Characterization of Minerals, Metals, and Materials 2019 [1st ed.] 978-3-030-05748-0, 978-3-030-05749-7

Table of contents :
Front Matter ....Pages i-xxvi
Front Matter ....Pages 1-1
Commentary—Are There Still Places for Gallium FIB? (Jian Li)....Pages 3-9
Structural Characterization of Four Chinese Bituminous Coals by X-Ray Diffraction, Fourier-Transform Infrared Spectroscopy and X-Ray Photoelectron Spectroscopy (Shuxing Qiu, Shengfu Zhang, Xiaohu Zhou, Rongjin Zhu, Guibao Qiu, Yue Wu et al.)....Pages 11-22
In Situ Characterization at High Temperature of VDM Alloy 780 Premium to Determine Solvus Temperatures and Phase Transformations Using Neutron Diffraction and Small-Angle Neutron Scattering (C. Solís, J. Munke, M. Hofmann, S. Mühlbauer, M. Bergner, B. Gehrmann et al.)....Pages 23-32
Study of the Adsorption of Humic Acid with Zn2+ by Molecular Dynamic Simulation and Adsorption Experiments (Shengpeng Su, Yanfang Huang, Guihong Han, Zibiao Guo, Fengning Liu)....Pages 33-41
Front Matter ....Pages 43-43
Structure, Phase Composition, and Properties of Ceramics Based on AlMgB14, Obtained from Various Powders (Ilia Zhukov, Pavel Nikitin, Alexander Vorozhtsov)....Pages 45-49
Characterization of Modified Nickel Silicate Anode Material for Lithium–Ion Batteries (Yunyun Wei, Guihong Han, Yanfang Huang, Duo Zhang)....Pages 51-57
Sinterability of Y-Doped BaZrO3 with Micro- and Nano-CaO Additives and Its Interaction with Titanium Alloy (Juyun Kang, Guangyao Chen, Baobao Lan, Shihua Wang, Xionggang Lu, Chonghe Li)....Pages 59-67
The Influence of Microstructure and Emissivity of NiO-Doped Fe3O4 Spinel Structure on Near- and Middle-Infrared Radiation (Jian Zhang, Bai Hao, Xu Zhang, Huanmei Yuan, Zefei Zhang, Liyun Yang)....Pages 69-77
Incorporation of Silver Nanoparticles in Zinc Oxide Matrix in Polyester Thermoplastic Elastomer (TPE-E) Aiming Antibacterial Activity (Leonardo Guedes Marchini, Duclerc Fernandes Parra, Vijaya Kumar Rangari)....Pages 79-88
Front Matter ....Pages 89-89
Adsorption Behavior of Cu(II) to Silica-Humics Composite Aerogels (Guihong Han, Pengfei Tang, Hongyang Wu, Jun Ma, Xiaomeng Yang, Yongsheng Zhang)....Pages 91-96
Inter- and Transgranular Nucleation and Growth of Voids in Shock Loaded Copper Bicrystals (Elizabeth Fortin, Benjamin Shaffer, Saul Opie, Matthew Catlett, Pedro Peralta)....Pages 97-108
Alloying and Annealing Effects on Grain Boundary Character Evolution of Al-alloy 7075 Thin Films: An ACOM-TEM Analysis (Prakash Parajuli, Rubén Mendoza-Cruz, Miguel José Yacamán, Arturo Ponce)....Pages 109-119
Front Matter ....Pages 121-121
Evolution of Precipitates During Rolling and Annealing Process in Non-Oriented Electrical Steel (Qiang Ren, Lifeng Zhang, Yan Luo, Lin Cheng, Piotr Roman Scheller)....Pages 123-129
Structure and Magnetic Properties of a Medium-Entropy Fe46Co34Ni20 Alloy Powder (Anuj Rathi, Tanjore V. Jayaraman)....Pages 131-142
Evolution of Microstructure and Mechanical Properties of 20Cr13 Under Cavitation Erosion (Guiyan Gao, Zheng Zhang)....Pages 143-151
Investigating the Mechanical Response Under Quasi-static Compression of Cold-Rolled Lean Duplex Stainless Steel 2101 (Tayla M. Nankivell, Ali A. H. Ameri, Juan P. Escobedo-Diaz, Md. Z. Quadir, C. Logos, Simon S. Higgs)....Pages 153-160
Preparation of Magnesium Aluminum Ferrite Spinel by Microwave Sintering (Huimin Tang, Zhiwei Peng, Foquan Gu, Lei Ye, Liancheng Wang, Leixia Zheng et al.)....Pages 161-169
Front Matter ....Pages 171-171
Two Fibers Used in the Colombian Amazonia and Their Use as Potential Reinforcement for Composite Materials (Henry A. Colorado, Claudio Aguilar, Sergio Neves Monteiro)....Pages 173-178
Influence of Albizzia Lebbeck Benth Pods Particulate on Mechanical Properties of Low-Density Polyethylene (Oluwashina Philips Gbenebor, Emmanuel Isaac Akpan, Festus Omo Osabumwenre, Samson Oluropo Adeosun)....Pages 179-185
Front Matter ....Pages 187-187
Friction Stir Welding of Aluminum Alloys and Steels: Issues and Solutions (Mian Wasif Safeen, Pasquale Russo Spena)....Pages 189-200
Magnetic Characterization of CarTech® Hypocore™ Alloy at Cryogenic Temperatures (V. M. Meka, E. M. Fitterling, T. V. Jayaraman)....Pages 201-208
Front Matter ....Pages 209-209
Advances in Scratch Characterization of Automotive Clearcoats (Pierre Morel, Linqian Feng, Nadia Benhamida, Warren Denning, Brandon Frye, Andrew T. Detwiler et al.)....Pages 211-224
Microwave-Assisted Solid-State Synthesis of Fluorinated Hydroxyapatite (Qian Peng, Huimin Tang, Zhangui Tang, Zhiwei Peng)....Pages 225-235
Properties of ZnO Micro/Nanostructures on Aluminum Substrates (Shadia J. Ikhmayies, Hassan K. Juwhari, Bashar Lahlouh)....Pages 237-246
Synthesis and Electrochemical Properties of Molybdenum Disulfide/Graphene Composites (Guihong Han, Wei Wang, Yanfang Huang, Yongqian Duan, Weijun Peng)....Pages 247-253
Synthesis and Characterization of PVP/CaCO3-Ag Blend Hydrogel by Gamma Irradiation: Study of Drug Delivery System and Antimicrobial Activity (Angelica Tamiao Zafalon, Vinícius dos Santos Juvino, Luiz Gustavo Hiroki Komatsu, Duclerc Fernandes Parra, Ademar Lugao, Temesgen Samuel et al.)....Pages 255-265
Front Matter ....Pages 267-267
Microplastics: A Novel Method for Surface Water Sampling and Sample Extraction in Elechi Creek, Rivers State, Nigeria (Example Briggs, Esperidiana A. B. de Moura, Helio A. Furusawa, Marycel E. B. Cotrim, Emeka E. Oguzie, Ademar B. Lugao)....Pages 269-281
Leaching Zinc from Crystallization Slag by Acid Leaching: Process Optimization Using Response Surface Methodology (Guojiang Li, Yongguang Luo, Tingfang Xie)....Pages 283-290
Study on Recovery of Zinc from Metallurgical Solid Waste Residue by Ammoniacal Leaching (Aiyuan Ma, Xuemei Zheng, Shengyou Shi, Haiye He, Yanhong Rao, Guoyan Luo et al.)....Pages 291-300
Optimization of Fine Ilmenite Flotation Performed with Collectors (Yankun Wu, Shengpeng Su, Weijun Peng, Yongsheng Zhang, Guixia Fan, Guihong Han et al.)....Pages 301-309
Arsenic Reduction and Cobalt Removal in the Arsenic-Containing Leachate from Alkali Leaching of Arsenic-Containing Cobalt/Nickel Residue (Jinxi Qiao, Shuang Long, Zhiqiang Liu, Xintao Sun, Zhaoming Sun, Hualei Miao et al.)....Pages 311-318
Front Matter ....Pages 319-319
A Comparison Between ZnO Hexagonal Micro/Nanoprisms Deposited on Aluminum and Glass Substrates (Shadia J. Ikhmayies)....Pages 321-328
Microwave-Assisted One-Step Synthesis of FeCo/Graphene Nanocomposite for Microwave Absorption (Jianhui Peng, Zhiwei Peng, Liancheng Wang, Leixia Zheng, Zhongping Zhu, Guanghui Li et al.)....Pages 329-340
Front Matter ....Pages 341-341
Effect of Metallic Iron Sinter Feed on Sinter Mineralogy and Quality (Mingming Zhang, Marcelo Andrade)....Pages 343-350
Effect of Microstructure on Resistance to Buildups Formation of Carbon Sleeves in Continuous Annealing Furnace for Silicon Steel Production (Mingsheng He, Xiongkui Wang, Wangzhi Zhou, Xuecheng Gong, Jing Zhang, Jian Xu)....Pages 351-359
Influence of Cr2O3 and Basicity on Viscosity of Ti-Bearing Blast Furnace Slag (Guibao Qiu, Jian Wang, Shiyuan Liu, Qingjuan Li)....Pages 361-369
Raman Spectroscopy on the KBF4–KF–KCl Molten Salt System (Xianwei Hu, Bo Li, Jiangyu Yu, Zhongning Shi, Bingliang Gao, Zhaowen Wang)....Pages 371-377
Thermodynamic Characteristics of Ferronickel Slag Sintered in the Presence of Magnesia (Foquan Gu, Zhiwei Peng, Yuanbo Zhang, Huimin Tang, Lei Ye, Weiguang Tian et al.)....Pages 379-388
Characterization on the Properties of Calcium Stannates Synthesized Under Different Atmospheres (Benlai Han, Zijian Su, Yuanbo Zhang, Bingbing Liu, Manman Lu, Tao Jiang)....Pages 389-398
Front Matter ....Pages 399-399
Use of Municipal Solid Waste Incinerator (MSWI) Fly Ash in Alkali Activated Slag Cement (Kang Huang, Xiaohui Fan, Min Gan, Zhiyun Ji)....Pages 401-410
Reliability Increasing of an Estimation of Rocks Strength by Non-destructive Methods of Acoustic Testing Due to Additional Informative Parameters (A. S. Voznesenskii, M. N. Krasilov, Ya. O. Kutkin, M. N. Tavostin)....Pages 411-423
Characterization of Water/Ethanol/Bentonite Dispersions (Margarita Bobadilla, Thamyres C. Carvalho, Antonio H. Munhoz Junior, Maria das Graças da Silva-Valenzuela, Francisco R. Valenzuela-Diaz)....Pages 425-432
Front Matter ....Pages 433-433
A Study of the Load Stages by the Displacement of Mortars Composed of Ornamental Stone Residues by the Method of Squeeze Flow (P. I. Moreira, L. F. Ciribelli, G. C. Xavier, J. Alexandre, G. C. M. Carvalho, A. R. G. Azevedo et al.)....Pages 435-440
Alpha-Alumina Synthesis Using Gamma-Alumina Powders (Antônio Hortencio Munhoz Junior, Gustavo Figueiredo Galhardo, Fernando dos Santos Ortega, Nelson Batista de Lima, Dênison Angelotti Moraes, Leila Figueiredo de Miranda et al.)....Pages 441-451
An Investigation of Mechanical and Thermal Properties of Polypropylene Reinforced with Different Clays (Alex S. Monteiro, Daili A. S. Barreira, Jaqueline S. Silva, Rene R. Oliveira, Francisco R. Valenzuela-Díaz, Esperidiana A. B. Moura)....Pages 453-463
Analysis of Rheological Behavior by the Method Squeeze Flow in Mortars Incorporated with Ornamental Stone Residue (G. C. M. Azevedo, P. I. Moreira, L. F. Ciribelli, G. C. Xavier, J. Alexandre, A. R. G. Azevedo et al.)....Pages 465-472
Analysis of the Feasibility of the Use Waste from the Foundry Process in Green Sands in the Manufacturing of Soil-Cement Blocks (Niander A. Cerqueira, Victor B. Souza, Guilherme M. R. Coutinho, Lucas X. P. da Silva)....Pages 473-483
Analysis of the Life Extension of ASTM A-36 Steel Structures Using the Concepts of Fracture (Kayan A. Carneiro, Victor B. Souza, Niander A. Cerqueira, Lucas Costa, Amanda C. Lima, Afonso R. G. Azevedo et al.)....Pages 485-494
Ceramic Properties: Clay Smectite Synthetic (Thamyres C. Carvalho, Camila N. Maggi, Margarita Bobadilla, E. Hildebrando, Roberto F. Neves, Francisco R. Valenzuela-Diaz)....Pages 495-502
Chemical and Instrumental Characterization of a Sulphosalt Lead Type Jamesonite (M. Reyes Pérez, Elia Guadalupe Palacios Beas, Francisco R. Barrientos, Miguel Pérez Labra, Julio Cesar Juárez Tapia, Iván Alejandro Reyes Domínguez et al.)....Pages 503-510
Characterization of a Composite of High-Impact Polystyrene, Pseudoboehmite and Graphene Oxide (Antônio Hortencio Munhoz Junior, Caroline Valadão Pacheco, Henrique Tadeu T. S. Melo, Renato Meneghetti Peres, Leonardo Gondim de Andrade e Silva, Leila Figueiredo de Miranda et al.)....Pages 511-522
Characterization of Antistatic Packaging Based on PET/rGO (Leila Figueiredo de Miranda, Antônio Hortêncio Munhoz Jr, Terezinha Jocelen Masson, Leonardo Gondin de Andrade e Silva, Karl Friehe)....Pages 523-534
Characterization of Oxides from Al–Mg–Zn Alloys with Heat Treatment, with Scanning Electron Microscopy and Fluorescence Microscopy (Aline Hernández, Bernardo Campillo, Sergio Serna, Álvaro Torres, Natalia Loera)....Pages 535-541
Characterization of Printed Circuit Boards of Obsolete (PCBs) Aimed at the Production of Copper Nanoparticles (Thamiris Auxiliadora Gonçalves Martins, Karen Espina Gomes, Carlos Gonzalo Alvarez Rosario, Denise Crocce Romano Espinosa, Jorge Alberto Soares Tenório)....Pages 543-551
Comparative Analysis of Dynamic Impact Tests Between the Charpy V-Notch Test and the Drop Tower Test (Chaitanya Gunturi, Juan P. Escobedo, M. A. Islam)....Pages 553-560
Comparative Study of the Use of Rice Husk Ashes and Graphite as Fillers in Polypropylene Matrix Composites (Alex S. Monteiro, Daili A. S. Barreira, Suellen Signer Bartolomei, Rene R. Oliveira, Esperidiana Augusta Barreto de Moura)....Pages 561-570
Development of Biocomposite Materials from Biodegradable Polymer and Bio-hydroxyapatite Derived from Eggshells for Biomedical Applications (Pedro R. S. Reis, Julyana G. Santana, Rene R. Oliveira, Vijaya K. Rangari, Felipe R. Lourenço, Esperidiana A. B. Moura)....Pages 571-581
Development of Methodology for the Characterization and Incorporation of Waste from the Paper Industry in Cementitious Materials (A. R. G. Azevedo, J. Alexandre, M. T. Marvila, E. B. Zanelato, B. C. Mendes, N. A. Cerqueira et al.)....Pages 583-590
Differences in Properties of Pro-degradant Added PP and Gamma-Irradiated PP Under Environmental Aging (Rebeca da Silva Grecco Romano, Washington Luiz Oliani, Vijaya Rangari Kumar, Duclerc Fernandes Parra, Ademar Benévolo Lugão)....Pages 591-603
Effect of Phosphate Antioxidant on Resisting to Buildups Formation of Carbon Sleeves in Continuous Annealing Furnace for Silicon Steel Production (Mingsheng He, Xiongkui Wang, Xuecheng Gong, Jing Zhang, Wangzhi Zhou, Jian Xu)....Pages 605-615
Effect of the Incorporation of Iron Ore Tailings on the Properties of Clay Bricks (Beatryz Cardoso Mendes, Leonardo Gonçalves Pedroti, Rita de Cássia S. S. Alvarenga, Mauricio Paulo Ferreira Fontes, Pedro Cota Drumond, Anderson Almeida Pacheco et al.)....Pages 617-627
Effect Study of the Incorporation of the Green Lake Clay in the Polypropylene Homopolymer Properties (J. N. Sales, P. N. S. Poveda, A. Ortiz, F. R. Valenzuela-Diaz, L. A. Silva)....Pages 629-636
Electron Beam Effect on the Thermal and Mechanical Properties Analysis of DGEBA/EPDM Compound (Anderson dos Santos Mesquita, Ian Trolles Cavalcante, Leonardo Gondim de A e Silva)....Pages 637-646
Evaluation of Technological Properties of Soil-Cement Blocks Using Experimental Design of Mixtures (A. R. G. Azevedo, J. Alexandre, M. T. Marvila, E. B. Zanelato, G. C. Xavier, N. A. Cerqueira et al.)....Pages 647-655
Exploration of Humic Acids as the Binder of Silicon-Based Anode for Lithium-Ion Batteries (Shuzhen Yang, Guihong Han, Yanfang Huang, Jiongtian Liu)....Pages 657-663
Impact Response of Bamboo Guadua Angustifolia Kunth (Julian Rua, M. F. Buchely, Henry A. Colorado)....Pages 665-672
Incorporation of EVA Residue for Production of Lightweight Concrete (R. O. Machado, L. C. K. M. Pereira, E. B. Zanelato, A. L. F. Manhães, A. R. G. Azevedo, M. T. Marvila et al.)....Pages 673-681
Innovation of Building Materials: Ecological Bricks, Characterization of Complementary Inorganic Raw Materials (Javier Flores-Badillo, Adriana Rojas-León, Alma Delia Román-Gutiérrez, Juan Hernández-Ávila, Eleazar Salinas-Rodríguez, Christopher Contreras-López)....Pages 683-692
Investigation on Mechanical Behaviors of Polyamide 11 Reinforced with Halloysite Nanotubes (Danae Lopes Francisco, Lucilene Betega de Paiva, Wagner Aldeia, Ademar B. Lugão, Esperidiana A. B. Moura)....Pages 693-701
Measurement of SnO2 Nanoparticles Coating on Titanium Dioxide Nanotube Arrays Using Grazing-Incidence X-Ray Diffraction (Yunhui Tang, Bo Wang, Hongyi Li, Mingsheng He)....Pages 703-711
Microstructural Characterisation of a High Strength Steel Subjected to Localised Blast Loading (Simon Higgs, Ali Ameri, Juan Pablo Escobedo-Diaz, Brodie McDonald, Huon Bornstein, Zakaria Quadir et al.)....Pages 713-720
Mortars with Pineapple Fibers for Use in Structural Reinforcement (M. T. Marvila, A. R. G. Azevedo, J. Alexandre, E. B. Zanelato, S. N. Monteiro, D. Cecchin et al.)....Pages 721-728
Performance of Epoxy Matrix Reinforced with Fique Fibers in Pullout Tests (Michelle Souza Oliveira, Artur Camposo Pereira, Fabio da Costa Garcia Filho, Luana Cristyne da Cruz Demosthenes, Sergio Neves Monteiro)....Pages 729-734
Production and Characterization of a Hybrid Composite of Polypropylene Reinforced with Piassava (Attalea funifera Martius) Fiber and Light Green Clay (Sabrina A. Correia, Pedro V. Cruz, Tasson C. Rodrigues, Alex Monteiro, Francisco R. V. Diaz, Esperidiana A. B. Moura)....Pages 735-746
Proposal of Dosing of Mortars Using Simplex Network (M. T. Marvila, A. R. G. Azevedo, J. Alexandre, E. B. Zanelato, S. N. Monteiro, N. A. Cerqueira)....Pages 747-756
Recycled Gypsum Particles Incorporation in Recycled Expanded Polystyrene by Biodegradable Solvent—Preparation and Characterization (Suellen Signer Bartolomei, Esperidiana Augusta Barreto de Moura, Helio Wiebeck)....Pages 757-763
Structural Analysis of Sintered Products of BaTiO3 Doped with Sm3+ (J. P. Hernández-Lara, M. Pérez-Labra, C. C. Gutierrez-Hernández, F. R. Barrientos-Hernández, J. A. Romero-Serrano, A. Hernández-Ramírez et al.)....Pages 765-772
Study of the Electrical Properties of rGO Obtained by Different GO Reduction Methods (Leila Figueiredo Miranda, Paulo Victor Cedini Gomes, Fabio Jesus Moreira de Almeida, Leonardo Gondim Andrade e Silva, Antonio Hortencio Munhoz Junior, Terezinha Jocelen Masson)....Pages 773-785
Study of the Influence of Organic Peroxide and Elastomeric Modifier in the Mechanical and Flow Properties of the Recycled Polypropylene (Patricia N. S. Poveda, Leonardo G. A e Silva)....Pages 787-792
Back Matter ....Pages 793-804

