al. (2005a), corrosion protection of stainless steel was highly increased via the deposition of TiO2 NPs by the sol gel technique as well as post treatment with hydrothermal process (Shen et al. 2005b). Stainless steel surface was protected by following the same technique and by the formation of a coating film composed of three or four layers (464 nm thick) of TiO2 NPs. Such coating reduced the corrosion current density by three times and improved the corrosion resistance to approximately 10 times higher than that of bare steel. Another important methodology that confers an integrated protection over the surface is referred to as atomic layer deposition (ALD). This method causes no pinholes or cracks compared with the other depositing methods like chemical vapour deposition, spray pyrolysis and physical vapour deposition (Abdeen et al. 2019). This method depends mainly on forming an amorphous phase of NPs and hence a dense and a strong film is generated (Shan et al. 2008). Yet, it has been observed that formation of multiple layers improves the resistance of nano coatings but to certain limits as applying five or six layers increases the susceptibility of coating deformation (Abdeen et al. 2019). According to Deyab and Keera (2014), decreasing the size of TiO2 NPs resulted in better corrosion resistance of carbon steel in H2 SO4 . Formation of nano coatings made up of alumina offers excellent mechanical properties as well as corrosion resistance. Therefore, they have been applied in various industrial fields including; gas diffusion barriers (Ali et al. 2014), anti-reflection layers (Wuu et al. 2015) and surface passivation (Calle et al. 2016). Díaz et al. (2011a) demonstrated

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that incorporation of alumina nano coating over stainless steel type 316L exhibited a better anti-corrosion performance. Nonetheless, certain types of carbon steel did not withstand processing at high temperatures, so deposition on carbon steel was recommended to take place at low or room temperatures. Díaz et al. (2011b) performed a study in which alumina was deposited on carbon steel type 100Cr6 at 160°C. It was observed that coating thickness needed to be higher than 10 nm to inhibit corrosion and to avoid any defects in carbon steel structure. Pentoxide (Ta2 O5 ) is an attractive metal which is characterized by unique structural, physical, electrical and optical features such as high hardness (Chaneliere et al. 1998), high dielectric strength (Rahmati et al. 2016) and high chemical attack resistance under severe conditions (Díaz et al. 2012a, b). It is implemented in different fields ranging from microelectronic to chemical and biomedical industries, synthesis of capacitors, sensor layers, anti-reflection coatings and optical waveguides (Abdeen et al. 2019). Research investigations related to pentoxide nanocoating showed enhancement in corrosion properties. Hu et al. (2016) reported that coating Ti-6Al4 V alloy with β-Ta2 O5 resulted in conferring anti-corrosion resistance by forming a passive oxide layer on its surface in NaOH solution. Electrochemical measurements showed high corrosion potential values and low corrosion current density when compared with the uncoated Ti-6Al-4 V alloy. In another study performed by Díaz et al. (2012a, b), no dissolution of 50 nm tantalum oxide coated carbon steel took place in acidic medium. Impairment of equipment because of corrosion is a great problem in chemical and petrochemical industries. Several environmental parameters affect the corrosion of pipe materials, such as, temperature, salinity, pH, etc. These factors exhibit an important role in inducing corrosion of construction materials. Corrosion can be reduced either by altering such environmental factors but sometimes these factors are hard to control, or by repairing the damaged equipment themselves. As previously mentioned, coating is one of the important techniques for corrosion control, particularly epoxy coating. Epoxy coatings have attracted great attention owing to its wide applications as flame retarding additive and anti-corrosion coating. It is important to emphasize that the combination between organic phases (usually polymers) with inorganic particles became very enthusiastic. This is because NPs help in enhancing the mechanical features of the polymer (Hussein et al. 2016). In a recent study performed by Khodair et al. (2019), the anti-corrosion effect of epoxy coating was tested against mild steel in different aqueous solutions at different operating conditions. Corrosion rate was followed up by weight loss technique. Corrosion rate of mild steel was evaluated as a function of temperature, pH, and salt concentration in presence and absence of epoxy coating. It was found that epoxy coating achieved corrosion inhibition efficiency of about 97% in acidic solution, whereas the effect of epoxy coating was weak in saline solution. An attempt was carried out to increase the efficiency of epoxy coating by the incorporation of sol gel prepared magnesium oxide (MgO) NPs. MgO NPs upgraded the efficiency of epoxy coating in saline solution with a maximum coating efficiency of 93.7%. This was confirmed via SEM which showed less damage in presence of coating along with the prepared MgO NPs.

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It is important to keep in mind that most of the reported data regarding the use of nanomaterials in oil and gas facilities are based upon laboratory experiments. Nonetheless, few field trials have been carried out. Listed below two examples of these field trials: • In Saudi Arabia, carbon-based fluorescent nanoparticles proved to be highly stable in harsh formation conditions. Results showed high recovery percentage of up to 86% (Kosynkin and Kanj 2011). • In Colombia, aluminum oxide nanosilica have been used and after eight months of injection, the oil rate has increased by 300bbl/d (Franco et al. 2017).

4.7 Conclusions and Challenges Facing Nanotechnology in Oil and Gas Industries Even with the increasing number of studies with respect to the high possibility of using NPs, there are some challenges that are still controversial. Regarding economic feasibility, some NPs are relatively higher in cost compared to conventional materials. The reason behind the high cost is mainly due to the shortage of commercially available NPs for oil and gas applications, even though there is a good number of major oil services companies which invest a lot in terms of research and development with respect to nanotechnology. The second challenge is related to their effectiveness when applied to a pilot scale in the field rather than the laboratory scale experiments. This challenge requires better cooperation between oil companies and researchers to validate their application on large scale. The third challenge comes from the impact of NPs on human health, safety and surrounding environment. They can be lethal and might lead to intense health issues, since they have higher potential to be inhaled or absorbed through skin. This is due to their distinctive features in terms of size and surface-to area ratio. Accordingly, principles, regulations, working guidance, recommended practices are being established by regulatory agencies like local and international Environmental Protection Agencies (EPA), International Standardization Organization (ISO), American Society for Testing and Materials (ASTM) to minimize or avoid associated risks during handling of nanoparticles.

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Chapter 5

Biologically Fabricated Nanomaterials for Mitigation of Biofouling in Oil and Gas Industries

Abstract Oil and gas industries suffer from a severe problem represented in biofouling. Biofouling occurs due to the colonization of micro-and macro-organisms on the surface of metallic structures. Biofouling has catastrophic economical, financial, environmental and health implications. It results in loss/contamination of products, high energy and fuel consumption, air pollution, etc. Hence, anti-biofouling strategies have been extensively investigated in the last few years. These strategies include the usage of biocides and protective paints and coatings. However, the worldwide new trend is to employ nanobiotechnology to eradicate biofouling negative impacts. Nanobiotechnology is a science in which different scientific fields are combined altogether including; nanotechnology, biotechnology, materials science, physics, chemistry and biology. Although, physical and chemical synthesis approaches produce nanoparticles with definite size and shape, nevertheless, these synthetic methodologies have some disadvantages such as complication, high costs, production of hazardous byproducts which are lethal to the environment as well as human health. Moreover, physical and chemical synthesis methods require the presence of external chemical reducing and capping agents. Biological synthesis of nanoparticles depends on using biological entities such as bacteria, fungi, actinomycetes, algae, agro-industrial wastes and plant extracts. This chapter summarizes the different biological entities that can be used as nano-bio-factories. It also emphasizes the-state-of the-art of the possible use of biogenic nanomaterials as effective biocides to mitigate biofouling. Keywords Biofouling mitigation · Nanobiotechnology · Biological synthesis · Nanoparticles · Nano-bio-factories

5.1 Introduction Nanotechnology has been considered as the next industrial revolution. Nanotechnology basically deals with the manufacturing of nanomaterials or particles with a dimension between 1 and 100 nm (Alghuthaymi et al. 2015). Metal and metal oxide nanoparticles have gained significant interest in the past decade because of © Springer Nature Switzerland AG 2020 B. A. Omran and M. O. Abdel-Salam, A New Era for Microbial Corrosion Mitigation Using Nanotechnology, Advances in Material Research and Technology, https://doi.org/10.1007/978-3-030-49532-9_5

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their unique physio-chemical properties as they have the potential to be used in a wide range of applications. Although, physical and chemical methodologies used for synthesizing nanoparticles produce excellent shapes with definite size control; however, they are largely restricted. The physical and chemical methods are complicated, expensive and produce hazardous toxic wastes that are hazardous to environment as well as human health. To solve this problem, synthesis of nanoparticles using biological entities became an innovative approach, because of its simplicity, rapid synthesis, controlled toxicity, controlled size characteristics, and its eco-friendliness (Schröfel et al. 2014). To fulfil the growing need to develop environmentally friendly nanoparticle synthesis methods, it was desirable to take advantage of extracts of plant parts, cell filtrates of microorganisms including; bacteria, yeast and fungi. Extracts of agro-industrial wastes can be also consumed for the biological synthesis of NPs (Nava et al. 2017; Omran et al. 2018a; Ajmal et al. 2019). Microorganisms have recently been explored as potential eco-friendly bio-nano-factories for the synthesis of metallic NPs such as, gold nanoparticles (AuNPs) (Tahar et al. 2019), copper nanoparticles (CuNPs) (Shantkriti et al. 2014), cobalt nanoparticles (CoNPs), platinum nanoparticles (PtNPs) and iron NPs (Saif et al. 2016) and silver nanoparticles (AgNPs) (Manimaran and Kannabiran 2017; Omran et al. 2018b, c). Extracts of agro-industrial wastes and plant parts offer another option for synthesis of NPs as natural sources free from toxic chemicals as reported by Omran et al. (2018a) and Seifpour et al. (2020). In recent trends, nanoparticles synthesized via biological sources have been found to be effective, eco-friendly and non-toxic means against micro-fouling (Pugazhendhi et al. 2018). The employment of nanotechnology and nanobiotechnology have attracted a worldwide attention to control biofouling problems as demonstrated in several studies (Zhang et al. 2012; Inbakandan et al. 2013; Kumar et al. 2014 and Martinez-Gutierrez et al. 2014; Shankar et al. 2016; Yang et al. 2016; Omran et al. 2018c).