Citation preview

Characterization of Minerals, Metals, and Materials 2019

Edited by

Bowen Li Jian Li Shadia Ikhmayies Mingming Zhang Yunus Eren Kalay John S. Carpenter Jiann-Yang Hwang Sergio Neves Monteiro Chenguang Bai Juan P. Escobedo-Diaz Pasquale Russo Spena Ramasis Goswami

The Minerals, Metals & Materials Series

Bowen Li Jian Li Shadia Ikhmayies Mingming Zhang Yunus Eren Kalay John S. Carpenter Jiann-Yang Hwang Sergio Neves Monteiro Chenguang Bai Juan P. Escobedo-Diaz Pasquale Russo Spena Ramasis Goswami •

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Editors

Characterization of Minerals, Metals, and Materials 2019

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Editors Bowen Li Michigan Technological University Houghton, MI, USA

Jian Li CanmetMATERIALS Hamilton, ON, Canada

Shadia Ikhmayies Al-Isra University Amman, Jordan

Mingming Zhang ArcelorMittal Global R&D East Chicago, IN, USA

Yunus Eren Kalay Middle East Technical University Ankara, Turkey

John S. Carpenter Los Alamos National Laboratory Los Alamos, NM, USA

Jiann-Yang Hwang Michigan Technological University Houghton, MI, USA

Sergio Neves Monteiro Military Institute of Engineering Rio de Janeiro, Brazil

Chenguang Bai Chongqing University Chongqing, China

Juan P. Escobedo-Diaz UNSW Canberra Campbell, ACT, Australia

Pasquale Russo Spena Free University of Bozen-Bolzano Bolzano, Italy

Ramasis Goswami Naval Research Laboratory Washington, DC, USA

ISSN 2367-1181 ISSN 2367-1696 (electronic) The Minerals, Metals & Materials Series ISBN 978-3-030-05748-0 ISBN 978-3-030-05749-7 (eBook) https://doi.org/10.1007/978-3-030-05749-7 Library of Congress Control Number: 2018964041 © The Minerals, Metals & Materials Society 2019 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, express 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. Cover illustration: From Chapter ‘Comparative Study of the Use of Rice Husk Ashes and Graphite as Fillers in Polypropylene Matrix Composites’, Alex S. Monteiro, Daili A.S. Barreira, Suellen Signer Bartolomei, Rene R. Oliveira, Esperidiana Augusta Barreto de Moura, pages 561–570, Figure 4: FE-SEM images of neat PP (a) and its composites with GA (b) and RHA(c), magnitude of 1000x. https://doi.org/10.1007/978-3-030-05749-7_56. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

Preface

The interrelationships among composition, structure, property, process, and performance of a material is the fundamental for materials research, development, manufacturing, and application. Materials characterization is the key to reveal these relationships throughout the entire circulation process of materials, from raw materials selection, through various process stages, final products, and applications, up to materials recycling and reuse. Characterization provides accurate and realistic information for in-depth understanding of a material, such as how the material fails, how to improve the performance, how to simulate a material, and what is the lifetime of the material. Sponsored by the Materials Characterization Committee of The Minerals, Metals & Materials Society (TMS), the symposium Characterization of Minerals, Metals, and Materials is focused on the advancements of characterization of various minerals, metals, and materials from the bulk down to the nanoscale, and on the applications of characterization results on the processing of these materials. The subjects of the symposium include extraction and processing of various minerals, and the process– structure–property relationship of metal alloys, glasses and ceramics, polymers, composites, and carbon used as functional and structural materials. All characterization methods and techniques and their applications are covered in this symposium. Advanced methodology and instrumentation for materials characterization are emphasized. The characterization symposium is one of the largest and broadest symposia in terms of scientific coverage during TMS Annual Meetings, which attract materials scientists, mineralogists, metallurgists, mechanical engineers, chemists, physicists, microsporidians, and instrumental experts from academia and industry across the world. For the TMS 2019 Annual Meeting held in San Antonio, Texas, USA, the characterization symposium received 188 abstract submissions, of which 107 were accepted for oral presentation in 13 technical sessions, and 74 accepted as posters. This volume includes 79 peer-reviewed manuscripts of original research. The manuscripts were invited or contributed by the researchers from the fields of materials science, engineering, metallurgy, physics, chemistry, manufacturing, and applications. The authors of the papers represent diversity from more than 25 countries in the v

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Preface

North America, South America, Asia, Europe, Australia, and Africa. Although the papers were divided into 14 sections based on the technical sessions of the symposium, the topics of this collection cover a wide range of materials characterization from composition, structure, process, property, and performance, and their interrelations in the materials from bulk-scale down to microscale and nanoscale. The material sequence and related processes were widely covered which include minerals, metals, and alloys, ceramics, polymers and composites, semiconductors, energy, optical, electronic, magnetic, environmental materials, and concrete. Among these papers, metallic materials and various composite materials make up the major portion of the proceedings. This book is a valuable reference for academic and industry readers from advanced undergraduates to experienced professionals who wish to learn about all types of characterization methods, their development and applications in general, specifically in the minerals, metals, and materials. The collection provides up-todate achievements on many types of materials for the scientists and engineers engaged in research, development, and production. Readers will enjoy the diversity of topics in this book with novel approaches to materials, micro- and nanostructures, performance, and relationships in practical uses. The editors of this book are very grateful to the authors for their contribution of the manuscripts and willingness to share their new findings with the materials community. The editors would also like to express appreciation to the TMS for giving this symposium the opportunity to publish a stand-alone volume. They also thank the Materials Characterization Committee and Extraction and Processing Division for sponsoring this symposium. The editors also thank the publisher, Springer, for their production of this book. Finally, they acknowledge the efforts by the past chairs and members of the Materials Characterization Committee, who continuously built this great symposium and who attracted talented and creative people and research groups from around the world to the committee and symposium. Bowen Li Lead Organizer

Contents

Part I

Characterization Method Development

Commentary—Are There Still Places for Gallium FIB? . . . . . . . . . . . . Jian Li Structural Characterization of Four Chinese Bituminous Coals by X-Ray Diffraction, Fourier-Transform Infrared Spectroscopy and X-Ray Photoelectron Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . Shuxing Qiu, Shengfu Zhang, Xiaohu Zhou, Rongjin Zhu, Guibao Qiu, Yue Wu and Guangsheng Suo In Situ Characterization at High Temperature of VDM Alloy 780 Premium to Determine Solvus Temperatures and Phase Transformations Using Neutron Diffraction and Small-Angle Neutron Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C. Solís, J. Munke, M. Hofmann, S. Mühlbauer, M. Bergner, B. Gehrmann, J. Rösler and R. Gilles Study of the Adsorption of Humic Acid with Zn2+ by Molecular Dynamic Simulation and Adsorption Experiments . . . . . . . . . . . . . . . . . Shengpeng Su, Yanfang Huang, Guihong Han, Zibiao Guo and Fengning Liu Part II

3

11

23

33

Process and Characteristics of Advanced Ceramics and Glasses

Structure, Phase Composition, and Properties of Ceramics Based on AlMgB14, Obtained from Various Powders . . . . . . . . . . . . . . . . . . . . Ilia Zhukov, Pavel Nikitin and Alexander Vorozhtsov

45

Characterization of Modified Nickel Silicate Anode Material for Lithium–Ion Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Yunyun Wei, Guihong Han, Yanfang Huang and Duo Zhang

51

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Sinterability of Y-Doped BaZrO3 with Micro- and Nano-CaO Additives and Its Interaction with Titanium Alloy . . . . . . . . . . . . . . . . . Juyun Kang, Guangyao Chen, Baobao Lan, Shihua Wang, Xionggang Lu and Chonghe Li The Influence of Microstructure and Emissivity of NiO-Doped Fe3O4 Spinel Structure on Near- and Middle-Infrared Radiation . . . . . Jian Zhang, Bai Hao, Xu Zhang, Huanmei Yuan, Zefei Zhang and Liyun Yang Incorporation of Silver Nanoparticles in Zinc Oxide Matrix in Polyester Thermoplastic Elastomer (TPE-E) Aiming Antibacterial Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Leonardo Guedes Marchini, Duclerc Fernandes Parra and Vijaya Kumar Rangari Part III

59

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79

Non-ferrous Metals and Processes

Adsorption Behavior of Cu(II) to Silica-Humics Composite Aerogels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Guihong Han, Pengfei Tang, Hongyang Wu, Jun Ma, Xiaomeng Yang and Yongsheng Zhang Inter- and Transgranular Nucleation and Growth of Voids in Shock Loaded Copper Bicrystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . Elizabeth Fortin, Benjamin Shaffer, Saul Opie, Matthew Catlett and Pedro Peralta

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Alloying and Annealing Effects on Grain Boundary Character Evolution of Al-alloy 7075 Thin Films: An ACOM-TEM Analysis . . . . . 109 Prakash Parajuli, Rubén Mendoza-Cruz, Miguel José Yacamán and Arturo Ponce Part IV

Ferrous Materials and Processes

Evolution of Precipitates During Rolling and Annealing Process in Non-Oriented Electrical Steel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123 Qiang Ren, Lifeng Zhang, Yan Luo, Lin Cheng and Piotr Roman Scheller Structure and Magnetic Properties of a Medium-Entropy Fe46Co34Ni20 Alloy Powder . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131 Anuj Rathi and Tanjore V. Jayaraman Evolution of Microstructure and Mechanical Properties of 20Cr13 Under Cavitation Erosion . . . . . . . . . . . . . . . . . . . . . . . . . . . 143 Guiyan Gao and Zheng Zhang

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Investigating the Mechanical Response Under Quasi-static Compression of Cold-Rolled Lean Duplex Stainless Steel 2101 . . . . . . . 153 Tayla M. Nankivell, Ali A. H. Ameri, Juan P. Escobedo-Diaz, Md. Z. Quadir, C. Logos and Simon S. Higgs Preparation of Magnesium Aluminum Ferrite Spinel by Microwave Sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161 Huimin Tang, Zhiwei Peng, Foquan Gu, Lei Ye, Liancheng Wang, Leixia Zheng, Weiguang Tian, Mingjun Rao, Guanghui Li and Tao Jiang Part V

Polymer and Composite Materials

Two Fibers Used in the Colombian Amazonia and Their Use as Potential Reinforcement for Composite Materials . . . . . . . . . . . . . . . . . 173 Henry A. Colorado, Claudio Aguilar and Sergio Neves Monteiro Influence of Albizzia Lebbeck Benth Pods Particulate on Mechanical Properties of Low-Density Polyethylene . . . . . . . . . . . . . 179 Oluwashina Philips Gbenebor, Emmanuel Isaac Akpan, Festus Omo Osabumwenre and Samson Oluropo Adeosun Part VI

Analysis of Surfaces and Interfaces

Friction Stir Welding of Aluminum Alloys and Steels: Issues and Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189 Mian Wasif Safeen and Pasquale Russo Spena Magnetic Characterization of CarTech® Hypocore™ Alloy at Cryogenic Temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 V. M. Meka, E. M. Fitterling and T. V. Jayaraman Part VII

Characterization and Synthetic Process of Materials

Advances in Scratch Characterization of Automotive Clearcoats . . . . . . 211 Pierre Morel, Linqian Feng, Nadia Benhamida, Warren Denning, Brandon Frye, Andrew T. Detwiler, Leslie T. Baker and Deepanjan Bhattacharya Microwave-Assisted Solid-State Synthesis of Fluorinated Hydroxyapatite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225 Qian Peng, Huimin Tang, Zhangui Tang and Zhiwei Peng Properties of ZnO Micro/Nanostructures on Aluminum Substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237 Shadia J. Ikhmayies, Hassan K. Juwhari and Bashar Lahlouh

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Synthesis and Electrochemical Properties of Molybdenum Disulfide/Graphene Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247 Guihong Han, Wei Wang, Yanfang Huang, Yongqian Duan and Weijun Peng Synthesis and Characterization of PVP/CaCO3-Ag Blend Hydrogel by Gamma Irradiation: Study of Drug Delivery System and Antimicrobial Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255 Angelica Tamiao Zafalon, Vinícius dos Santos Juvino, Luiz Gustavo Hiroki Komatsu, Duclerc Fernandes Parra, Ademar Lugao, Temesgen Samuel and Vijaya Rangari Part VIII

Mineral Processing and Extraction

Microplastics: A Novel Method for Surface Water Sampling and Sample Extraction in Elechi Creek, Rivers State, Nigeria . . . . . . . . . . . 269 Example Briggs, Esperidiana A. B. de Moura, Helio A. Furusawa, Marycel E. B. Cotrim, Emeka E. Oguzie and Ademar B. Lugao Leaching Zinc from Crystallization Slag by Acid Leaching: Process Optimization Using Response Surface Methodology . . . . . . . . . 283 Guojiang Li, Yongguang Luo and Tingfang Xie Study on Recovery of Zinc from Metallurgical Solid Waste Residue by Ammoniacal Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291 Aiyuan Ma, Xuemei Zheng, Shengyou Shi, Haiye He, Yanhong Rao, Guoyan Luo and Fang Lu Optimization of Fine Ilmenite Flotation Performed with Collectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301 Yankun Wu, Shengpeng Su, Weijun Peng, Yongsheng Zhang, Guixia Fan, Guihong Han and Yijun Cao Arsenic Reduction and Cobalt Removal in the Arsenic-Containing Leachate from Alkali Leaching of Arsenic-Containing Cobalt/Nickel Residue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311 Jinxi Qiao, Shuang Long, Zhiqiang Liu, Xintao Sun, Zhaoming Sun, Hualei Miao, Jinyang Chen and Ailiang Chen Part IX

Nanostructure and Characterization of Materials

A Comparison Between ZnO Hexagonal Micro/Nanoprisms Deposited on Aluminum and Glass Substrates . . . . . . . . . . . . . . . . . . . . 321 Shadia J. Ikhmayies

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Microwave-Assisted One-Step Synthesis of FeCo/Graphene Nanocomposite for Microwave Absorption . . . . . . . . . . . . . . . . . . . . . . . 329 Jianhui Peng, Zhiwei Peng, Liancheng Wang, Leixia Zheng, Zhongping Zhu, Guanghui Li and Tao Jiang Part X

Metallurgical Process

Effect of Metallic Iron Sinter Feed on Sinter Mineralogy and Quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343 Mingming Zhang and Marcelo Andrade Effect of Microstructure on Resistance to Buildups Formation of Carbon Sleeves in Continuous Annealing Furnace for Silicon Steel Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351 Mingsheng He, Xiongkui Wang, Wangzhi Zhou, Xuecheng Gong, Jing Zhang and Jian Xu Influence of Cr2O3 and Basicity on Viscosity of Ti-Bearing Blast Furnace Slag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361 Guibao Qiu, Jian Wang, Shiyuan Liu and Qingjuan Li Raman Spectroscopy on the KBF4–KF–KCl Molten Salt System . . . . . . 371 Xianwei Hu, Bo Li, Jiangyu Yu, Zhongning Shi, Bingliang Gao and Zhaowen Wang Thermodynamic Characteristics of Ferronickel Slag Sintered in the Presence of Magnesia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379 Foquan Gu, Zhiwei Peng, Yuanbo Zhang, Huimin Tang, Lei Ye, Weiguang Tian, Guoshen Liang, Joonho Lee, Mingjun Rao, Guanghui Li and Tao Jiang Characterization on the Properties of Calcium Stannates Synthesized Under Different Atmospheres . . . . . . . . . . . . . . . . . . . . . . . 389 Benlai Han, Zijian Su, Yuanbo Zhang, Bingbing Liu, Manman Lu and Tao Jiang Part XI

Construction Materials

Use of Municipal Solid Waste Incinerator (MSWI) Fly Ash in Alkali Activated Slag Cement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401 Kang Huang, Xiaohui Fan, Min Gan and Zhiyun Ji Reliability Increasing of an Estimation of Rocks Strength by Non-destructive Methods of Acoustic Testing Due to Additional Informative Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 411 A. S. Voznesenskii, M. N. Krasilov, Ya. O. Kutkin and M. N. Tavostin

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Characterization of Water/Ethanol/Bentonite Dispersions . . . . . . . . . . . 425 Margarita Bobadilla, Thamyres C. Carvalho, Antonio H. Munhoz Junior, Maria das Graças da Silva-Valenzuela and Francisco R. Valenzuela-Diaz Part XII