5.2 Definition of Nanobiotechnology Several decades ago, metal nanoparticles (NPs) attracted significant attention because of their superior physicochemical characteristics. They were basically synthesized via different chemical and physical techniques. Nevertheless, these methods had the potential to successfully synthesize NPs with the desirable size and shape, yet they are quite complicated, expensive and the synthesis procedures involve the use of toxic chemical substances (Remya et al. 2017; Omran et al. 2018a, b; El-Gendy and Omran 2019). Therefore, extensive research has been performed to overcome such disadvantages of the chemical and physical synthesis techniques. Synthesis of NPs via green chemistry approaches is simple, one pot, cost effective, eco-friendly approach and can be easily scaled up to large-scale production (Govindappa et al. 2016; Yadav et al. 2017). Two of the most promising technologies of the 21st century are nanotechnology and biotechnology (El-Gendy and Omran 2019). Bionanotechnology/nanobiotechnology are recent terms that refer to “the intersection between

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biology and nanotechnology” (Fortina et al. 2007). Bionanotechnology is usually defined as “the study of how the objectives of nanotechnology can be directed and reached via biological “machines” and how they can be adapted to improve the existing nanotechnological techniques or via creating new techniques”. Biological synthesis of NPs does not involve the addition of any external reducing, capping and stabilizing agents as they become replaceable by the biological molecules existed within the used biological entity. These biological entities are referred to as “nano-bio-factories” (Jeevanandam et al. 2016).

5.3 Biological Entities Employed for Generation of NPs The key practical objectives of nanobiotechnology are making usage of biological constituents to fabricate nanoscale materials. These biogenic materials have diverse applications including biological and non-biological ones. Biological applications include medicine and biology. While, non-biological applications involve computing and electronics. The purpose of the following section is to show the wide range of applications of biologically fabricated metal and mrtal oxide NPs. Table 5.1 summarizes some selected examples of the state-of the-art publications regarding the synthesis of biogenic nanomaterials, their characteristics (size and shape) and their possible applications. Figure 5.1 shows a schematic representation of the different biological entities used for the synthesis of nanoparticles, optimization of process parameters and the different characterization techniques.

5.3.1 Use of Microorganisms for Production of Nanomaterials Microorganisms paly an alternative role for the synthesis of NPs as the existed biomolecules like proteins and enzymes within the microbial biomass act as reducing and capping agents during synthesis (Khandel and Shahi 2018; El-Gendy and Omran 2019). Numerous microorganisms have the potential to synthesize NPs. The use of microorganisms as biological entities for the production of nano-sized materials is an innovative methodology. So far, microorganisms are extremely diverse living creatures across the globe mainly due to their enriched genetic diversity. Biological synthesis of NPs using microorganisms has plenty of advantages. It is a cost effective route of synthesis, less complicated, less time consuming and most significantly non-toxic. Moreover, it has been realized that some of the applications of NPs are only feasible via the biological mode of synthesis i.e. clinical and medical applications (Malik et al. 2014). Another exciting aspect of microbially derived NPs is the provision of an excellent yield in a particular time span. An additional advantage is the fact that it is a bottom-up approach which requires less energy consumption, less input wastage and more control of the reaction constituents (Malik et al. 2014).

CuNPs

AgNPs

AgNPs

AuNPs

PtNPs, PdNPs, AuNPs

AgNPs

AgNPs

AuNPs, AgNPs

Arsenic sulfide

AuNPs

ZrO2 NPs

Bacillus sphaericus and Zeuxine gracilis

Pseudomonas sp.

Rhodobacter sphaeroides

Shewanella loihica PV-4

Pseudomonas aeruginosa

Bacillus subtilis KMS2-2

Photorhabdus luminescens

Engineered Escherichia coli

Paracoccus haeundaensis BC74171

Acinetobacter sp. KCSI1

Type of produced NPs

Shewanella oneidensis

Bacteria

Biological entity

Spherical Spherical Spherical

Spherical

246 ± 381 20.93 ± 3.46

15 ± 2

Spherical

14–46

18–153

Chellamuthu et al. (2018)

Aiswarya et al. (2019)

Mathivanan et al. (2019)

Quinteros et al. (2019)

Ahmed et al. (2018)

Italiano et al. (2018)

Singh et al. (2018)

Cytotoxic activity

Suriyaraj et al. (2019)

Antioxidant activity, Patil et al. (2019) antiproliferative effect



Larvicidal activity

Antimicrobial activity

Antimicrobial activity

Spherical

25 ± 8

Degradation of nitroaromatic Compounds

Antimicrobial activity

Catalytic activity

Spherical

10 ± 3

Kimber et al. (2018)

References

Larvicidal, ovicidal, Kovendan et al. (2018) adulticidal activities

Catalytic activity

Application

PtNPs (2–10), PdNPs Spherical (2–12), AuNPs (2–15)

Irregular

Irregular

Spherical

Shape

10–40

50

20–40

Size (nm)

Table 5.1 Selected examples of biologically fabricated metal and metal oxide nanoparticles, size, shape and their possible applications

(continued)

162 5 Biologically Fabricated Nanomaterials for Mitigation …

Penicillium italicum

Fungi

AgNPs

Nocardiopsis dassonvillei DS013 AgNPs

CuO NPs

Streptomyces zaomyceticus Oc-5 and Streptomyces pseudogriseolus Acv-11

33

30–80

Streptomyces zaomyceticus Oc-5 (78), Streptomyces pseudogriseolus Acv-11 (80)

Irregular

Circular

Spherical



Antimicrobial activity

Antibacterial activity

Antimicrobial, antioxidant, cytotoxic, larvicidal efficacy

Antimicrobial and cytotoxic activities

AgNPs

Streptomyces sp. AU2



Antifungal and anti-biofilm activities

Spherical

10 ± 5

AgNPs

Acinetobacter sp.

Antifungal and cytotoxic activities

Antimicrobial activity

Application

Antimicrobial and cytotoxic activities

Spherical

Spherical

Shape

S. calidiresistens IF11 Spherical (5–50), S. calidiresistens IF17 (5–20)

12.7

20–70

Size (nm)

Streptomyces calidiresistens IF11 AgNPs and IF17 strains

Pilimelia columellifera subsp. pallida SL19

AgNPs

AgNPs

Pseudomonas strain

Actinomycetes

Type of produced NPs

Biological entity

Table 5.1 (continued)

Nayak et al. (2018)

Dhanaraj et al. (2020)

Hassan et al. (2019)

Baygar et al. (2019)

Nadhe et al. (2019)

Wypij et al. (2018)

Wypij et al. (2017)

John et al. (2020)

References

(continued)

5.3 Biological Entities Employed for Generation of NPs 163

Type of produced NPs

SeNPs

AgNPs

Cobalt oxide NPs

AgNPs

PtNPs

PdNPs

AgNPs

AuNPs

ZnO NPs

CuO NPs

Co3 O4

Biological entity

Aspergillus oryzae

Trichoderma longibrachiatum

Aspergillus nidulans

Aspergillus brasiliensis

Fusarium oxysporum

Phanerochaete chrysosporium

Cladosporium cladosporioides

Fusarium oxysporum

Cochliobolus geniculatus

Penicillium chrysogenum

Aspergillus brasiliensis ATCC 16404

Table 5.1 (continued)

20–27

10.7

2–6

22–30

30–60

10–14

25

6–21

20.29

1–25

55

Size (nm)

Quasi spherical

Spherical

Quasi spherical

Spherical and hexagonal

Spherical

Spherical

Cubical, spherical and truncated triangular

Spherical

Spherical

Spherical

Spherical

Shape

Antimicrobial activity

Antimicrobial activity



Antibacterial activity

Antimicrobial and antioxidant activities

Catalytic activity

Antimicrobial, antioxidant and photocatalytic activities

Antimicrobial activity

Energy storage

Antifungal activity

Antimicrobial activity

Application

Omran et al. (2019)

El-Batal et al. (2019)

Kadam et al. (2019)

(continued)

Naimi-Shamel et al. (2019)

Hulikere and Joshi (2019)

Tarver et al. (2019)

Gupta and Chundawat (2019)

Omran et al. (2018b)

Vijayanandan and Balakrishnan (2018)

Elamawi et al. (2018)

Mosallam et al. (2018)

References

164 5 Biologically Fabricated Nanomaterials for Mitigation …

SeNPs

AuNPs

Trichoderma sp.

Fusarium solani ATLOY—8

AgNPs

AgNPs

Selenium sulphide 6–153 NPs

Rhodotorula sp. strain ATL72

Candida glabrata

Saccharomyces cerevisiae

Nanorods

AgNPs

Lantana camera

Maclura pomifera

Leaf extracts

Extracts of different plant parts

AgNPs

12

10–20

2–15

8.8–21.4

160–220

AgNPs

Cryptococcus laurentii and Rhodotorula glutinis

2–20

40–45

20–220

Size (nm)

Saccharomyces cerevisiae

Yeast

Type of produced NPs

Biological entity

Table 5.1 (continued)

Spherical

Nanorods

Spherical

Spherical

Spherical, oval

Spherical

Spherical

Needle and flower like structures with spindle shape

Spherical

Shape

Antimicrobial activity

Biological activity

Antifungal and cytotoxic activities

Antimicrobial activity

Antimicrobial activity

Antifungal activity



Anticancer activity



Application

(continued)

Azizian-Shermeh et al. (2017)

Rajiv et al. (2017)

Asghari-Paskiabi et al. (2019)

Jalal et al. (2018)

Soliman et al. (2018)

Fernández et al. (2016)

Korbekandi et al. (2016)

Clarance et al. (2020)

Diko et al. (2020)

References

5.3 Biological Entities Employed for Generation of NPs 165

AuNPs

ZnO NPs, AgNPs, ZnO NPs (12.9), ZnO/Ag NPs AgNPs (32.8), ZnO/Ag NPs (19.3 to 67.4)

ZnO NPs

CuO NPs

AgNPs

Alcea rosea

Mirabilis jalapa

Costus igneus

Ruellia tuberosa

Diospyros lotus

20

83.23

26.55

4–95

22–94

ZnO NPs

Bauhinia tomentosa

Size (nm)

Type of produced NPs

Biological entity

Table 5.1 (continued)

Antibacterial activity

Application

Spherical

Rods

Hexagonal

Antibacterial and catalytic activities

Antibacterial activity and dye degradation (Fabrication over textile fabrics)

Anti-diabetic, anti-biofilm and anti-oxidant activities

ZnO NPs Biological activity (needle like), AgNPs (spherical), ZnO/Ag NPs (plates, sheets, and spherical)

Triangular, Antioxidant and pentagonal, catalytic activities hexagonal and spherical

Hexagonal

Shape

(continued)

Hamedi and Shojaosadati et al. (2019)

Vasantharaj et al. (2019)

Vinotha et al. (2019)

Sumbal et al. (2019)

Khoshnamvand et al. (2019)

Sharmila et al. (2019)

References

166 5 Biologically Fabricated Nanomaterials for Mitigation …

AgNPs

Fe NPs

AgNPs

AgNPs

Rauvolfia tetraphylla

Rhamnella gilgitica

Melia azedarach

Capparis zeylanica

AuNPs

AgNPs

AgNPs

Elettaria cardamomum

Salvia hispanica L.