Poster Session

A Study of the Load Stages by the Displacement of Mortars Composed of Ornamental Stone Residues by the Method of Squeeze Flow . . . . . . . 435 P. I. Moreira, L. F. Ciribelli, G. C. Xavier, J. Alexandre, G. C. M. Carvalho, A. R. G. Azevedo, S. N. Monteiro, E. B. Zanelato and M. T. Marvila Alpha-Alumina Synthesis Using Gamma-Alumina Powders . . . . . . . . . . 441 Antônio Hortencio Munhoz Junior, Gustavo Figueiredo Galhardo, Fernando dos Santos Ortega, Nelson Batista de Lima, Dênison Angelotti Moraes, Leila Figueiredo de Miranda and Francisco Rolando Valenzuela-Diaz An Investigation of Mechanical and Thermal Properties of Polypropylene Reinforced with Different Clays . . . . . . . . . . . . . . . . . 453 Alex S. Monteiro, Daili A. S. Barreira, Jaqueline S. Silva, Rene R. Oliveira, Francisco R. Valenzuela-Díaz and Esperidiana A. B. Moura Analysis of Rheological Behavior by the Method Squeeze Flow in Mortars Incorporated with Ornamental Stone Residue . . . . . . . 465 G. C. M. Azevedo, P. I. Moreira, L. F. Ciribelli, G. C. Xavier, J. Alexandre, A. R. G. Azevedo and S. N. Monteiro Analysis of the Feasibility of the Use Waste from the Foundry Process in Green Sands in the Manufacturing of Soil-Cement Blocks . . . . . . . . . 473 Niander A. Cerqueira, Victor B. Souza, Guilherme M. R. Coutinho and Lucas X. P. da Silva Analysis of the Life Extension of ASTM A-36 Steel Structures Using the Concepts of Fracture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485 Kayan A. Carneiro, Victor B. Souza, Niander A. Cerqueira, Lucas Costa, Amanda C. Lima, Afonso R. G. Azevedo and Daniel P. Gallo Ceramic Properties: Clay Smectite Synthetic . . . . . . . . . . . . . . . . . . . . . 495 Thamyres C. Carvalho, Camila N. Maggi, Margarita Bobadilla, E. Hildebrando, Roberto F. Neves and Francisco R. Valenzuela-Diaz

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Chemical and Instrumental Characterization of a Sulphosalt Lead Type Jamesonite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503 M. Reyes Pérez, Elia Guadalupe Palacios Beas, Francisco R. Barrientos, Miguel Pérez Labra, Julio Cesar Juárez Tapia, Iván Alejandro Reyes Domínguez, Mizraim Uriel Flores Guerrero, Michell Aislinn Teja Ruiz and Carlos Elías Gutiérrez García Characterization of a Composite of High-Impact Polystyrene, Pseudoboehmite and Graphene Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . 511 Antônio Hortencio Munhoz Junior, Caroline Valadão Pacheco, Henrique Tadeu T. S. Melo, Renato Meneghetti Peres, Leonardo Gondim de Andrade e Silva, Leila Figueiredo de Miranda and Marcos Romero Filho Characterization of Antistatic Packaging Based on PET/rGO . . . . . . . . 523 Leila Figueiredo de Miranda, Antônio Hortêncio Munhoz Jr, Terezinha Jocelen Masson, Leonardo Gondin de Andrade e Silva and Karl Friehe Characterization of Oxides from Al–Mg–Zn Alloys with Heat Treatment, with Scanning Electron Microscopy and Fluorescence Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535 Aline Hernández, Bernardo Campillo, Sergio Serna, Álvaro Torres and Natalia Loera Characterization of Printed Circuit Boards of Obsolete (PCBs) Aimed at the Production of Copper Nanoparticles . . . . . . . . . . . . . . . . . 543 Thamiris Auxiliadora Gonçalves Martins, Karen Espina Gomes, Carlos Gonzalo Alvarez Rosario, Denise Crocce Romano Espinosa and Jorge Alberto Soares Tenório Comparative Analysis of Dynamic Impact Tests Between the Charpy V-Notch Test and the Drop Tower Test . . . . . . . . . . . . . . . 553 Chaitanya Gunturi, Juan P. Escobedo and M. A. Islam Comparative Study of the Use of Rice Husk Ashes and Graphite as Fillers in Polypropylene Matrix Composites . . . . . . . . . . . . . . . . . . . 561 Alex S. Monteiro, Daili A. S. Barreira, Suellen Signer Bartolomei, Rene R. Oliveira and Esperidiana Augusta Barreto de Moura Development of Biocomposite Materials from Biodegradable Polymer and Bio-hydroxyapatite Derived from Eggshells for Biomedical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571 Pedro R. S. Reis, Julyana G. Santana, Rene R. Oliveira, Vijaya K. Rangari, Felipe R. Lourenço and Esperidiana A. B. Moura

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Development of Methodology for the Characterization and Incorporation of Waste from the Paper Industry in Cementitious Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583 A. R. G. Azevedo, J. Alexandre, M. T. Marvila, E. B. Zanelato, B. C. Mendes, N. A. Cerqueira, S. N. Monteiro, G. C. Xavier, L. G. Pedroti and V. Souza Differences in Properties of Pro-degradant Added PP and Gamma-Irradiated PP Under Environmental Aging . . . . . . . . . . . . 591 Rebeca da Silva Grecco Romano, Washington Luiz Oliani, Vijaya Rangari Kumar, Duclerc Fernandes Parra and Ademar Benévolo Lugão Effect of Phosphate Antioxidant on Resisting to Buildups Formation of Carbon Sleeves in Continuous Annealing Furnace for Silicon Steel Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605 Mingsheng He, Xiongkui Wang, Xuecheng Gong, Jing Zhang, Wangzhi Zhou and Jian Xu Effect of the Incorporation of Iron Ore Tailings on the Properties of Clay Bricks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617 Beatryz Cardoso Mendes, Leonardo Gonçalves Pedroti, Rita de Cássia S. S. Alvarenga, Mauricio Paulo Ferreira Fontes, Pedro Cota Drumond, Anderson Almeida Pacheco, Márcia M. S. Lopes and Afonso R. G. de Azevedo Effect Study of the Incorporation of the Green Lake Clay in the Polypropylene Homopolymer Properties . . . . . . . . . . . . . . . . . . . 629 J. N. Sales, P. N. S. Poveda, A. Ortiz, F. R. Valenzuela-Diaz and L. A. Silva Electron Beam Effect on the Thermal and Mechanical Properties Analysis of DGEBA/EPDM Compound . . . . . . . . . . . . . . . . . . . . . . . . . 637 Anderson dos Santos Mesquita, Ian Trolles Cavalcante and Leonardo Gondim de A e Silva Evaluation of Technological Properties of Soil-Cement Blocks Using Experimental Design of Mixtures . . . . . . . . . . . . . . . . . . . . . . . . . 647 A. R. G. Azevedo, J. Alexandre, M. T. Marvila, E. B. Zanelato, G. C. Xavier, N. A. Cerqueira, V. B. Souza, T. E. S. Lima and S. N. Monteiro Exploration of Humic Acids as the Binder of Silicon-Based Anode for Lithium-Ion Batteries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657 Shuzhen Yang, Guihong Han, Yanfang Huang and Jiongtian Liu Impact Response of Bamboo Guadua Angustifolia Kunth . . . . . . . . . . . 665 Julian Rua, M. F. Buchely and Henry A. Colorado

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Incorporation of EVA Residue for Production of Lightweight Concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 673 R. O. Machado, L. C. K. M. Pereira, E. B. Zanelato, A. L. F. Manhães, A. R. G. Azevedo, M. T. Marvila, J. Alexandre, S. N. Monteiro and L. T. Petrucci Innovation of Building Materials: Ecological Bricks, Characterization of Complementary Inorganic Raw Materials . . . . . . . . . . . . . . . . . . . . . 683 Javier Flores-Badillo, Adriana Rojas-León, Alma Delia Román-Gutiérrez, Juan Hernández-Ávila, Eleazar Salinas-Rodríguez and Christopher Contreras-López Investigation on Mechanical Behaviors of Polyamide 11 Reinforced with Halloysite Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693 Danae Lopes Francisco, Lucilene Betega de Paiva, Wagner Aldeia, Ademar B. Lugão and Esperidiana A. B. Moura Measurement of SnO2 Nanoparticles Coating on Titanium Dioxide Nanotube Arrays Using Grazing-Incidence X-Ray Diffraction . . . . . . . . 703 Yunhui Tang, Bo Wang, Hongyi Li and Mingsheng He Microstructural Characterisation of a High Strength Steel Subjected to Localised Blast Loading . . . . . . . . . . . . . . . . . . . . . . 713 Simon Higgs, Ali Ameri, Juan Pablo Escobedo-Diaz, Brodie McDonald, Huon Bornstein, Zakaria Quadir, Tayla Nankivell and Wayne Hutchison Mortars with Pineapple Fibers for Use in Structural Reinforcement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 721 M. T. Marvila, A. R. G. Azevedo, J. Alexandre, E. B. Zanelato, S. N. Monteiro, D. Cecchin and L. F. Amaral Performance of Epoxy Matrix Reinforced with Fique Fibers in Pullout Tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 729 Michelle Souza Oliveira, Artur Camposo Pereira, Fabio da Costa Garcia Filho, Luana Cristyne da Cruz Demosthenes and Sergio Neves Monteiro Production and Characterization of a Hybrid Composite of Polypropylene Reinforced with Piassava (Attalea funifera Martius) Fiber and Light Green Clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735 Sabrina A. Correia, Pedro V. Cruz, Tasson C. Rodrigues, Alex Monteiro, Francisco R. V. Diaz and Esperidiana A. B. Moura Proposal of Dosing of Mortars Using Simplex Network . . . . . . . . . . . . . 747 M. T. Marvila, A. R. G. Azevedo, J. Alexandre, E. B. Zanelato, S. N. Monteiro and N. A. Cerqueira

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Recycled Gypsum Particles Incorporation in Recycled Expanded Polystyrene by Biodegradable Solvent—Preparation and Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757 Suellen Signer Bartolomei, Esperidiana Augusta Barreto de Moura and Helio Wiebeck Structural Analysis of Sintered Products of BaTiO3 Doped with Sm3+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 765 J. P. Hernández-Lara, M. Pérez-Labra, C. C. Gutierrez-Hernández, F. R. Barrientos-Hernández, J. A. Romero-Serrano, A. Hernández-Ramírez, M. Reyes-Pérez, J. C. Juárez-Tapia and V. E. Reyes-Cruz Study of the Electrical Properties of rGO Obtained by Different GO Reduction Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 773 Leila Figueiredo Miranda, Paulo Victor Cedini Gomes, Fabio Jesus Moreira de Almeida, Leonardo Gondim Andrade e Silva, Antonio Hortencio Munhoz Junior and Terezinha Jocelen Masson Study of the Influence of Organic Peroxide and Elastomeric Modifier in the Mechanical and Flow Properties of the Recycled Polypropylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 787 Patricia N. S. Poveda and Leonardo G. A e Silva Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 793 Subject Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 797

About the Editors

Bowen Li is a Research Professor in the Department of Materials Science and Engineering and Institute of Materials Processing at Michigan Technological University. His research interests include materials characterization and analysis, metals extraction, ceramic process, antimicrobial additives and surface treatment, porous materials, applied mineralogy, and solid waste reuse. He has published more than 110 technical papers in peer-reviewed journals and conference proceedings, authored/coauthored three books, and edited/ coedited seven books. He also holds 15 patents and has delivered more than 30 invited technical talks. Dr. Li. received a Ph.D. in Mineralogy and Petrology from China University of Geosciences Beijing in 1998, and a Ph.D. in Materials Science and Engineering from Michigan Technological University in 2008. He has been an active member of The Minerals, Metals & Materials Society (TMS); Society for Mining, Metallurgy, and Exploration (SME); and China Ceramic Society. At TMS, he is the current Chair of the Materials Characterization Committee and member of the Powder Materials Committee and Biomaterials Committee, a former Extraction and Processing Division Award Committee member, a JOM Subject Advisor, and a Key Reader for Metallurgical and Materials Transactions A. He is the organizer/co-organizer of a number of international symposia and sessions. He also served as the

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About the Editors

editorial board member of the Journal of Minerals and Materials Characterization and Engineering, SciFed Journal of Metallurgical Science, and FUTO Journal Series. Jian Li is a senior research scientist at Canmet MATERIALS in Natural Resources Canada. He obtained his B.Sc. in Mechanical Engineering from Beijing Polytechnic University, M.Sc. in Metallurgical Engineering from Technical University of Nova Scotia (TUNS), and Ph.D. in Materials and Metallurgical Engineering from Queen’s University, Kingston, Ontario, Canada. He has broad experience in materials processing and characterization including alloys deformation, recrystallization, and micro-texture development. He has extensive experience in focused ion beam (FIB) microscope techniques. He is also an expert in various aspects of SEM-EDS and EPMA techniques. He holds a patent, has authored three book chapters, and has published more than 140 papers in scientific journals and conference proceedings. Shadia Ikhmayies received a B.Sc. and M.Sc. from the physics department at the University of Jordan in 1983 and 1987 respectively, and a Ph.D. on the topic of producing CdS/CdTe thin film solar cells from the same university in 2002. She now works at Isra University in Jordan as an associate professor. Her research is focused on producing and characterizing semiconductor thin films, and thin film CdS/CdTe solar cells. She also works in characterizing quartz in Jordan for the extraction of silicon for solar cells and characterizing different materials by computation. She has published 48 research papers in international scientific journals, 73 research papers in conference proceedings, and 3 chapters in books. She is the author of two books for Springer, Silicon for Solar Cell Applications and Performance Optimization of CdS/CdTe Solar Cells (both in production), editor of the book Advances in II-VI Compounds Suitable for Solar Cell Applications (Research Signpost), the book Advances in Silicon Solar Cells (Springer), an eBook series about material science (in development with Springer), and several TMS proceedings publications. She is the winner of the

About the Editors

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TMS Frank Crossley Diversity Award (2018), and the World Renewable Energy Congress 2018 (WREC-18) Pioneering Award. Dr. Ikhmayies is a member of the The Minerals, Metals & Materials Society (TMS) and the World Renewable Energy Network (WREN). She is a member of the international organizing committee and the international scientific committee in the European Conference on Renewable Energy Systems (ECRES2015– ECRES2018). She is a member of the editorial board of the International Journal of Materials and Chemistry (Scientific and Academic Publishing), and has served as a technical advisor/subject editor for JOM (2014 and 2019). She has been a guest editor for topical collections from the European Conference on Renewable Energy Systems in the Journal of Electronic Materials, and an editorial advisory board member for Recent Patents on Materials Science (Bentham Science). She is a reviewer for 24 international journals, was the Chair of the TMS Materials Characterization Committee (2016–2017), and has been lead organizer of more than four symposia at the TMS Annual Meeting and Exhibition. Mingming Zhang is a lead research engineer at ArcelorMittal Global R&D in East Chicago, Indiana. His main responsibilities include raw material characterization and process efficiency improvement in mineral processing and ironmaking areas. He also leads a technical relationship and research consortium with university and independent laboratory members and manages pilot pot-grate sintering test facility at ArcelorMittal Global R&D East Chicago. Dr. Zhang has more than 15 years of research experience in the field of mineral processing, metallurgical and materials engineering. He obtained his Ph. D. in Metallurgical Engineering from The University of Alabama and his master’s degree in Mineral Processing from General Research Institute for Non-ferrous Metals in China. Prior to joining ArcelorMittal, he worked with Nucor Steel Tuscaloosa, Alabama where he was metallurgical engineer leading the development of models for simulating slab solidification and secondary cooling process.

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About the Editors

He has conducted a number of research projects involving mineral beneficiation, thermodynamics and kinetics of metallurgical reactions, electrochemical processing of light metals, energy-efficient-, and environmental cleaner technologies. He has published more than 50 peer-reviewed research papers and is the recipient of several U.S. patents. He also serves as editor and reviewer for a number of prestigious journals including Metallurgical & Materials Transactions A and B, JOM, Journal of Phase Equilibria and Diffusion, and Mineral Processing and Extractive Metallurgy Review. Dr. Zhang has made more than 20 research presentations at national and international conferences including more than 10 keynote presentations. He is the recipient of 2015 TMS Young Leaders Professional Development Award. He has been invited by a number of international professional associations to serve as conference organizer and technical committee member. These associations include The Minerals, Metals & Materials Society (TMS) and the Association for Iron & Steel Technology (AIST). Yunus Eren Kalay is an Associate Professor of Metallurgical and Materials Engineering and Assistant to the President at METU Ankara, Turkey. He received his Ph.D. with Research Excellence award from Iowa State University in 2009. His Ph.D. topic was related to the metallic glass formation in Al-based metallic alloy systems. Following his Ph.D., he pursued his postdoctoral research at Ames National Laboratory, where he practiced Atom Probe Tomography. In 2011, he joined the Department of Metallurgical and Materials Engineering (METE) of Middle East Technical University (METU) as an Assistant Professor and in 2014 he was promoted to Associate Professor. His research interests span microstructural evolution in metallic alloys, rapid solidification of metallic alloys, nanostructured and amorphous alloys, lead-free solders, electronic packaging, and advanced characterization techniques such as scanning and transmission electron microscopy, electron and X-ray spectroscopy, and application of synchrotron X-ray scattering in materials research. He was awarded the METU Prof. Dr. Mustafa Parlar Foundation Research Incentive Award, which is

About the Editors

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a prestigious award that recognizes young scientists in Turkey with exceptional achievements and research productivity. Dr. Kalay is an active member of the Materials Characterization Committee and Phase Transformations Committee of TMS, and has served on the organizing committees of three international and one national congress including IMMC, MS&T, and TMS. He has also been involved in many synergistic activities such as serving as founder editor of Turkey’s first undergraduate research journal, MATTER (http://matter.mete. metu.edu.tr/), and has organized materials science camps for K-12 students. John S. Carpenter is a scientist within the manufacturing and metallurgy division at Los Alamos National Laboratory. He received his Ph.D. in Materials Science and Engineering from The Ohio State University in 2010 after performing his undergraduate studies at Virginia Tech. His research focus is on enabling advanced manufacturing concepts through experiments employing novel processing techniques, advanced characterization, and small-scale mechanical testing. Currently, he is working on projects related to the qualification of additively manufactured components and using high-energy X-rays to study phase transformations during solidification in MIG cladding. Throughout his career, he has utilized many characterization techniques including neutron scattering, X-ray synchrotron, XCT, PED, TEM, EBSD, and SEM. Dr. Carpenter has more than 55 journal publications, 1 book chapter, and 25 invited technical talks to his credit. With regard to TMS service, he currently serves as the Extraction & Processing Division (EPD) representative on the Program Committee, the Structural Materials Division representative on the Content Development and Dissemination Committee, chair of the Advanced Characterization, Testing, and Simulation Committee, and the EPD liaison on the Additive Manufacturing Bridge Committee. He is a participating member of the Mechanical Behavior of Materials Committee and has served as chair of the Characterization Committee in the past. John serves as a Key Reader for Metallurgical and Materials Transactions A and has coedited special

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About the Editors

sections in JOM related to neutron diffraction, coherent X-ray diffraction imaging methods, and modeling in additive manufacturing. He is the 2012 recipient of the EPD Young Leaders Professional Development Award. Jiann-Yang Hwang is a Professor in the Department of Materials Science and Engineering at Michigan Technological University. He is also the Chief Energy and Environment Advisor at the Wuhan Iron and Steel Group Company, a Fortune Global 500 company. He has been the editor-in-chief of the Journal of Minerals and Materials Characterization and Engineering since 2002. He has founded several enterprises in areas including water desalination and treatment equipment, microwave steel production, chemicals, flyash processing, antimicrobial materials, and plating wastes treatment. Several universities have honored him as a Guest Professor, including the Central South University, University of Science and Technology Beijing, Chongqing University, Kunming University of Science and Technology, and Hebei United University. Dr. Hwang received his B.S. from National Cheng Kung University 1974, M.S. in 1980 and Ph.D. in 1982, both from Purdue University. He joined Michigan Technological University in 1984 and has served as its Director of the Institute of Materials Processing from 1992 to 2011 and the Chair of Mining Engineering Department in 1995. He has been a TMS member since 1985. His research interests include the characterization and processing of materials and their applications. He has been actively involved in the areas of separation technologies, pyrometallurgy, microwaves, hydrogen storage, ceramics, recycling, water treatment, environmental protection, biomaterials, and energy and fuels. He has more than 28 patents and has published more than 200 papers. He has chaired the Materials Characterization Committee and the Pyrometallurgy Committee in TMS and has organized several symposia. He is the recipient of TMS Technology Award and the Michigan Tech Bhata Rath Research Award.

About the Editors

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Sergio Neves Monteiro graduated as metallurgical engineer (1966) at the Federal University of Rio de Janeiro (UFRJ). He received his M.Sc. (1967) and Ph. D. (1972) from the University of Florida, followed by a course 1975 in Energy at the Brazilian War College and postdoctorate (1976) at the University of Stuttgart. He joined (1968) the Metallurgy Department as full professor of the postgraduation program in engineering (COPPE) of the UFRJ; was elected head of department (1978), coordinator of COPPE (1982) and UnderRector for Research (1983); and was invited as UnderSecretary of Science for the State of Rio de Janeiro (1985) and Under-Secretary of College Education for the Federal Government (1989). He retired in 1993 from the UFRJ and joined the State University of North Rio de Janeiro (UENF), from where he retired in 2012. He is now Professor at the Military Institute of Engineering (IME), Rio de Janeiro, and has published over 1200 articles in journals and conference proceedings and has been honored with several awards including the ASM Fellowship. He is top researcher (1A) of the Brazilian Council for Scientific and Technological Development (CNPq) and Top Scientist of State of Rio de Janeiro (FAPERJ). He was President of the Superior Council of the State of Rio de Janeiro Research Foundation, FAPERJ (2012), and currently is coordinator of the Engineering Area of this foundation. He is also president of the Brazilian Association for Metallurgy, Materials and Mining (ABM, 2017–2019), a consultant for the main Brazilian R&D agencies, and a member of the editorial board of five international journals as well as associate editor of the Journal of Materials Research and Technology.

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About the Editors

Chenguang Bai is a Professor in the Department of Metallurgical Engineering, School of Materials Science and Engineering at Chongqing University, China. He received his B.S. in 1982, M.S. in 1987, and Ph.D. in 2003 from Chongqing University. He also furthered his study in the Department of Metallurgy and Materials, University of Toronto as a visiting scholar between October 1995 and January 1997. He has been actively involved in the teaching and scientific research works in ferrous metallurgy, especially in the field of comprehensive utilization of vanadium–titanium magnetite resources. He has more than 20 patents and has published more than 200 research articles, about 60 of which were in the international metallurgical periodicals. He also is Vice Chairman of Chongqing Society for Metals, and was a Member of Advisory Committee of Experts, Department of Engineering and Materials Science, NSFC. He was the Vice President from 2009 to 2011, and the Vice Chairman of University Council of Chongqing University from 2011 to 2016. Juan P. Escobedo-Diaz is a Senior Lecturer in the School of Engineering and Information Technology (SEIT) at UNSW Canberra. He obtained his doctoral degree in Mechanical Engineering at Washington State University. Prior to taking up this academic appointment, he held research positions at the Institute for Shock Physics and Los Alamos National Laboratory. His main research interests center on the dynamic behavior of materials under extreme conditions, in particular high pressure and high strain rate. His focus has been on investigating the effects of microstructural features on the dynamic fracture behavior of metals and metallic alloys. He has published primarily in the fields of shock physics and materials science. He has been a member of The Metals, Minerals & Materials Society (TMS) since 2011. During this time he has co-organized more than five symposia at the Annual Meetings including the symposium on Characterization of Minerals, Metals and Materials since 2014. He was awarded a 2014 SMD Young Leaders Professional Development Award.

About the Editors

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Pasquale Russo Spena is assistant professor of Manufacturing Technology and Systems in the Faculty of Science and Technology of the Free University of Bozen/Bolzano (Italy). Dr. Russo Spena received his M.Sc. in Materials Engineering and his Ph.D. in Industrial Production Systems Engineering (topic: metallurgical engineering) from Politecnico di Torino (Italy). In 2009, he started working as research assistant in the Department of Management and Production Engineering of the Politecnico di Torino; his work was mainly focused in metal processing and characterization and in developing models and tools for the management of product information in manufacturing processes. In 2010, Dr. Russo Spena was appointed as assistant professor of Manufacturing Technology and Systems at the Faculty of Science and Technology of the Free University of Bozen/Bolzano. Dr. Russo Spena’s research interests are in the field of manufacturing and materials engineering, particularly concerning joining techniques for metals, metals and welded joints characterization, and product quality assessment. Currently, his work focuses on understanding the relationship between welding processes (e.g., joining parameters) and mechanical/microstructural properties of welded joints, especially for the automotive industry. This research involves the use of several characterization techniques including, X-ray diffraction, EBSD, SEM, image analysis by digital image correlation techniques. Dr. Russo Spena is member of several national and international scientific organizations. He has published more than 50 articles in refereed journals, conference proceedings, and book chapters. With regard to TMS service, he has served as a member of the Materials Characterization Committee, as well as a symposium co-organizer and session chair.

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About the Editors

Ramasis Goswami is a scientist with the Multifunctional Materials Branch of the Materials Science and Technology Division at Naval Research Laboratory, Washington, DC, USA. He obtained his bachelor degree in Metallurgical Engineering from Bengal Engineering College, Shibpur, India. He then earned his master’s and Ph.D. degrees in Materials Engineering from Indian Institute of Science, Bangalore. He is a recipient of the Alexander von Humboldt fellowship. His current areas of research include the study of dislocation structures ahead of the crack tip, the microstructure and property relationship in metals, alloys and in multilayered thin films, and the study of interfaces and defects in semiconducting thin films. He has published more than 90 peer-reviewed articles in scientific literature.