Tectona grandis

Seeds

Type of produced NPs

Biological entity

Table 5.1 (continued)

10–30

7

15.2

28

23

21

40

Size (nm)

Oval and spherical

Spherical

Spherical

Spherical

Spherical

Spherical

Spherical

Shape

References

Antimicrobial activity

Antibacterial activity

Antioxidant, antibacterial and anticancer activities

Antimicrobial and anti -proliferation activities

Antifungal activity

Rautela et al. (2019) (continued)

Hernández-Morales et al. (2019)

Rajan et al. (2017)

Nilavukkarasi et al. (2020)

Jebril et al. (2020)

Antibacterial and Iqbal et al. (2020) antifungal activities, anticancer potential, brine shrimp cytotoxicity, antioxidant capacity, antileishmanial potential

Anticancer, Vinay et al. (2019) antioxidant and antimitotic activities

Application

5.3 Biological Entities Employed for Generation of NPs 167

ZNo NPs

AgNPs

Hydroxyapatite NPs

Type of produced NPs

AgNPs

FeNPs

ZnO NPs

AuNPs

AgNPs

Dragon fruit

Citrus maxima

Lycopersicon esculentum (tomato), Citrus sinensis (orange), Citrus paradisi (grapefruit) and Citrus aurantifolia (lemon)

Vitis vinifera

Dimocarpus longan

Agro-industrial waste extracts and Peels

Thymus vulgaris L

Thyme waste

Senna alata

Bark extracts

Parkia biglobosa

Pulp extracts

Biological entity

Table 5.1 (continued)

Spherical Irregular spherical

38.6 ± 7.0

Polyhedral

20–40

Irregular

9.7 ± 3

Spherical

Cubical, rectangle, radial hexagonal and rod

Spherical

Irregular

Shape

10–100

25–26

10–35

10–35

17.5–26.3

Size (nm)

References

Antibacterial activity

Anticancer and cytotoxic activities

Photocatalytic activity

Removal of heavy metals

Antibacterial activity



Antimicrobial activity

Antibacterial activity

Application

(continued)

Phongtongpasuk et al. (2017)

Nirmala et al. (2017)

Nava et al. (2017)

Wei et al. (2016)

Phongtongpasuka et al. (2016)

Abolghasemi et al. (2019)

Ontong et al. (2019)

Ibraheem et al. (2019)

168 5 Biologically Fabricated Nanomaterials for Mitigation …

AgNPs

TiO2 NPs

Tangerine

AuNPs

Dragon fruit

Citrus macroptera

AgNPs

Grape and orange

Nanocellulose

ZnO NPs

Punica granatum

FeO NPs

AgNPs

Longan fruit

Punica granatum

AgNPs

Citrus sinensis

Pyrus pyrifolia

Type of produced NPs

Biological entity

Table 5.1 (continued)

Spherical and cubic

10.32 ± 2.87

50–150

Undefined

Spherical

Spherical

20.5 ± 6.3

16

Spherical, oval and triangular

Spherical

Spherical and hexagonal

Rounded

Spherical

Shape

10–20

Grape (3–14), orange (5–50)

32.98

20

15

Size (nm)

References



Anti-biofilm activity

Anticancer activity



Anticancer activity

Antimicrobial and antibacterial activities

Antibacterial and cytotoxic activities

Antiproliferative, antioxidant and photocatalytic activities



Application

Rueda et al. (2020)

Majumdar et al. (2020)

Yusefi et al. (2020)

Chen et al. (2019)

Divakaran et al. (2019)

Soto et al. (2019)

Sukri et al. (2019)

Khan et al. (2018)

Omran et al. (2018a)

5.3 Biological Entities Employed for Generation of NPs 169

Fig. 5.1 Schematic representation showing synthesis, optimization and characterization techniques

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5.3 Biological Entities Employed for Generation of NPs

171

Biological synthesis of NPs also enhances the biocompatibility, stability and reduced toxicity chiefly because of the coating by the biological molecules and the natural capping agents (Schröfel et al. 2014). The interaction between metals and microbes has been extensively studied in multiple biological fields such as bioremediation, bioleaching, biocorrosion and biomineralization (Klaus-Joerger et al. 2001).

5.3.1.1

Biological Synthesis of NPs Using Bacteria (Prokaryotic Micro-machine)

Early studies revealed that bacteria are among the first microorganisms being employed for synthesis of metal NPs because they are easily cultivated and manipulated. Bacterial synthesis of metal NPs occurs as a defence mechanism or resistance mechanism. The stress caused by the metal ions on bacterial cells is responsible for the synthesis of metal NPs (Saklani and Suman 2012). Generally, the biological molecules such a proteins and enzymes are involved in the bioreduction of metal ions to their nano-scale particles (Mukherjee et al. 2008). Bacterial synthesis of nanomaterials takes place either extracellularly or intracellularly as illustrated in Fig. 5.2. Roh et al. (2001) demonstrated the capability of magnetotatic bacteria Magnetospirillium magneticum to biologically synthesize magnetic NPs. Two types of NPs were generated i.e. magnetite nanoparticles (Fe3 O4 ) in chains in addition to greigite (Fe3 S4 ) NPs. Husseiny et al. (2007) reported the synthesis of gold nanoparticles (AuNPs) using Pseudomonas aeruginosa supernatant. Interestingly, bacterial cell free filtrate possesses an important role in controlling shape, size and polydispersity of the prepared NPs. Lengke et al. (2007) investigated the ability of a filamentous cyanobacterium Plectonema boryanum UTEX485 to biologically biotransform gold ions into AuNPs. Kalabegishvili et al. (2012) reported the biological synthesis of AuNPs by some Arthrobacter genera (e.g. Arthrobacter globiformis). Srivastava et al. (2013) reported the biosynthesis of 50 nm sized AuNPs via E. coli K 12. Shantkriti and Rani (2014) reported the biosynthesis of CuNPs and CuO NPs via Pseudomonas fluorescens. CoNPs were synthesized using Bacillus thuringiensis as reported by Marimuthu et al. (2013). Elbeshehy et al. (2015) performed a study in which different Bacillus sp. were able to synthesize AgNPs with a size ranging from 77 to 92 nm including; B. pumilus, B. persicus and B. licheniformis. Likely, Desulfovibrio desulfuricans NCIMB 8307 is a sulfate-reducing bacterium which had the potential to synthesize palladium NPs in presence of exogenous electron donor (Omajali et al. 2015). Ezzat and Abou El-Hassayeb (2016) investigated the biosynthesis of AgNPs via Pseudomonas aeruginosa ATCC 9027. Rajora et al. (2016) reported the synthesis of extracellular AgNPs from P. stutzari AG259 which was isolated from silver mines. Likewise, Omajali and his colleagues demonstrated the ability of Bacillus benzeovorans to produce palladium NPs (PdNPs). Lactobacillus species which are usually found in butter milk were reported to synthesize well defined gold, silver and gold-silver nano crystals (Khandel and Shahi 2018). The reaction between P. boryanum and the aqueous solution of Au (S2 O3 ) and HAuCl−4 resulted in synthesis of cubic and octahedral AuNPs. Pyrococcus furiosus,

Fig. 5.2 Representative scheme showing the extracellular and intracellular biological synthesis of nanomaterials using bacterial cultures

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5.3 Biological Entities Employed for Generation of NPs

173

Thermotoga maritime, Geobacter sulfurreducens and Pyrobalaculum islandicum were reported to have the potential to extracellularly reduce metallic gold ions into AuNPs in presence of hydrogen as an electron donor (Ahmed and Aljaeid 2016).

5.3.1.2

Biological Synthesis of NPs Using Actinomycetes (Prokaryotic Micro-machine)

Actinomycetes are microorganisms that possess properties relevant to both fungi and bacteria and secrete lots of secondary metabolites (Manimaran and Kannabiran 2017). Actinomycetes managed to develop numerous adaptation mechanisms in extreme habitats such as enzyme transduction, metabolism regulation, maintenance of membrane function and structure. Golinska et al. (2014) demonstrated the ability of extremophilic actinomycetes such as Thermomonospora sp. to produce AuNPs extracellularly. Actinomycetes such as Streptomyces rochei MHM13 (Abd-Elnaby et al. 2016), Streptacidiphilu durhamensis (Buszewski et al. 2016), and Streptomyces graminofaciens (Kamel et al. 2016) were reported to synthesize AgNPs. Składanowski et al. (2016) performed a study in which AgNPs and AuNPs were biologically fabricated from a soil isolated strain Streptomyces sp. strain NH21 with a size of approximately 44 nm. Streptomyces sp. had the ability to synthesize AgNPs as demonstrated by Al-Hulu (2018).