Part I

Characterization Method Development

Commentary—Are There Still Places for Gallium FIB? Jian Li

Abstract Since developed in the mid-1980s, focused ion beam (FIB) technology has become quite mature. From the initial single Ga ion beam system to nowadays dual-beam FIB, and from application only in semiconductor industry to applications to biological, mineral and materials engineering, FIB systems seemed to have almost maxed out their capability. The question arises is if the Ga FIB will still hold its place after the release of the new generation of plasma FIB in 2015. This paper provides a high-level overview of the two FIB systems. Keywords FIB · Microscopy · Milling · PFIB · LMIS · Resolution

Evolution of FIB Microscopy The concept of focused ion beam (FIB) technique using the liquid gallium ion source (LMIS) was first introduced by Seliger and Fleming [1] in 1974, where they were able to focus a 60 keV ion beam down to 3.5 µm diameter for doping semiconductor devices. In the span of the next 10 years, the technology improved and allowed to focus ion beams produced by LMIS down to about 50 nm. Orloff and Sudraud [2] proposed a design of a FIB system for maskless ion implantation, etching and deposition. One of the most successful early FIB system from Micrion was widely used by semiconductor industry. In the late 1990s, Phaneuf [3] demonstrated the application of FIB microscopy in materials science related research using a 50 kV, 10 nA Micrion-2500 FIB system. With the invention of TEM lift out technique, Giannuzzi and Stevie [4] opened up a new era of FIB applications. The application of FIB microscopy techniques in materials science bloomed in the early 2000s with a flurry of publications [e.g. 5–10].

J. Li (B) CanmetMATERIALS, Natural Resources Canada, 183 Longwood Road South, Hamilton, ON L8P 0A5, Canada e-mail: [email protected] © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_1

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In 1993, FEI introduced the first commercial DualBeamTM instrument that integrated a Ga ion FIB column into a SEM column. In the next 20 years leading to today, dual-beam FIBs have almost completely replaced single beam FIB systems, and has become a powerful microscopy instrument for imaging, analysis and prototype fabrication at the nanometer scale. Nowadays, FIB microscopy has been widely used in various types of studies including but not limited to the following areas: • • • • • • •

Semiconductor micro fabrication, device modifications and failure analysis Cross sectioning and imaging Site-specific TEM specimen preparation Micro–Nanostructure deposition Cryo FIB for biological and nonconductive specimens Tomography (serial sectioning and imaging) 3D EDS and EBSD

Recently, there has been lots of interest to develop capabilities for ultrafine milling steps for nanostructures and biomedical related applications. Phaneuf demonstrated an impressive automated ~3 nm per slice milling process using a Zeiss CrossBeamTM system [11]. However, on the other side of spectrum, there has also been a general need to speed up the milling process to remove a large amount of materials to investigate larger areas. Unfortunately, FIBs with LMIS sources can only provide limited beam current. Table 1 lists the beam current range of a few state-of-the-art FIB microscopes on the market. When milling structural materials, large ion doses are usually required for milling due to limited sputtering yield. For example, under a 30 kV, 65 nA beam current, it takes about 8 h to mill a 100 × 50 × 50 µm trench on Ni-based superalloys. To expedite milling, FEI released the first plasma FIB (Vion) in 2015 that can produce beam current up to 2000 nA. This new plasma FIB, using an ionized Xe beam, can cut through much larger volume of materials within much shorter time. Such high milling rate has enabled research in new areas like investigating concrete structure that requires serial sectioning of large areas (larger than 500 × 500 µm × 300 µm sections).

Table 1 Beam current range of selected FIB systems with LMIS

FIB systems

Beam current

Zeiss CrossBeam

1 pA–100 nA

FEI Helios NanoLab

1 pA–65 nA

JEOL JIB-4610F

Up to 90 nA

Hitachi NX2000

Up to 100 nA

Tescan S8000G

Up to 100 nA

Commentary—Are There Still Places for Gallium FIB?

5

Do We Still Need Ga FIB? Since its release, Plasma FIB (PFIB) has gained lots of attention in the “FIB world”. Its ability to perform rapid ion beam milling at speed that “old timer” FIB operators cannot even imagine a few years back. The simplicity of ion column design and the “unlimited” ion source supply shows superior potential over Ga FIB at which typical LMIS source life is only about 1000 h. A common question is if we are at the stage where we see the end of glorious era of Ga FIB. To answer the question, we need to look into a few aspects that the two types of FIBs can offer.

Resolution Smith et al. [12] showed spot sizes (d 50 ) as a function of ion beam currents. At current below 60 nA, Ga LMIS provide smaller spot size than that of the Xe source. Shown in Fig. 1, under 30 keV, Xe ion beam diameters are about five times larger than the Ga ion beam in low current range. This can translate to about 80 times beam density difference. The smaller Ga ion beam diameter yields to much better resolution at low current range. For ion beam current above 60 nA, Ga ion beam becomes much diffused compared to that of Xe beam in PFIB. It is obvious that PFIB presents great advantage at high beam current range. With tighter beam and large beam current, PFIB can cut through materials extremely fast. In contrast, in fine polishing stage to achieve high-quality cross-sectioned surfaces, Ga FIB is preferred when tighter beam and higher beam density is desired. After the rough cutting with large beam current, finely focused beam with tighter spot size is always required to produce high-quality FIB polished sections for imaging or 3D EBSD work. The beam current required for final polishing is usually on the order

Fig. 1 Comparison of the spot size of Ga FIB and PFIB [12]. d 50 is the beam diameter containing 50% of the primary ions

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Fig. 2 Subset of 3D EBSD from Ga FIB serial sections at 300 nm intervals

of 2.5 nA (on an FEI Helios Ga FIB). This is where Ga FIBs show advantage over the PFIB. Figure 2 is a small subset of 3D-EBSD from a carbon steel where 300 nm slices were cut in a FEI Helios NanoLab Ga FIB using 800 pA beam current under 30 kV.

Artifacts It is well known that FIB with LIMS source suffers, in certain degree, from Ga implantation. Whether it is on FIB sections or TEM foils, small amount of Ga exists inevitably. For some metals, low-temperature Ga-rich intermetallic phase can also form on the surface [13]. However, the Ga implantation is a well-known fact, and as long as one is aware of such artifact, it usually does not cause serious concerns. On the other end, the PFIB milling could introduce Xe bubbles near the surface because of Xe implantation [14]. Thus, if the analysis is about void formation (e.g. void from Helium production after thermal neutron penetration into Ni-based alloys), TEM specimen prepared by PFIB can cause some confusions.

Commentary—Are There Still Places for Gallium FIB?

7

Beam Heating Li and Liu [15] studied specimen temperature increase during FIB milling (with Ga LMIS source). At small beam current (2.5 nA), milling by Ga beam can result in a few degrees of local temperature rise in aluminum alloys. For metal with slightly poor thermal conductivity (woods metal), temperature rise is limited to less than 50 °C. However, at the final stage of TEM specimen preparation, temperature rise can be significant due to limited heat conduction path. For milling with PFIB, there is currently no data on specimen temperature rise. With such large energy input into relatively small milling area at short duration, local temperature rise could be a serious concern. Work is planned to characterize local temperature rise during PFIB milling.

Beam Damage There has been numerous reports on beam damage by FIB milling using Ga LMIS [e.g. 16]. Ga ion beam damage mainly includes surface amorphization, Ga ion implantation, short-range dislocation production, and in some cases low-temperature Ga phase formation [13]. Amorphization has been one of the primary concerns especially for TEM foils prepared by FIB. Under 30 keV Ga ion beam, the surface amorphized layers can be as thick as 22 nm (on each side of the TEM foil that are usually less than 100 nm in total thick). Technique of milling at low kV (2 kV) is frequently used at the final stage of FIB TEM sample preparation to reduce the amorphized layer thickness. Small amount of Ga implantation is almost inevitable when plan view secondary ion images are acquired. On TEM foils, small amount of Ga is always present even when the beam incident angle is close to 90°. Amount of Ga ion beam induced dislocations increases when milling lighter metal alloys (e.g. aluminum and magnesium alloys). The so-called “salt and pepper” type of damage is a combination of ion implantation and shortrange dislocations. This makes it very difficult for TEM analysis of nano precipitates and dislocation structure. For heavy metals (steel, Ni-based superalloys), this type of defects are not as pronounced. Low-temperature Ga-rich phases only form when milling along certain crystallographic orientations of some metal alloys (for example along of Cu where the lattice of more open allowing significant Ga ion channelling) [13]. PFIB milling eliminated adverse effects from Ga. However, although there has been no report yet, surface amorphization can also be of concern due to much broader beam at low beam current range. If the amorphized layer starts to approach 50 nm in thickness, it can result in significant problem for 3D-EBSD tomography as EBSD diffraction patterns largely come from the top ~50 nm layer. Instead of Ga implantation, PFIB milling introduces Xe implantation that can form Xe bubble. Due to in addition, one also should pay attention to potential phase transformation (or thermal

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aging) of metal alloys. Aging of some aluminum and magnesium alloys could start at temperature as low as 100 °C. Thus, one has to be able to defend the nano precipitates observed on TEM foils are truly from the metal alloy, and not a result of FIB milling.

Two Pennies from the Author The introduction of Xe PFIB has shown great potential. With beam current ~20 times larger than Ga FIB, Xe PFIB can remove large amount of materials rapidly. This allows researchers to make much larger cross sections for subsurface microstructure investigation. However, it does not translate to larger TEM specimen since large foil tends to bend from residual stress. In terms of milling quality, Ga FIB is still advantageous due to much tighter beam at current level of less than 60 nA. Thus, at this stage of technology, there is still a place for Ga FIB. Acknowledgements The authors would like to thank financial support from Her Majesty the Queen in Right of Canada, as represented by the Minister of Natural Resources.

References 1. Seliger RL, Fleming WP (1974) Focused ion beams in micro-fabrication. J Appl Phys 45:1416–1422 2. Orloff J, Sudraud P (1985) Design of a 100 kV high resolution focused ion beam column with a liquid metal ion source. Microelectron Eng 3:161–165 3. Phaneuf MW (1999) Imaging, spectroscopy and spectroscopic imaging with an energy-filtered field emission TEM. Micron 30:277–288 4. Giannuzzi LA, Stevie FA (1999) A review of focused ion beam milling techniques for TEM specimen preparation. Micron 30:197–204 5. Phaneuf MW, Li, J, Malis T (1998) FIB techniques for analysis of metallurgical specimens. Microsc Microanal 4:492–493 6. Li J, McMahon GS, Phaneuf MW (2001) In: Proceedings of the microscopically society of Canada, vol XXVIII, pp 26–27 7. Anderson R (2002) Comparison of FIB TEM specimen preparation methods. In: Proceeding of microscopy and microanalysis, vol 8, pp 44–45 8. Li J (2006) Focused ion beam microscope—more than a precision ion milling machine. J Metal 58(3):27–31 9. Jian L, Malis T, Dionne S (2006) Recent advances in FIB TEM specimen preparation techniques. J Mater Charact 57:64–70 10. Li J, Elboujdaini M, Gao M, Revie RW (2008) Formation of plastic zone at the SCC tip in a pipeline experienced hydrostatic testing. Mater Sci Eng A 486:496–502 11. Phaneuf MW (2018) Presentation at 11th annual FIB SEM workshop, McMaster University, Hamilton, Ontario, Canada, 30 Apr–2 May 2018 12. Smith NS et al (2006) High brightness inductively coupled plasma source for high current focused ion beam applications. J Vacuum Sci Technol B 24(6):2902–2906 13. Phaneuf MW, Jian L, Shuman RF, Noll K, Casey JD Jr (2003) Apparatus and method for reducing differential sputter rates. US patent #6,641,705. Issued 04 Nov 2003

Commentary—Are There Still Places for Gallium FIB?

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14. Baillet J et al (2018) Surface damage on polycrystalline-SiC by xenon ion irradiation at high fluence. J Nucl Mater 503:140–150 Elsevier 15. Li Jian, Liu P (2015) Specimen temperature rise considerations during FIB milling. J Microsc 63(1):3–10 16. Jian L (2008) Advances in materials engineering using state-of-the-art microstructural characterization tools. In: Olivante LV (ed) New Material Science Research. Nova Science Publisher. ISBN-13 978-1-60021-654-1

Structural Characterization of Four Chinese Bituminous Coals by X-Ray Diffraction, Fourier-Transform Infrared Spectroscopy and X-Ray Photoelectron Spectroscopy Shuxing Qiu, Shengfu Zhang, Xiaohu Zhou, Rongjin Zhu, Guibao Qiu, Yue Wu and Guangsheng Suo

Abstract Four Chinese bituminous coals were analyzed using X-ray diffraction, Fourier-transform infrared spectroscopy and X-ray photoelectron spectroscopy, and the relationships between structural parameters and coal rank were then established. X-ray diffraction analysis reveals that amorphous and crystalline carbon types exist in coals, and average stacking heights and lateral sizes of the layer structures are various. Good correlations between coal crystalline volume, aromaticity and maximum vitrinite reflectance exist, reflecting their level of maturity. The Fourier-transform infrared spectroscopy analysis shows that A-factor, reflecting the coal hydrocarbongenerating potential, decreases with the increase of maximum vitrinite reflectance. Meanwhile, small values of C-factor and C=O/C=C show little amount of C=O components in coal samples. A good correlation between CH2 /CH3 and R0 indicates that the length of aliphatic chains declines with the increase of coal rank. X-ray photoelectron spectroscopy analysis shows that the relative amounts of C–C and C–O groups rise with the increase of R0 value. The higher the R0 is, the lower the amount of C vacancy exists, which results in coal reactivity decreasing, all of which suggest that the variety of coal structure mainly depends on the coal rank. Keywords Bituminous coals · Carbon structure · Functional groups · Coal rank

S. Qiu · S. Zhang (B) · X. Zhou · R. Zhu · G. Qiu · Y. Wu · G. Suo College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China e-mail: [email protected] S. Qiu · S. Zhang · G. Qiu Chongqing Key Laboratory of Vanadium-Titanium Metallurgy and Advanced Materials, Chongqing University, Chongqing 400044, China © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_2

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Introduction The chemical structure of coal plays an important role in the coking process because of its influence on the reactivity of the combustion, pyrolysis and gasification. A clear understanding of coal structure is beneficial to predict and control the process that affects coke’s properties. However, it is difficult to characterize thoroughly the coal chemical structure because of the extreme complexity, heterogeneity, and diversity of coal properties. Consequently, a comprehensive study of the fundamental coal structure is required. Modern characterization techniques, including X-ray diffraction (XRD), Fouriertransform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), Roman spectroscopy, and X-ray photoelectron spectroscopy (XPS) were used to investigate the complex chemical structure of coal. XRD is considered to be the most useful tool to analyze carbon structure of coal. The characterization of the crystalline structure, including the interlayer spacing, average stacking height and lateral size, can be calculated by classical Scherrer’s equations [1, 2]. FTIR provides important information on functional structure and is widely employed to analyze organic matters in coal [3]. Moreover, the curve-fitting analysis was commonly used to determine the various C=O functional groups, aliphatic and aromatic C–H contents of coal [4–6]. Application of XPS to coal characterization mainly focused on studying the formation of carbon–oxygen functional groups [7, 8]. Coal is abundant in China and its chemical structure is important for the environmental development and utilization. Reflectance is a better maturation parameter than carbon content and aromaticity over the studied maturation range [9]. Therefore, the chemical structure, including crystalline structure, functional groups, was studied by XRD, FTIR and XPS in this work. Furthermore, the relationships between the chemical structure and coal rank were established.

Experimental Samples. Four Chinese bituminous coals (coal A, B, C and D) obtained from Anshan Iron and Steel Group Co. Ltd (located at northeast of China) were used in this study. The samples were pushed into powder (200 mush) and analyzed for proximate (moisture, volatile, fixed carbon and ash), elements analysis (C, H, O, N and S) and maximum vitrinite reflectance. The detailed chemical analysis of coal samples is summarized in Table 1. According to ISO 11760, coal rank rises with the increase of maximum vitrinite reflectance. XRD analysis. XRD was employed to analyze the coal carbon structure by a Rigaku D/MAX 2500 PC with monochromator and a copper Kα X-ray source. The accelerating voltage and current were 40 kV and 150 mA, respectively. The sample was scanned at 4°/min over the angular range of 5°–90° with the scanning interval of 0.02°/step. The broad peak in 2θ ranging from 15 to 35° was fitted by two Gaussian

2.34 1.74 2.30 1.70

34.40 31.72 22.25 18.34

60.94 61.72 71.90 70.30

7.12 9.61 7.52 13.92

84.30 85.49 87.97 88.80

5.66 5.10 4.95 4.51

Hdaf

Cdaf

Ad

Elements analysis (wt%)

FCd

Mad

Vdaf

Proximate analysis (wt%) 8.87 6.28 5.11 5.23

Odaf

0.94 1.36 1.45 1.25

Nd

M moisture, V volatile, FC fixed carbon, A ash, ad air dry, d dry, daf dry-ash-free basis, R0 maximum vitrinite reflectance

Coal A Coal B Coal C Coal D

Coal

Table 1 Proximate and elements analysis of coal samples

0.15 1.47 0.37 1.06

Sd 0.85 1.008 1.228 1.713

R0 (%)

Structural Characterization of Four Chinese Bituminous Coals … 13

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peaks between 20° and 26°, representing γ band and π band (002), respectively [10]. Then, the resultant peak position, intensity, area and full width at half maximum (FWHM) were determined. Consequently, the aromaticity (f a ) was obtained by Eq. (1). f a  Car /(Car + Cal )  Aπ /( Aπ + Aγ )

(1)

The interlayer spacing (d 002 ), average stacking height (L c ) and lateral size (L a ) of carbon crystallite were calculated using the classical Scherrer’s equations [11, 12]: d002  λ/2sinθ002

(2)

L c  0.91λ/(β002 cos θ002 )

(3)

L a  1.84λ/(β100 cos θ100 )

(4)

where λ is the wavelength of X-ray, β002 is the FWHM, and θ002 is the corresponding scattering angle. As well known, the coal carbon structure is closer to graphite structure which described as a regular, vertical stacking of hexagonal aromatic layers. Therefore, the carbon crystallite volume was obtained by assuming coal carbon structure as the cylinder with multiple multi-aromatic rings arranged in parallel in this work, which can be described as the following equation: √ 3 3 × L 2a × L c (5) Vc  8 V c is the crystallite volume, L a is the lateral size, and L c is the average stacking height FTIR analysis. FTIR was used to characterize the evolution of organic functional groups on a Thermo Fisher Scientific Nicolet iS5 spectrometer with the KBr pellet technique. The FTIR spectrum was recorded by co-adding 100 scans in the range of wavenumbers 4000–400 cm−1 at a resolution of 4 cm−1 . Characteristic FTIR band assignments were identified according to the previous works [13, 14]. Furthermore, the FTIR structural parameters, CH2 /CH3 , A-factor, C-factor, C=O/C=C, and Aar /Aal , were calculated by the following equations [15, 16]: CH2 /CH3  (A2920 cm−1 )/(A2950 cm−1 ) −1

−1

A−factor  (A3000−2800 cm )/(A3000−2800 cm

(6) −1

+ A1650−1520 cm ) (7)

C−factor  (A1800−1650 cm−1 )/(A1800−1650 cm−1 + A1650−1520 cm−1 ) (8) −1

−1

CO/CC  (A1800−1650 cm )/(A1650−1520 cm )

(9)

Structural Characterization of Four Chinese Bituminous Coals …

Aar /Aal  (A1650−1520 cm−1 )/(A3000−2800 cm−1 )

15

(10)

XPS analysis. The coal sample was molded into a disc with a diameter of 10 mm and performed on a Thermo Fisher Thetaprobe system with an AlKα X-ray source (1486.7 eV). Charge neutralization was achieved by a dual flood gun system providing simultaneously low kinetic energy electrons (1–2 eV) and Ar+ ions to the sample surface. Data assessment was obtained by the supplier’s Avantage software package using the software implemented so-called smart background subtraction, which was derived from the Shirley one. The background level was iteratively adjusted in a way that it does not go above the data curve [17].

Results and Discussion Carbon structure analysis. Figure 1 shows X-ray diffraction spectrums of four coal samples. It can be seen that high background intensity exists in the coal samples because of amorphous carbon in coal. Furthermore, two peaks at 2θ  26° and 43° existed in coal samples are the characteristic of π band (002) and 100 band of crystalline structure. Therefore, carbon structure in the coal can be regarded as the combination of amorphous and crystalline carbon, which can be described as class structure of graphitization. Two obvious peaks fitted by Gaussian functions are shown in Fig. 1. The characteristic parameters (f a , d 002 , L c , L a and V c ) calculated by curve-fitting of the γ and π bands are listed in Table 2. The values of aromaticity (f a ) vary from the different coal samples and range from 0.598 to 0.793. Average stacking heights (L c ) and lateral sizes (L a ) of the layer structures increase (2.091–2.349 nm and 5.340–8.564 nm) ranging from coal A to coal D. The values of interlayer spacing (d 002 ) almost remain

Fig. 1 XRD spectrums and curve-fitting of two Gaussian peaks for four coal samples in 2θ ranging from 15° to 35°

16 Table 2 Structural parameters obtained from the curve-fitting of XRD spectrums

S. Qiu et al.

Coke samples

fa

d 002 /Å

L c /nm

L a /nm

V c /nm3

Coal A Coal B Coal C Coal D

0.598 0.637 0.716 0.793

3.516 3.514 3.517 3.497

2.091 2.113 2.210 2.349

5.340 5.793 6.423 8.564

39.592 46.054 59.222 111.890

Fig. 2 FTIR spectrums of four coal samples

constant (3.497–3.517 Å) in coal samples. The crystallite volume values increase from coal A to coal D, indicating that degree of class structure of graphitization rises from coal A to coal D. Functional group analysis. Figure 2 shows the FTIR spectrums of four coal samples. A broad peak located at 3411 cm−1 corresponds to the vibration of O–H in all spectrums. The peak at 3040 cm−1 is due to the sp2 -bonded C–H stretching vibration obtained from aromatic structure. The sharp intense bands located at 2920 and 2850 cm−1 can be assigned to aliphatic C–H stretching vibration. The band located at 1590 cm−1 is attributed to the C=O and C=C aromatic ring stretching vibrations. The medium low-intensity band at 1438 cm−1 is due to the aliphatic CH2 and CH3 deformation. The bands located at 1035 and 1009 cm−1 are related to the C–O–R stretching vibration. The region between 900 and 700 cm−1 is attributed to the various aromatic out-of-plane frequencies. The aliphatic C–H stretching bands can be used to evaluate length of aliphatic chains in the macromolecular structure of coal. The C=O functional group, which is well known to play a significant role in coal structure, has a significant effect on various coal reactions and conversion processes. In this work, the differences in the aliphatic groups and C=O components in coal samples were represented by CH2 /CH3 , A-factor, C-factor and C=O/C=C, respectively. However, the peaks for functional groups cannot be confirmed accurately in raw coal spectrum. Thus,

Structural Characterization of Four Chinese Bituminous Coals …

17

Fig. 3 Curve-fitting of four Gaussian peaks for coal A with region ranging from 3000 to 2800 cm−1

Table 3 Structural parameters derived from FTIR of coal samples

Coal samples

CH2 /CH3 A-factor

C-factor

C=O/C=C Aar /Aal

Coal A

2.250

0.324

0.038

0.057

2.091

Coal B

2.000

0.318

0.043

0.064

2.148

Coal C

1.900

0.318

0.028

0.042

2.143

Coal D

1.810

0.232

0.036

0.046

3.315

the curve-fitting method is used to obtain the actual spectral intensity of functional groups. Figure 3 shows four obvious peaks fitted by Gaussian functions. The CH3 asymmetrical stretching vibration (2950 cm−1 ) and the CH2 asymmetrical stretching vibration (2920 cm−1 ) can be clearly separated among these bands to calculate the CH2 /CH3 ratio [18]. The values of CH2 /CH3 (2920 cm−1 /2950 cm−1 ) ratio are ranging from 2.250 to 1.810 (described in Table 3), indicting aliphatic chain length shortens from coal A to coal D. Moreover, the region from 1800 to 1500 cm−1 was curve-fitted to obtain the A-factor, C-factor, C=O/C=C and Aar /Aal . The detailed structural parameters are shown in Table 3. It can be seen that the values of A-factor have the descending tendency ranging from coal A to coal D. Combined with Table 1, the higher A-factor value agrees with the higher volatile and hydrogen content in coal samples, implying that the better hydrocarbon-generating potential takes place in the coal. Meanwhile, small values of C-factor and C=O/C=C reveal that little amount of C=O components exists in coal samples. And values of Aar /Aal are various, indicting the different contents of aromatic compounds exist in the coal samples. XPS analysis. The XPS spectrums of coal samples are shown in Fig. 4. C1s peak, which represents sp2 carbon in C=C bonds in aromatic rings and aliphatic chains, is near 283 eV. Additionally, O1s is near 531 eV. The more detailed peak position, area and area ratio are shown in Table 4. The area ratios calculated from the wide energy spectrums of coal samples are various, indicating the atomic carbon and

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Fig. 4 XPS spectrums of coal samples

Table 4 Atomic carbon content, atomic oxygen content calculated from XPS spectrums of coal samples

Coal samples

E

P (eV)

I

A

R

Coal A

C

283.63

13,340.74

38,773.31

0.47

O

530.87

14,177.12

44,016.70

0.53

Coal B

C

283.82

16,275.80

42,108.11

0.46

O

531.00

16,368.85

48,701.51

0.54

Coal C

C

283.75

15,782.16

41,268.61

0.54

O

531.01

11,276.04

35,077.27

0.46

Coal D

C

283.43

17,692.63

46,449.40

0.52

O

530.80

12,823.17

42,303.55

0.48

E elements, P peak position, I intensity, A area, R relative area ratio

oxygen contents are different in the coal samples, which match the carbon and oxygen element analysis in Table 1. Figure 5a shows C1s and its fitting peaks of coal A. The broadening and asymmetry of the peak cannot be ascribed uniquely to a Gaussian broadening or a multielectron screening on the core hole potential. Instead, other components due to sp3 and carbon–oxygen are identified on the high binding energy side [19]. Therefore, C1s peak was fitted by Gaussian and Lorentzian functions with peaks at the binding energies of 283.8, 284.8, 285.3, 286.3, 287.5, 288.6 and 291.2 eV which are related to the C vacancy, C–C, C–H, C–O, C=O O–C O and π-π, respectively [19, 20]. Figure 5b shows relative content of functional groups carried out by Gaussian–Lorentzian functions. It can be seen that the relative amounts of C–C and C–O increase while that of C vacancy, C–H have a descending tendency ranging from coal A to coal D.