5.3.1.3

Biological Synthesis of NPs Using Fungi (Eukaryotic Micro-machine)

Fungi belong to a kingdom of multicellular eukaryotic microorganisms that are heterotrophic and play an important role in nutrient cycling. Fungi reproduce both sexually and asexually. They have symbiotic relationships with bacteria and plants. Fungi include moulds, mildews, yeast as well as mushrooms (Duhan et al. 2017). Myconanotechnology refers to “the biological synthesis of nanoparticles using fungi” (Omran et al. 2018b, c). Nowadays, fungi are considered one of the best nano-biofactories (Gulhane et al. 2016; Sriramulu and Sumathi 2017) as they possess many advantages over the other microorganisms (Madakka et al. 2018). Fungal mycelia have the potential to resist agitation, flow pressure and many other stress conditions compared with bacteria. They are easy to handle and grow easily. Additionally, fungal mycelia produce more proteins and enzymes than bacteria which are directly involved in the bioreduction and stabilization of the synthesized NPs. Besides, it can be easily handled in downstream processing. Fungi are considered as the most effective candidates for metal NPs synthesis in a large scale production compared with bacteria. This is because fungi secrete more amounts of proteins (Zomorodian et al. 2016). Additionally, they have very high wall binding capacity (Alghuthaymi et al. 2015). Moreover, fungi are highly tolerant for metal uptake compared with bacteria (Longoria et al. 2012). Metal ions attach to fungal cell surface via electrostatic interactions because of the presence of sticky adhesive substances. Fungi synthesize NPs

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both extracellularly and intracellularly (Omran et al. 2019). The presence of metabolites and enzymes leads to the conversion of toxic matter into non-toxic ones (Owaid and Ibraheem 2017). Mycogenesis of NPs has a great potential because of the wide diversity and availability of fungi. Trichoderma reesei was reported to synthesize AgNPs extracellularly (Velhal et al. 2016). Fungal-mediated synthesis of NPs has been proposed by either the action of nitrate reductase or electron shuttle quinones or both. Verticillium sp. was found to have the ability to reduce AuCl−4 and synthesize monodispersed AuNPs. The endophytic fungus Colletotrichum sp. isolated from Geranium leaf was used for the mycosynthesis of AuNPs (Kitching et al. 2015). The prepared AuNPs were highly stable with different shapes and sizes. It was suggested that the fungus contains enzymes and polypeptides which might act as reductants.

5.3.1.4

Biological Synthesis of NPs Using Yeast (Eukaryotic Micro-machine)

According to Narayanan and Sakthivel (2010), yeast driven metal NPs are mainly exploited for the manufacture of semiconductors. The controlled growth of yeast and the easiness in handling aids in their use in synthesis of NPs. Thakkar et al. (2010) demonstrated the capability of MKY3 a silver-tolerant yeast species to produce AgNPs extracellularly. Shenton et al. (1999) reported the capability of Candida glubrata to synthesize monodispersed spherically shaped cadmium sulphide (CdS) quantum crystallites intracellularly. C. albicans was reported to synthesize AuNPs as revealed by Chauhan et al. (2011). Additionally, C. utilis was proved to synthesize AgNPs as demonstrated by Waghmare et al. (2015). Furthermore, in a study conducted by Fernández et al. (2016), supernatant of both Rhodotorula glutinis and Cryptococcus laurentii was used successfully to synthesize AgNPs.

5.3.1.5

Biological Synthesis of NPs Using Viruses

Viruses are unicellular microorganisms and another type of biological entities that can be employed as a bio-template for the synthesis of NPs. Shah et al. (2015) demonstrated the capability of Tobacco mosaic virus (TMV) to synthesize semiconductor nano crystalline silicon dioxide (SiO2 ), CdS, zinc sulphide (ZnS), iron oxide (Fe2 O3 ) NPs. Interestingly, capsid proteins cover the viral surface for defense purposes, thus the surface becomes a highly reactive surface which is capable of interacting with metallic ions (Makarov et al. 2014).

5.3.2 Biological Synthesis of NPs Using Algae Algae are characterized by their ability to accumulate heavy metal ions. Chlorella vulgaris is a unicellular algae and it possesses the potential to reduce HAuCl−4 ions

5.3 Biological Entities Employed for Generation of NPs

175

into AuNPs as demonstrated by Luangpipat et al. (2011). The generated AuNPs were tetrahedral, decahedral and icosahedral in shape. Additionally, AgNPs were synthesized using the extract of same algal species C. vulgaris at room temperature as reported by Xie et al. (2017). It was conducted that the proteins present in the extract acted as reducing, shape controlling and stabilizing agents during the biosynthesis process. Sargassum weightii is a marine alga which was capable of synthesizing Au, Ag and Au/Ag bimetallic NPs extracellularly (Madhiyazhagan et al. 2015). Abdel-Raouf et al. (2017) used Galaxaura elongata for the extracellular synthesis of AuNPs. Synthesis of AuNPs and AgNPs was also reported by Castro et al. (2013) from the red and green algae Chondrus crispus and Spirogyra insignis, respectively. Iravani et al. (2014) reported the intracellular synthesis of AuNPs using Tetraselnis Kochinensis. Laminaria japonica (Ghodake and Lee 2011), Chlorella pyrenoidusa (Oza et al. 2012) and Sargassum myriocystum (Priya et al. 2013) were used for the biological synthesis of AuNPs. Saber et al. (2017) recorded the ability of aqueous extracts of Sargassum dentifolium and Jania rubens to biologically synthesize AgNPs. Pugazhendhi et al. (2018) reported the successful preparation of AgNPs using marine red algae Gelidium amansii.

5.3.3 Use of Plant Extracts for Nanoparticle Synthesis (Phytonanotechnology) Plants have been reported to be capable of synthesizing NPs. Phytonanotechnology possesses several advantages including; biocompatibility, low cost, environmental friendliness, one pot reactions and scalability to be applied in medical applications as water is the sole solvent being used (Singh et al. 2016). Different plant parts can be exploited in the synthesis of NPs for instance; the extracts of seeds, leaves, stems, roots and bark (Amooaghaie et al. 2015; El-Gendy and Omran 2019). Yet, the precise mechanism of plant mediated synthesis of NPs is still unclear. However, presence of biologically originated components such as amino acids, vitamins, proteins, carbohydrates, sugars, flavones, terpenoids, phenols, carbonyl groups, amines, amides, and alkaloids play significant role in metal salt reduction and in providing a biological shield around the synthesized NPs (Duan et al. 2015). Henceforth, ensuring the stabilization of the plant derived NPs (Tyagi 2016). Presence of different classes of phytoconstituents enables the steps of reduction, capping and stabilization to act properly (Mohanta et al. 2017; El-Gendy and Omran 2019). Philip (2011) demonstrated that the phytosynthesis of well-dispersed AgNPs with a size range of 20 nm was possible by using Mangifera indica leaf extract. The prepared AgNPs exhibited different shapes e.g. hexagonal, triangular and spherical shapes. In a study performed by Sekhar et al. (2016), AgNPs were synthesized by using the extracts of both leaves and bark of Limonia acidissima. The leaves and bark extracts of L. acidissima were found to involve several phytoconstituents such as saponins, phytosterols, phenolic compounds and quinines. Khalil et al. (2012) managed to synthesize AuNPs using

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olive leaf extract. Parkia speciosa Hassak pods’ extract was reported to possess the capability to synthesize AgNPs as demonstrated by Fatimah et al. (2016). Nickel oxide (NiO) NPs were successfully synthesized via Neem leaves’ extract as reported by Helan et al. (2016). Cobalt oxide (Co3 O4 ) NPs were successfully fabricated using the aqueous leaf extract of Sageretia thea (Osbeck.) as conducted by Khalil et al. (2020).

5.3.4 Use of Agro-Industrial Wastes for Nanoparticle Synthesis Different agro-industrial wastes are yielded from the food and juice processing industries during the separation of the edible parts from non-edible ones (Balavijayalakshmi and Ramalakshmi 2017). Huge quantities of agro-industrial wastes are generated annually worldwide including sugarcane bagasse, rice bran, wheat bran, corn cob, etc. Solid waste management (SWM) refers to “the process of gathering and treating all solid wastes” (Bello et al. 2016). This process involves different techniques for instance recycling, upcycling and disposal. The accumulation of agro-industrial wastes became a critical public issue which influences human health as well as the environment. It is worth mentioning that, waste management is not only restrained to the collection of wastes and their disposal but also involves the management processes which deal with collection, transportation, sorting and recycling/upcycling of such wastes. Milik (2011) demonstrated that SWM is majorly affected by people’s culture and their level of awareness. Consequently, environmental concerns related to such wastes started to increase. The leftover such as orange, lemon and pomegranate peels, shrimp shells, egg shells in addition to the organic fraction of the municipal solid wastes could be upscaled and valorized to valuable compounds (Ahmad et al. 2016; Reenaa and Menon 2017; El-Gendy and Omran 2019). An important part of biological synthesis of NPs is concerned with the utilization of vegetable and fruit waste peels in addition to agricultural wastes (Saxena et al. 2012). These readily available agro-industrial wastes act as natural reductants and capping agents to provide one pot reaction for the synthesis of NPs. Saxena et al. (2016) showed that the biological synthesis of NPs using extracts of different plant parts as well as the agro-industrial wastes are more advantageous than the microbially originated NPs as they are devoid from the steps of culturing and cell maintenance (Saxena et al. 2016). For instance, citrus fruits are predominantly consumed by humans either as fresh fruits or as processed juices. After the juice is extracted from the fruit, some wastes remain involving seeds, peels and rags (cores and membranes) (Mamma and Christakopoulos 2008). According to Nassar (2008), 50% of the total weight of citrus fruits remains as a waste, hence extreme amounts of waste by-products are yielded each year (Parida et al. 2011). According to United States Department of Agriculture (USDA 2017), the global production of Citrus reticulum (mandarin/tangerine) for 2016/17 reached approximately 28.4 million metric tons. Mandarin is one of the most commercial fruits

5.3 Biological Entities Employed for Generation of NPs

177

produced in Egypt. According to USDA (2017), Egypt is one of the main contributors in mandarin production. Mandarin peels represent approximately 25% of the total fruit weight. As a result, Egypt suffers from a huge amount of mandarin peels’ waste leading to an enormous waste management problem. It is worth mentioning that Egypt’s main competitors in the international marketplace are recorded to be Turkey, Spain, Morocco and South Africa. Other competitors include United States, China, Australia, and Argentina. Balady mandarin (Citrus reticulatum, Blanco) is one of the most important citrus fruits in Egypt after Balady orange and has a good flavour and odour (Mohamed 2015). Mandarin peels are considered as the waste product obtained from the mandarin fruit which extensively cause significant waste issue particularly for juice shops and industries. The largest and the most cultivated fruit grown worldwide is Citrus sinensis (sweet orange) as it accounts for approximately 70% of the total annual production of Citrus species (Favela-Hernández et al. 2016). According to FRUIT LOGISTICA (2015), Egypt is considered the official partner country at the leading international trade fair for the fresh citrus producers. Egypt’s main exports are primarily to Russia, Saudi Arabia and Great Britain. Iraq, United Arab Emirates, Libya and Italy. Netherlands and Kuwait are also important customers. Export volumes rose from 1.7 million tonnes in the 2005/2006 season to 2.9 million tons in the 2013/2014 season, with an increment of 69%. According to Global Agricultural Information Network (GAIN), Egypt is ranked as the world’s sixth largest orange producer and the second biggest exporter in 2013/2014 (Hamza 2013). Many orange varieties are produced in Egypt but six are the most dominant: baladi orange, valencia orange, blood orange, navel orange, khalily orange and sweet orange (sukari). During orange juice production, approximately 50–60% of the processed fruit weight is converted to wastes including; peels, seeds, and membrane residues (Garcia-Castello et al. 2011). Henceforth, huge amounts of orange peels are produced annually and small portion of it is used as raw material in animal feed production. However, these wastes are sometimes left to rot or to be incinerated, which exert serious environmental threats (Miran et al. 2015). The reuse of industrial orange peel wastes is vital to meet twin objectives of resource upcycling/valorization and waste minimization. Thereby, producing valuable products and saving the environment from the deleterious effects produced from the accumulation of such waste. Basavegowda and Lee (2013) reported the biosynthesis of AgNPs using Satsuma mandarin (Citrus unshiu) peel extract. Mango peel extract has been utilized to synthesize AgNPs with a size range of 7–27 nm (Yang and Li 2013). The water extract of corn leaf waste of Zea mays was reported to have the capability to biologically synthesize AgNPs as demonstrated by Patra and Hyun-Beak (2017). Agricultural wastes such as banana peel (Bankar et al. 2010) and apple peels (Roopan et al. 2011) have been used to produce palladium nanoparticles (PdNPs). Lakshmipathy et al. (2014) reported that watermelon (Citrullus lanatus) peels had the potential to synthesize PdNPs. Punica granatum (pomegranate) peel extract was successfully used in the biosynthesis of AuNPs as reported by Ahmad et al. (2012). Carica papaya peel mediated the synthesis of AgNPs as reported by Balavijayalakshmi and Ramalakshmi (2017). Ulla et al. (2014) and Bibi et al. (2017) used a cost effective green synthesis method to synthesize cobalt oxide nanoparticles

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by using cobalt nitrate and pomegranate peel at ambient temperature. The synthesized cobalt oxide nanoparticles were 49 nm in size.

5.4 Critical Parameters Affecting the Biological Synthesis of NPs Different chemical and physical factors affect the synthesis of NPs such as metal ion/biomass (bio-extract) concentrations, pH, temperature, stirring rate and reaction time (Radhika et al. 2016) (Fig. 5.3). According to Ahmad et al. (2016), these factors are referred to as “altering factors” which need to be optimized during synthesis Biological synthesis Metal

Biological entities i.e. different plant parts and agro-industrial waste extracts Production of heterogeneous NPs with low yield

Optimization of process parameters

Processing parameters: 1- Reaction time 2- Mixed ratio of metal salt and extract concentrations 3- Temperature 4- pH 5- Shaking rate 6- Illumination

Modification of process

Production of homogenous capped and stabilized nanoparticle s with high yield

Controlled shape and morphology of the prepared NPs Fig. 5.3 Parameters which affect the production of monodispersed, stable, and high yielded biologically synthesized nanoparticles

5.4 Critical Parameters Affecting the Biological Synthesis of NPs

179

of NPs. In a study performed by Pimprikar et al. (2009), biomolecules which were involved in biological synthesis of NPs were inactivated under extremely acidic conditions. Contrary, formation of NPs is achieved promptly in both neutral and basic environments. This may be attributed to the ionization of the existed active groups. Temperature is considered one of the important physical factors which affect synthesis of NPs. Liang et al. (2017) revealed that synthesis of NPs increases with the increase in reaction temperature.

5.5 Employment of Biologically Synthesized Nanoparticles as Biocides and Corrosion Inhibitors Extract of marine sponge A. elongate was reported to possess the potential to reduce silver ions to yield uniform AgNPs as demonstrated by Inbakandana et al. (2013). Different 16 marine biofilm forming strains were isolated and collected from air—seawater interface at the bottom of a hull of a fishing vessel at Ennore harbor located North of Chennai Port, Chennai, India. The isolated strains were identified using 16S rDNA sequence analysis. The bacterial isolates were identified as Myroides odoratimimus; Micrococcus luteus; Halomonas aquamarina; Proteus mirabilis; Micrococcus luteus; Exiguobacterium aurantiacum; Exiguobacterium arabatum; Exiguobacterium arabatum; Jeotgalibacillus alimentarius; Bacillus megaterium; Bacillus pumilus; Bacillus pumilus; Bacillus pumilus; Bacillus megaterium; Halotalea alkalilenta; and Arthrobacter mysorens. Zone of inhibition (ZOI) confirmed the bactericidal potential and the anti-microfouling capability of the biologically synthesized AgNPs. In a study performed by Zhang et al. (2014), biogenic silver nanoparticles (bio-Ag0 ) was biologically fabricated using Lactobacillus fermentum LMG 8900. Zhang and co-workers prepared different concentrations of (bio-Ag0 ) and embedded it in polyethersulfone (PES) membranes via the phase-inversion technique. Silver nanoparticles were homogenously distributed on membrane surface as observed by SEM. Incorporation of bio-Ag0 increased the hydrophilicity of the PES membrane and improved the permeation flux. Two bacterial strains Pseudomonas aeruginosa and Escherichia coli, pure culture and a mixed culture of an activated sludge bioreactor were used to test the biocidal efficacy of bio-Ag0 /PES composite. It was found that the lowest concentration of biogenic silver (140 mg bio-Ag0 m2 ) exhibited an excellent antibacterial potential. Moreover, it managed to mitigate bacterial attachment to the membrane surface. Biofilm formation was decreased during the 9 weeks’ test. The anti-corrosive and the anti-biofouling effects of the biologically fabricated AgNPs against biofilm forming microbes and Artemia/Barnacles were demonstrated by Krishnan et al. (2015). Fresh samples of the brown alga Turbinaria ornata were collected from the coastal region of Mandapam in the Gulf of Mannar at the Bay of Bengal. Sterile seawater was used to clean the collected specimens. Afterwards,

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distilled water was used to remove any adhering debris associated with the specimens. Later, they were allowed to dry at room temperature for a week. The dried algal samples were converted to coarse powder using mortar and pestle. Structural composition of the prepared AgNPs was elucidated by SEM, FTIR, EDS, XRD. The derived AgNPs from T. ornata (TOAg-NPs) were evaluated against 15 biofilm forming bacterial isolates. The biologically synthesized TOAg-NPs was found to exert considerable biocidal activity against most of the bacterial isolates. Concentration of TOAg-NPs played a major role in the antimicrobial screening. Higher TOAg-NPs concentrations (80 µg/ml) expressed greater biocidal effect than the lower concentrations against all tested isolates. It was noted that the maximum inhibition zone was observed against Escherichia coli, whilst the minimum inhibition zone was noted against Micrococcus sp. Toxicity studies revealed 100% and 56.6% mortality for Balanus amphitrite and Artemia marina, respectively at a concentration of 250 µg/ml. Consquently, it can be denoted that TOAg-NPs is less toxic to non-target sea organisms. In a study performed by Sam et al. (2015), eleven brown, green and red sea weed extracts were evaluated for their capability to synthesize AgNPs. Padina boergesenii, Acanthophora najardiformis, Sargassum wightii represented the red seaweeds. Kappaphycus alvarazii and Gracilaria corticata represented the green seaweeds, while Gracilaria edulis, Caulerpa peltata, Caulerpa scalpelliforms, Ulva reticulata, Enteromorpha intestinalis and Ulva lactuca represented the brown seaweeds. Specimens were isolated from hare island, Tuticorin, India. The collected seaweeds were cleaned with tap water to remove any epi-fauna; debris and flora. Next, they were rinsed in double distilled water and were allowed to dry at room temperature for a fortnight. The dried seaweeds were ground and cleaned thoroughly for three times in an ultra-sonicator bath in order to get rid of any free salts and other debris. Then, one gram of the powdered seaweed was added to 100 ml of deionized water, heated, and maintained at 60°C for 20 min in order to obtain an aqueous extract for each one of the tested seaweeds. The prepared AgNPs was characterized using UV/Vis spectrophotometer. The UV/Vis spectra revealed the presence of a characteristic peak of AgNPs at 430 nm. SEM and TEM revealed the presence of spherical shaped non-agglomerated AgNPs with sizes ranging from 20 to 50 nm. The biogenic AgNPs was used to coat polyvinylchloride (PVC) coupons and were immersed for 45 days in natural seawater to establish a biofilm. The surface potential of the marine biofilm ranged between −39 and −45 mV. The control PVC coupons were found to be highly corroded and were completely covered with algal biomass. Contrary, the coated PVC coupons with the biogenic AgNPs were free from any algal biomass coverage. Additionally, the bacterial density in control PVC coupon was 106 times greater than the coupons coated with AgNPs. AgNPs derived from U. lactuca extract showed the best microbicidal efficiency against the biofilm consortia. A toxicity study was also performed on non-target sea organisms i.e. Artemia salina. The biologically prepared AgNPs exhibited the least lethal effect on A. salina. It was observed that during the first hour of the experiment 85% of the populations were alive; then, the survival rates were almost equal in both the control and test systems.

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In a study presented by Zonaro et al. (2015), Se0 and Te0 -based NPs were biologically synthesized by two selenite and tellurite reducing bacterial strains. The bacterial strains were Ochrobactrum sp. MPV1 and Stenotrophomonas maltophilia SeITE02. They were isolated from different polluted sites. SEM observations indicated that both SeNPs and TeNPs were well dispersed and circular in shape. Characteristic peaks of the purified SeNPs were detected by EDX analysis and revealed the presence of absorption selenium characteristic peaks at 1.37, 11.22, and 12.49 keV. While, TeNPs characteristic absorption peaks appeared at 3.769 keV. Authors observed that the diameter of the biogenic SeNPs increased with the elongation of incubation time. As the incubation time increased from 24 to 48 h, the diameter of the SeNPs reached 345.2 nm. Conversely, the diameter of TeNPs remained stable over time with value of 78.5 nm. The microbially prepared zerovalent selenium and tellurium NPs were evaluated for their antimicrobial and anti-biofilm eradication capability against three biofilm forming bacterial strains namely Pseudomonas aeruginosa PAO1, Escherichia coli JM109 and Staphylococcus aureus ATCC 25923. Experiments were performed to test the biocidal effect against planktonic and sessile (biofilm) cultures. Results revealed that the prepared Se0 and Te0 NPs exhibited antimicrobial and biofilm eradication activity against Pseudomonas aeruginosa PAO1, Escherichia coli JM109 and Staphylococcus aureus ATCC 25923. The biocidal effect was attributed to the generation of reactive oxygen species (ROS) upon exposure to bacterial cultures. Additionally, the results revealed the extreme relation between the antimicrobial activity and the dimensions of the prepared nanoparticles. Indeed, the highest antimicrobial potential was observed by small-sized NPs. Moreover, the sessile bacteria in the biofilm mode responded to the treatment by Se0 and Te0 NPs. This highlights the capability of both Se0 and Te0 NPs to be promising antimicrobial agents with a remarkable biofilm mitigation capacity. Elhariry et al. (2016) investigated the antimicrobial and anti-biofilm potential of microbially produced AgNPs against Kocuria rhizophila and K. rosea. Cell free supernatant of Proteus mirabilis culture was employed to biosynthesize AgNPs. Synthesis of AgNPs was confirmed by observing the colour change to yellowish brown by the help of the present proteins and carbohydrates within the supernatant of P. mirabili. UV/Vis absorption spectroscopy revealed the presence of AgNPs characteristic absorption peak at 445 nm. The resultant peak was sharp, indicating the monodispersity of the prepared AgNPs. XRD showed that the prepared AgNPs was crystalline with face centred cubic silver structure. TEM images demonstrated that P. mirabili derived AgNPs were spherical shaped and monodispersed with an average diameter of 20 ± 2.9 nm. Attenuated Total Reflection-Fourier Transform Infrared (ATR-FTIR) was used to identify the possible interactions between AgNPs and the bioactive molecules. It provided an evidence for the presence of proteins as possible biomolecules which might be responsible for the stability of the prepared AgNPs. Different concentrations of biosynthesized AgNPs 12.5, 25, and 50 µg/mL were tested against K. rosea HMA12 and K. rhizophila HMA23. Results assured the ability of AgNPs to inhibit the growth of K. rosea and K. rhizophila. The recorded MIC value of AgNPs against both strains was 25 µg/mL. Yet, the concentrations of AgNPs up to 100 µg/mL were not enough for the complete removal of already established

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biofilms. It achieved only a maximum removing percentage ranging between 30.5 and 34.9%. According to Narenkumar et al. (2018), plant derived AgNPs possessed anticorrosion potential and acted as an eco-friendly agent for the treatment of microbially influenced corrosion. This is the first report to disclose the application of bioengineered AgNPs as potent anti-corrosive inhibitor by forming a protective film on mild steel in cooling water towering systems. AgNPs were biologically fabricated via surface functionalization of the leaf extract of Azadirachta indica. A. indica leaf extract acted as a reductant and as a stabilizing agent. Characterization of the bioprepared AgNPs was performed by EDX, TEM, FTIR, DLS, zeta potential and singlearea electron diffractions. The anti-corrosion experiments were performed using mild steel (MS1010) and the corrosion causing bacterium, Bacillus thuringiensis EN2. B. thuringiensis was isolated from cooling water towering system. Corrosion was evaluated based on gravimetric techniques, electrochemical impedance spectroscopy (EIS), and surface analysis via infrared spectroscopy. The studies demonstrated that AgNPs strongly inhibited the biofilm on MS1010 surface and decreased the corrosion rate (CR) from 0.5 to 2.2 mm/y by using the plant extract alone. Authors revealed that the inhibition efficiency percentage upon using AgNPs reached 77%, while in case of the plant extract alone it recorded 52%. Further surface analysis by infrared spectra revealed that AgNPs formed a protective layer of self-assembled film on the surface of MS1010. Additionally, EIS along with surface analysis revealed that the AgNPs was clearly adsorbed onto the metal surface; thereby it could have formed a protecting layer and inhibited the bacterial attachment upon metal surface. So, corrosion was inhibited and the bacterial biofilm pits were reduced on MS1010. A study performed by Omran et al. (2018c) showed the capability of Trichoderma longibrachiatum DSMZ 16517 to effectively mitigate the corrosive sulphate reducing bacteria (SRB) via mycosynthesis of AgNPs. The mycelial cell-free filtrate (MCFF) of the tested fungus managed to bioreduce silver ions (Ag+ ) to its nanoparticle state (Ag0 ). This was presumptively observed by the change of T. longibrachiatum DSMZ 16517 MCFF colour to dark brown suspension (Fig. 5.4). This was further confirmed by the appearance of the characteristic absorbance peak of AgNPs at L422 nm. Optimization of the different parameters that would affect the production of AgNPs was assessed via the one-factor-at a-time technique (OFAT). These parameters included the effect of time, temperature, pH, silver nitrate and fungal biomass concentrations, stirring rates and dark and illumination effects. DLS revealed the average size distribution of AgNPs as well as zeta potential values of 17.75 nm and −26.8 mV, respectively. Therefore, indicated the stability of the mycosynthesized AgNPs. XRD pattern confirmed the crystallinity of the prepared AgNPs, with an average size of 61 nm. FESEM and HRTEM revealed the presence of non-aggregated rounded, triangular and cuboid shapes of AgNPs with size range from 5 to 11 nm (Fig. 5.5). FTIR assured the role of MCFF which acted as both reducing and capping agents (Fig. 5.6). The mycosynthesized AgNPs exerted a potent biocidal activity against a mixed culture of a halotolerant planktonic SRB as observed by the most probable number (MPN) technique. HRTEM displayed a clear evidence for the alteration in cell morphology, disruption in SRB cell membranes, lysis in cell wall and a cytoplasmic leakage after

5.5 Employment of Biologically Synthesized Nanoparticles …

183

Fig. 5.4 UV/Vis spectrum of the prepared silver nanoparticles (AgNPs) (Omran et al. 2018c)

treatment with AgNPs (Figs. 5.7 and 5.8). These observations further confirmed the bactericidal effect of the mycosynthesized AgNPs. This research provides a helpful insight into the developing a new mycosynthesized biocidal agent that possesses an inhibitory effect against the corrosive SRB. Henceforth, it could be incorporated within the paints and coatings of pipelines. According to Pugazhendhi et al. (2018), marine red algae Gelidium amansii was used to biologically synthesize AgNPs. The prepared AgNPs was characterized via UV/Vis spectroscopy, FTIR and SEM. Further, the prepared AgNPs displayed prominent effect against some microfouling bacteria including; Staphylococcus aureus, Bacillus pumilus, Escherichia coli, Aeromonas hydrophila, Pseudomonas aeruginosa and Vibrio parahaemolyticus. Therefore, the prepared AgNPs from G. amansii extract could be used within anti-microfouling coatings in several environmental and biomedical applications. In a study investigated by Singh et al. (2018a), rhizome extracts of Rhodiola rosea were used to biologically fabricate AgNPs and AuNPs in order to inhibit biofilm formation. The produced NPs were quite stable and crystalline in nature with an average size diameter of 13–17 nm for AuNPs and 15–30 nm for AgNPs. Inductively coupled plasma mass spectrometry (ICP-MS) analysis revealed the concentrations of prepared NPs as 3.3 and 5.3 mg/ml for AuNPs and AgNPs, respectively. FTIR revealed the presence of terpenes, flavonoids and phenols around the nanoparticle surface. Such biological molecules were responsible for the reduction of gold (III) chloride trihydrate (HAuCl4 .3H2 O) and AgNO3 to their nanoparticle state and further stabilized them. Furthermore, biofilms of Pseudomonas aeruginosa and Escherichia coli were found to be inhibited by AgNPs. The recorded MIC value was 50 and 100 mg/ml against P. aeruginosa and E. coli, respectively. While, the

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5 Biologically Fabricated Nanomaterials for Mitigation … (a)

C

(b)

(c)

(d)

(111)

(Counts) (200) (220) (311)

(Position (2θ) (Copper (Cu)) (e)

(f)

Fig. 5.5 AgNPs characterization: particle size distribution by dynamic light scattering (DLS) (a); zeta potential measurement (b), energy dispersive X-ray (EDX) spectra (c), X-ray diffraction (XRD) pattern (d), Field emission scanning electron microscopic (FESEM) micrograph (e) and high resolution transmission electron microscopic (HRTEM) image (f) (Omran et al. 2018c)

minimum bactericidal concentration (MBC) values were 100 and 200 mg/ml against P. aeruginosa and E. coli, respectively. Lemon grass oil (Cymbopogon citratus) (LEO) is one of the essential oils that were explored for its antimicrobial potential. Citral has been proposed to be the major component in LEO. Citral is characterized by having antimicrobial potential due to the presence of an aldehyde group. Interestingly, essential oils are characterized with high volatility and biodegradability because of the low polar surface area (17.1 A−2 ) and low vapour pressure (9.13 × 10−2 mm Hg at 25°C) (Purwasena et al. 2019). Such

5.5 Employment of Biologically Synthesized Nanoparticles …

185

Fig. 5.6 FTIR spectra of T. Longibrachiatum DSM 16517 MCFF (a) and mycosynthesized AgNPs (b) (Omran et al. 2018c)

properties prevent the removal of LEO from the environment being applied in and once it is vaporized it converts into photochemical radicals. Consequently, LEO is an eco-friendly agent which can serve as a good alternative for glutaraldehyde to trigger biocorrosion and biofilm formation (Korenblum 2013). Yet, LEO’s hydrophobicity and volatility decreased its ability for application. This is because hydrophobicity induces hydrophobic effect, thus its emulsion becomes unstable. Moreover, volatility causes LEO to be released in gas phase and hence it becomes unable to reach the targeted biofilm. Such obstacles can be overcome by the help of nanotechnology. When LEO becomes encapsulated within biopolymer matrix, this leads to maximization of the bioavailability and stability of LEO. This is due to the hydrophobic interaction between essential oil components that will lead to minimization of vaporization because of the physical limitation caused by the added biopolymer matrix (Purwasena et al. 2019). Purwasena et al. (2019) presented a study to synthesize chitosan NPs in different sizes and shapes to evaluate their biocidal effect upon different microorganisms isolated from formation water from South Sumatran oil reservoir. Formation water is the water that is produced during oil recovery processes (Abdou et al. 2011).

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5 Biologically Fabricated Nanomaterials for Mitigation … (a)

(b)

(c)

(d)

Fe

double-layered cell wall

Fe amorphous dense coat flagellum

(e) FeS

FeS FeS

flagellum

Fig. 5.7 Different fields taken by HRTEM for the untreated planktonic SRB mixed culture; colonies of SRB (a–b); focus on a rod- (c) and vibrio- (d) shaped SRB, with more than one flagellum (e) and the produced nanoscale FeS particles within the cells of SRB (c–e) (Omran et al. 2018c)

The formulation was prepared by varying chitosan and tween 80 concentrations, as well as CS/TPP ratio. Two formulae were selected labelled as LNP and SNP. The optimum concentrations which yielded the smallest size of nanoparticles of approximately1.8 nm were obtained by 0.125% chitosan, 0.5% tween 80, and 6/1 ratio of CS/TPP. Pseudomonas sp. 1, Pseudomonas sp. 2 and Pannonibacter

5.5 Employment of Biologically Synthesized Nanoparticles … (a)

187

(b)

(c)

(d)

(e)

(f)

broken flagellum

broken flagellum

cytoplasm leakage

Fig. 5.8 Different fields taken by HRTEM for the treated planktonic SRB mixed culture by 2000 mgl−1 AgNPs (a–d); Focus on a shredded single bacterium with damaged cell membrane and broken flagella (e, f) (Omran et al. 2018c)

phragmitetus were the isolated bacteria. Minimum inhibitory concentration (MIC), minimum biofilm inhibitory concentration (MBIC) and minimum biofilm eradication concentration (MBEC) assays were determined. Both formulae inhibited the bacterial growth, but LNP showed higher antimicrobial potential when compared with SNP in cases of planktonic and sessile cells.

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Tavakoli et al. (2019) performed a study with an objective of improving the antibacterial properties and corrosion resistance of stainless steel 316 L. This was conducted by innovating a coating composed of polydimethylsiloxane (PDMS-SiO2 ) and CuO NPs. CuO NPs were biologically prepared using Aloe vera extract. A. vera extract was prepared by heating 25 g of chopped leaves in 30 ml deionized (DI) water at 110°C for 30 min. Afterwards, the solution was filtered to remove any solid particles. A. vera extract was then added to 0.6 mM aqueous copper chloride solution (CuCl2 .2H2 O), stirred for 30 min at 110°C and then kept at 100°C for 45 min in an electrical oven. Then, after 72 h an aqueous solution of 15 M NaOH was further added to the above reaction solution until the colour of mixture was changed to brown. Silica NPs were synthesized via the sol-gel method. PDMS-SiO2 –CuO coating contained different amounts of CuO NPs via the dip coating process. The physical and the structural characteristics of the prepared nanocomposite coating was characterized using XRD, FTIR and SEM. Incorporation of CuO NPs within PDMS-SiO2 coatings significantly endorsed the coating hydrophobic properties and upgraded surface roughness resulting in noticeable corrosion resistance. Incorporation of CuO NPs within the coatings remarkably improved the antibacterial rate of the prepared nanocomposite coating compared with PDMS-SiO2 coating alone. Nonetheless, authors recorded that the incorporation of > 0.5 wt% CuO NPs led to a reduction in the antibacterial effect because of the agglomeration of the prepared NPs. Biocompatible green synthesized AgNPs were examined for their photocatalytic degradation efficacy of methylene blue (MB) dye and anti-microfouling effect (Harinee et al. 2019). Seaweed extract of Sargassum muticum acted as a reductant to produce AgNPs. Different analytical techniques were used to determine the structural and textural properties of the synthesized AgNPs. S. muticum derived AgNPs attained a photocatalytic activity against MB dye up to 94.6% for 60 min under UV-light irradiation. Additionally, the as-prepared AgNPs displayed an antimicrofouling performance against marine biofilming bacteria (MBF) e.g. Bacillus flexus (MBF1 AB894825); Bacillus megaterium (MBF12 AB894828); and Pseudomonas sp., (MBF9 AB894829). S. muticum derived AgNPs showed a maximum inhibition zone (18 mm) in Pseudomonas sp., and minimal inhibition zone (12 mm) in Bacillus flexus. From the resultant data, authors signified that SM-AgNPs employed a biphasic phenomenon persuaded by osmotic shock and thymine-dimer formation on microbial cells which had a damaging effect on the tested bacterial strains M13 phage is a type of filamentous phage with nanoscale dimensions of 900 nm in length and 6.5 nm in width (Yang et al. 2020). The outer surface is surrounded by approximately 2700 units of highly ordered spiral structures of capsid proteins which form a rigid proteinaceous cylinder coat (Smith and Petrenko 1997). M13 phage does not cause any harm to humans as its main host is bacteria and has the advantage of being obtained in purified large quantities with low cost (Mao et al. 2009). Presence of reactive sites (amino residues) ensures the reproducibility and the chemical modification of M13 phage surface (Bernard and Francis 2014). Interestingly, M13 phages can act as biological reductants of metal ions due to the abundance of amino acid residues such as tyrosine, cysteine, tryptophan, glutamic acid and aspartic acid

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on M13 phage surfaces (Chung et al. 2014). In a study introduced by Setyawati et al. (2014), a wild type of M13 phage was found to act as a bio-reducing agent which reduced chloroauric acid (HAuCl4 ) in acid and neutral conditions at 37°C in 24 h. In addition, in a study conducted by Wang et al. (2016), it was proved that the reduction of HAuCl4 to AuNPs was accelerated within 90 min. Also, it was found that M13 phage had the capacity to reduce AgNO3 to Ag nanowires by expressing the tetra glutamic acid peptides on the major capsid protein of M13 phage. A green approach for the biological synthesis of AgNPs by the help of a wild type of M13 bacteriophage as bio-template was proposed by Yang et al. (2020). M13 phage acted as reducing and capping agents. The biologically prepared AgNPs by the M13 phages exhibited a good antibacterial activity against both Gram positive (i.e. S. aureus and B. subtilis) and Gram negative bacteria (i.e. E. coli, P. aeruginoa). Henceforth, AgNPs derived from M13 phage can be potentially employed as antibacterial agent and as a sensing probe for controlling and tracing corrosion process. In a study demonstrated by Ituen et al. (2020), extract of Citrus reticulata (tangerine) peels was used to biologically mediate the synthesis of copper nanoparticles (CuNPs). The as-prepared CuNPs was characterized using UV–Vis spectroscopy, SEM, EDX and TEM. The resultant data revealed that the synthesized CuNPs were circular in shape, monodispersed, non-aggregated crystals with sizes ranging between 54 and 72 nm. The biogenic CuNPs was evaluated as a corrosion inhibitor of steel corrosion induced by 1 M HCl and a biocidal agent against Desulfovibrio sp. Authors observed that C. reticulata derived CuNPs triggered a 3-log reduction in Desulfovibio sp. population with a minimum inhibitory concentration of 1.96 mg/L MIC. Biocorrosion inhibition efficiency was found to reach 79.8% and 68.4% at 303 K and 333 K, respectively. Additionally, 1.0 g/L of CuNPs inhibited acid corrosion with an efficiency of 95.3% and 84.6% at 303 K and 333 K, respectively. Authors suggested that the small size of the prepared CuNPs enabled them to easily permeate through bacterial cell wall and to alter their metabolic activities and growth than by testing the extract alone. In case of HCl solution, CuNPs were adsorbed spontaneously on the steel surface through physical and chemical mechanisms. CuNPs were capped by functional groups like CC, O–H, C–O and N–H which were derived from the phyto-constituents of C. reticulata extract.

5.6 Conclusions Biocorrosion takes place due to the undesirable adhesion and accumulation of micro- and macro-organisms on submerged structures. It involves two major stages (1) micro-fouling (adhesion of microorganisms) and (2) macro-fouling (adhesion of algae, sea urchins, shells and other marine organisms). Biofouling causes severe negative consequences for medical, marine, petroleum, gas and industrial sectors leading to health risks, economical losses and environmental hazards. Nanobiotechnology arose because of the increasing awareness towards the development of eco-friendly approaches to synthesize nanomaterials. Nanobiotechnology is

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concerned with the biological and green synthesis of metal and metal oxide nanoparticles via different biological entities such as bacteria, yeast, fungi, actinomycetes and extracts of different plant parts and agro-industrial wastes. Since nanobiotechnolgy is concerned with the synthesis of nanoparticles using biological systems, it became a much cleaner and greener approach for nanoparticle synthesis than the traditionally used chemically and physically synthetic techniques used to produce such particles. The biological synthesis of nanomaterials provides an avenue for healthier workplaces and communities, Furthermore, it protects human health and the surrounding environment and guarantees the production of safer products with less waste output. Nonetheless, large-scale synthesis studies are still required. Exploration of the precise mechanisms of biogenic nanomaterials formation, isolation and purification need further more in-depth investigations. Additionally, the mechanistic scenario behind the effectiveness of biologically fabricated nanomaterials as biocides is a promising areas of research which need further extensive studies.

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Glossary

Adenosine Triphosphate (ATP) A compound which consists of an adenosine molecule bonded to three phosphate groups and it is present in all living tissues. Agro-Industrial Wastes Wastes that are derived from agro-or industrial origin. Alloy It is a metal which is made by combining two or more metallic elements in order to provide more strength or resistance against corrosion. Anode It is the electrode of an electrochemical cell at which oxidation reaction takes place. Antimicrobial Activity Minimizing and inhibiting microbial growth particularly pathogenic microorganisms. Atomic Force Microscopy (AFM) It is a very high resolution type of scanning probe microscopy which demonstrates resolution on the order of nanometer fractions and it is more than 1000 times better than the optical diffraction limit. Atomic Layer Deposition (ALD) It is a thin-film deposition technique which is based on the sequential use of a gas phase chemical process. Biocide Material or substance which has the ability to destroy microorganisms. Biofilm Aggregates of microorganisms in which cells are frequently embedded within a self-produced matrix composed of extracellular polymeric substances and adhered to each other and/or to a surface. Biofouling The detrimental deposition of biological growth by both micro- and macroorganisms along with other constituents of natural water that causes defects in the performance and efficiency of industrial equipment and operations. Bottom-Up Approach It is the approach in which NPs are built from atoms, molecules and smaller particles/monomers. Carbon Steel Steel in which the chief alloying element is carbon. Cast Iron It is a hard or relatively brittle alloy composed of iron and carbon and possesses a higher proportion of carbon than steel. Cathode It is the electrode of an electrochemical cell at which reduction reaction takes place. Chlorination The process of addition of chlorine or chlorine compounds such as sodium hypochlorite to prevent the spread of pathogenic microorganisms. © Springer Nature Switzerland AG 2020 B. A. Omran and M. O. Abdel-Salam, A New Era for Microbial Corrosion Mitigation Using Nanotechnology, Advances in Material Research and Technology, https://doi.org/10.1007/978-3-030-49532-9

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Corrosion Inhibitor It is a substance which when added in small quantities to the environment results in a decrease in corrosion rate of a material particularly metals and alloys Corrosion It is a destructive damage in the properties of a metal and it is a natural process in which metals are converted into a more stable form such as oxides Crevice Corrosion It is a type of localized corrosion and it takes place in gaps and crevices formed either between metals or between a metal and a non-metal material Critical Micelle Concentration (CMC) It is the concentration of surfactants above which micelles are formed and all additional surfactants added to the system go to micelles. Denaturating Gradient Agro Gel Electrophoresis (DGGE) It is a technique that separates a mixture of DNA fragments according to their melting point and aids in analyzing microbial communities without cultivation. Deoxyribonucleic Acid (DNA) It is a molecule which is found inside every cell in almost every living organism. Dezincification The selective removal of zinc from brass especially those which exist in acidic medium. Drilling Fluid It is prepared from water clays, and chemicals circulated in oil-well drilling for lubricating and cooling the bit, flushing the rock cuttings and for plastering the side of the well. Electrochemical Impedance Spectroscopy (EIS) It is an analysis technique used to observe the changes of the interfacial properties of the electrode after the interaction of analytes with probing molecules immobilized on electrode surfaces. Embrittlement Loss of material flexibility and functionality thus making it brittle. Energy Dispersive X-ray (EDX) It is an analytical technique which is employed for elemental analysis or chemical characterization of a sample. Enzyme Linked Immunosorbent Assay (ELIZA) It is a biochemical procedure in which a signal is produced by an enzymatic reaction in order to detect and quantify the amount of a specific substance in a solution. Erosion Corrosion It is a type of corrosion in which metals are degraded due to mechanical action. Erosion The gradual destruction due to eroding by natural agents such as water wind, etc. Extracellular Polymeric Substances (EPS) Natural polymers with high molecular weight and secreted by microbial consortium into the surrounding environment. Fimbriae It is the Latin word for fringe (singular name is fimbria) it is a hair appendage on the bacterial surface which aid in their motility Flagellum It is a thin thread-like structure specifically a microscopic appendage which facilitates the motility of many protozoa, bacteria, spermatozoa, etc. Focused Ion Beam (FBI) It is a technique which is employed in semiconductor industry and in different biological fields for site-specific analysis and deposition of materials.

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Formation Water or Produced Water It is the term that usually describes the water which is produced as a by-product that accompanies the extraction of oil and natural gas. Fourier Transform Infrared Spectroscopy (FTIR) It is a technique employed to obtain an infrared spectrum of absorption or emission of a solid, liquid or gas. Galvanic Corrosion It is a type of corrosion that takes place when two different metals are in contact with each other in an electrolyte. Gasket It is a rubber shaped sheet or ring or any other material which seal the junction between two surfaces in an engine or any other device. Globe The whole world. Gross National Product It is the total value of the produced products and services provided by a country in one year and equal to the gross domestic product in addition to the net income from foreign investments. Hydraulic Fracturing It is a well stimulation technique in which rocks are fractured by a pressurized liquid. Hydrophilicity The property of a molecule to solubilize in water. Hydrophobicity The property of a molecule to repel water rather than absorbing it or dissolving in it. Isoelectric Point (IEP) It is pH at which a molecule carries no electrical charge or is electrically neutral. Linear Polarization Resistance (LPR) It is a method in which the electrochemical response of a corroding metal is investigated near its open circuit or corrosion potential. Localized Corrosion It is the type of corrosion that occurs at separate sites on a metal surface. Microbial Corrosion The degradation of materials by the action of microorganisms such as bacteria, molds, and fungi, etc. and their metabolites. Mild Steel It is a type of steel that contains only a small percentage of carbon and characterized by its fair strength. Mortality The quality or state of death. Most Probable Number It is a method in which the concentration of visible microorganisms can be estimated. Myconanotechnology Synthesis of nanoparticles using fungi. Nano It is the term which means extremely small and it originates from the Greek word “nanos” meaning “dwarf” in Greek. Nanobiotechnology It is the interface between biotechnology and nanotechnology. It also refers to the study of how the objectives of nanotechnology can be directed and reached via biological machines. Nanoreporters Refer to the engineered nanoparticles which can be used for the detection of hydrocarbons in oil-field rocks. Nanotechnology It is a field of research and innovation which is concerned with building ‘things’—generally, materials and devices—on the scale of atoms and molecules.

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Nuclear Magnetic Resonance (NMR) It is a technique which depends on absorption of electromagnetic radiation by a nucleus in the presence of an external magnetic field. Oil Based Mud It is a drilling fluid which is utilized in drilling engineering. It is composed of oil as a continuous phase and water as a dispersed phase in association with emulsifiers, gellants and wetting agents. Open Circuit Potential It is the potential at which there is no current in which experiments are based on potentiometric experiments. Oxygen Corrosion It is a type of corrosion in which metal degradation occurs in presence of oxygen to generate insoluble deposits as consequence of the rapid rate of oxidation. Part Per Billion (ppb) It is one part of solute per one billion parts of solvent. pH It is a scale that is used to specify how acidic or basic a solution might be. Phytonanotechnology Synthesis of nanoparticles using extracts of plant biomaterials. Pilli It is the Latin word for hair (singular name is pillus) it is a hair-like appendage existed on the surface of many microorganisms such as bacteria and archaea. Pitting corrosion It is the type of corrosion that is extremely localized and results in the creation of pits and pores with different depths. Point of Zero Charge (PZC) It is a concept which is related to the adsorption phenomenon and it describes the condition in which the electrical charge density on a surface is zero Potentiodynamic Polarization It is a technique in which the potential of the electrode is varied at a selected rate by application of a current through the electrolyte. Proppant It is a solid substance mainly sand (i.e. treated sand) or man-made ceramic materials which is designed to maintain an induced hydraulic fracture open, during or following a fracturing treatment. Quorum Sensing It is bacterial cell to cell communication and it refers to the ability to identify and respond to cell population density depending on gene regulation. Rusting It is the red or orange colored coating formed on the surface of iron after exposure to air and moisture. It is usually made up of ferric oxide and ferric hydroxide. Scanning Transmission X-Ray Microscopy (STMX) It is an imaging technique where a finely focused X-ray beam in the range of 20–25 nm is scanned over the surface of the specimen. Selective Leaching or Dealloying It is a type of corrosion in which a component is leached from the alloy. Sour Corrosion It is the type of corrosion that occurs on a metal surface because of the presence of highly acidic environment containing hydrogen sulfide. Stainless Steel A type of steel that contains chromium to confer resistance against rust. Stress Corrosion Cracking (SCC) It refers to the appearance of cracks because of a corrosive environment.

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Surface-Enhanced Raman Spectroscopy (SERS) It is a surface sensitive technique which enhances Raman scattering by adsorption of molecules on rough metal surfaces. Surfactant It is a substance that decreases the surface tension of a liquid in which it is dissolved. Sweet Corrosion It is a type of corrosion that takes place in the presence of carbon dioxide and carbonic acids. Tafel Polarization It is a mathematical technique in which corrosion current (Icorr ) or the corrosion potential (Ecorr ) can be measured in an electrochemical cell. Thermogravimetric Analysis (TGA) It is a method of thermal analysis in which the mass of a sample is measured within time as the temperature is changed. Top-Down Approach It is the approach which starts with the material of interest and then undergoes size reduction via physical and chemical processes to produce NPs. Uniform or General Corrosion It is a type of corrosion attack that is distributed in a uniform pattern over the entire attacked metal surface. Welding Joining metal parts together by the effect of heating to the point of melting by the help of electric arc blowpipe or other means and uniting both parts by pressing. X-ray photoelectron spectroscopy (XPS) It is a surface sensitive quantitative spectroscopic technique that measures the elemental composition at a range of parts per thousand.