Structural Characterization of Four Chinese Bituminous Coals …

19

Fig. 5 C1s peaks for the four coal samples: a fitting peaks, b relative content of functional groups on coal surface

The relationship between coal structural parameters and coal rank. Coal rank is an important parameter for predicting the coal structure. As shown in Fig. 6a, the crystalline volume and aromaticity obtained from X-ray diffraction are plotted against the maximum vitrinite reflectance. It can be seen that there are linear correlations between the above parameters (R2  0.95 and R2  0.95), respectively. The higher the R0 is, the larger the crystalline volume and aromaticity would become, which make higher degree of coal maturity. Figure 6b shows the relationships between structural parameters obtained from FTIR spectrums and R0 values. The values of A-factor decrease with the increase of R0 values, revealing that higher coal rank makes lower coal hydrocarbon-generating potential. The CH2 /CH3 ratio declines with the increase of R0 value, indicating the coal aliphatic chain length shortens with the ascending of coal rank. It can be seen that Aar /Aal has a good correlation with R0 in coal samples. The relationships between relative content of functional groups from XPS and R0 are shown in Fig. 6c. A linear correlation can be found between the relative content of C vacancy and maximum vitrinite reflectance, and higher R0 will make lower relative content of C vacancy. Therefore, the coal reactivity will decrease with the increase of coal rank because of easy oxidation by molecular oxygen as oxygen binds preferentially in the C vacancy defects. It can be also seen that good relationships between the relative amounts of C–C, C–H and maximum vitrinite reflectance exist. Furthermore, the inter-relations suggest that the variety of structural parameters depends on the coal rank.

Conclusions Structural parameters of four Chinese bituminous coals were analyzed using XRD, FTIR and XPS. The coals contain crystalline carbon with some amount of amorphous carbon. The average stacking heights and lateral sizes of the layer structures increase

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Fig. 6 The relationships between structural parameters and vitrinite reflectance: a crystalline volume, aromaticity and R0 , b structural parameters from FTIR and R0 , c relative content of functional groups from XPS and R0

Structural Characterization of Four Chinese Bituminous Coals …

21

with the increase of coal rank. Linear relationships between the crystalline volume, aromaticity and maximum vitrinite reflectance exist, which represent the level of maturity. The relationship between A-factor and R0 represents the coal hydrocarbongenerating potential decreases with the increase of maximum vitrinite reflectance. Small values of C-factor and C=O/C=C reflect that little amount of C=O components exists in coal samples. A good correlation between CH2 /CH3 and R0 exists, indicating the aliphatic chain length declines with the ascending of coal rank. The relative amounts of C–C and C–O groups obtained from XPS analysis increase with the ascending of R0 . The higher the R0 values, the lower the amount of C vacancy will be, resulting in coal reactivity declining. Furthermore, the inter-relations reflect the dependency of structural parameters on the coal rank. Acknowledgements This work was supported by the National Natural Science Foundation of China (Grant No. 51474042 & 51774061) and the Fundamental Research Funds for Central Universities (Grant No. 106112017CDJQJ138801). The authors also acknowledge the support provided by the Fund of Chongqing Science and Technology (Project No. cstc2018jscx-msyb0988).

References 1. Lu L, Sahajwalla V, Kong C et al (2001) Quantitative X-ray diffraction analysis and its application to various coals. Carbon 39:1821–1833 2. Saikia BK, Boruah RK, Gogoi PK (2009) A X-ray diffraction analysis on graphene layers of Assam coal. J Chem Sci 121:103–106 3. Cloke M, Gilfillan A, Lester E (1997) The characterization of coals and density separated coal fractions using FTIR and manual and automated petrographic analysis. Fuel 76:1289–1296 4. Sobkowiak M, Painter P (1992) Determination of the aliphatic and aromatic CH contents of coals by FT-IR: studies of coal extracts. Fuel 71:1105–1125 5. Sobkowiak M, Reisser E, Given P et al (1984) Determination of aromatic and aliphatic CH groups in coal by FT-IR: 1. Studies of coal extracts. Fuel 63:1245–1252 6. Riesser B, Starsinic M, Squires E et al (1984) Determination of aromatic and aliphatic CH groups in coal by FT-IR: 2. Studies of coals and vitrinite concentrates. Fuel 63:1253–1261 7. Perry DL, Grint A (1983) Application of XPS to coal characterization. Fuel 62:1024–1033 8. Gong B, Pigram PJ, Lamb RN (1998) Surface studies of low-temperature oxidation of bituminous coal vitrain bands using XPS and SIMS. Fuel 77:1081–1087 9. Mastalerz M, Bustin RM (1994) Variation in reflectance and chemistry of vitrinite and vitrinite precursors in a series of tertiary coals, Arctic Canada. Org Geochem 22:921–933 10. Sonibare OO, Haeger T, Foley SF (2010) Structural characterization of Nigerian coals by X-ray diffraction, Raman and FTIR spectroscopy. Energy 35:5347–5353 11. Qiu S, Zhang S, Zhang Q et al (2017) Effects of iron compounds on pyrolysis behavior of coals and metallurgical properties of resultant cokes. J Iron Steel Res Int 24(12):1169–1176 12. Gupta S, Sahajwalla V, Burgo J et al (2005) Carbon structure of coke at high temperatures and its influence on coke fines in blast furnace dust. Metall Mater Trans B 36:385–394 13. Qiu S, Zhang S, Wu Y et al (2018) Structural transformation of fluid phase extracted from coal matrix during thermoplastic stage of coal pyrolysis. Fuel 232:374–383 14. Drobniak A, Mastalerz M (2006) Chemical evolution of miocene wood: example from the Belchatow brown coal deposit, central Poland. Int J Coal Geol 66:157–178 15. Dutta S, Hartkopf-Fröder C, Witte K et al (2013) Molecular characterization of fossil palynomorphs by transmission micro-FTIR spectroscopy: implications for hydrocarbon source evaluation. Int J Coal Geol 115:13–23

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16. Wang S, Tang Y, Schobert HH et al (2011) FTIR and 13C NMR investigation of coal component of late permian coals from southern China. Energy Fuels 25:5672–5677 17. Geng W, Kumabe Y, Nakajima T et al (2009) Analysis of hydrothermally-treated and weathered coals by X-ray photoelectron spectroscopy (XPS). Fuel 88:644–649 18. Ibarra J, Moliner R, Bonet AJ (1994) FT-IR investigation on char formation during the early stages of coal pyrolysis. Fuel 73:918–924 19. Levi G, Senneca O, Causà M et al (2015) Probing the chemical nature of surface oxides during coal char oxidation by high-resolution XPS. Carbon 90:181–196 20. Pietrzak R, Grzybek T, Wachowska H (2007) XPS study of pyrite-free coals subjected to different oxidizing agents. Fuel 86:2616–2624

In Situ Characterization at High Temperature of VDM Alloy 780 Premium to Determine Solvus Temperatures and Phase Transformations Using Neutron Diffraction and Small-Angle Neutron Scattering C. Solís, J. Munke, M. Hofmann, S. Mühlbauer, M. Bergner, B. Gehrmann, J. Rösler and R. Gilles

Abstract New Ni-based superalloy VDM 780 Premium has been developed for higher service temperatures than the alloy 718. This paper describes the properties of this alloy by means of in situ neutron diffraction (ND) and in situ small-angle neutron scattering (SANS) measurements supported by scanning electron microscopy (SEM) images. ND experiments show the phases present in the alloy and their evolution with temperature, which allow us to derive their respective solvus temperatures and the misfit between the hardening phase and the matrix and its change with temperature. Keywords Ni-based superalloy · High-temperature alloy In situ neutron diffraction · In situ small-angle neutron scattering

Introduction Ni-based superalloys are used as gas turbine engine disc components for land-based power generation and aircraft propulsion due to their good mechanical properties at high temperatures together with their resistance to degradation in corrosive or oxiC. Solís (B) · J. Munke · M. Hofmann · S. Mühlbauer · R. Gilles Heinz Maier-Leibnitz Zentrum (MLZ), TU München, Lichtenbergstr. 1, 85748 Garching, Germany e-mail: [email protected] M. Bergner · J. Rösler Institut für Werkstoffe (ifW), Technische Universität Braunschweig, 38106 Braunschweig, Germany B. Gehrmann VDM Metals International GmbH, Kleffstraße 23, 58762 Altena, Germany © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_3

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dizing conditions [1, 2]. Among these, alloy 718 is the most widely used Ni-based superalloy, due to its unique mechanical properties and good processing characteristics [3]. However, as the turbine efficiency increases with the temperature, in the last few decades a great effort was undertaken to develop Ni-based alloys with operation temperatures above 650 °C while keeping the good processing characteristics of the alloy 718. The good mechanical properties at high temperatures of these Ni-based superalloys are mainly provided by the existence of high volume fraction of small Ni3 Al-type γ hardening precipitates in a Ni-based austenitic matrix (γ phase). Alloy 718 is also strengthened by intermetallic precipitates of Ni3 Nb-type γ phase. The existence of co-precipitates of both γ and γ phases with different morphologies (plate, needle, cube or disc shape) has also been observed [4, 5]. Other phases that can be formed are the high-temperature phases Ni3 Nb-based (δ) and the Ni3 Ti-based (η) phases. The limiting service temperature (650 °C) of the alloy 718 is due to the instability of the γ phase which transforms into δ phase resulting in a loss of creep resistance of the alloy. The existence of the different phases and the quantity, shape and size of the different precipitates and co-precipitates depend on composition, processing conditions and heat treatments. Especially, the determination of the different high-temperature phases present in the alloy is fundamental. It is therefore crucial to control the evolution of the different phases at high temperature in order to tailor the mechanical properties at high temperatures to ensure good performance of the final applications [6–9]. Waspaloy shows higher amounts of γ hardening phase than the alloy 718, which allows its use at higher temperatures, but on the other hand, the high γ solvus temperature results in poor hot formability [10]. Alloy 718Plus, in which half of the Fe of the alloy 718 is replaced by Co, shows no γ precipitates. This improves the performance at high temperatures, giving a rise of 60 °C in the operating conditions in comparison with alloy 718, while keeping its workability [11]. The new VDM alloy 780 Premium (Ni, Co, Cr, Nb, Mo, Al, Fe, and Ti) has been developed for even higher service temperature and its structure and performance is currently under investigation [10, 12, 13]. This work presents the structural characterization of a new Ni-based superalloy VDM 780 Premium, with high content of Co, by means of in situ neutron diffraction (ND) at room temperature (RT) and elevated temperatures. The morphology of the different phases is studied by scanning electron microscopy (SEM) and small-angle neutron scattering (SANS). Furthermore, the solvus temperature of the different phases forming this alloy, i.e. the γ hardening phase and the high-temperature (HT) phases, is determined by means of in situ high-temperature ND. From these data also the evolution of the γ/γ misfit as a function of temperature is studied. The misfit as a key parameter influences the mechanical strength of the alloy and more particularly its creep strength [14].

In Situ Characterization at High Temperature …

25

Table 1 Chemical composition of the Ni-based superalloy VDM 780 Premium Ni Co Cr Fe Mo Nb Al wt%

Balance

25

18

Zn(OH)(H2 O)5 > Zn(OH)2 (H2 O)4 , which can be attributed to the hydroxylation of zinc ions, reducing the electrostatic attraction of humic acid with Zn2+ . According to the adsorption experimental results, it was found that the pseudo-second-order kinetic model could be the best one to describe the adsorption process of Zn2+ onto humic acid surface. The pH-dependent experimental results indicated that the amount of Zn2+ adsorbed rose abruptly with the increase of pH at pH < 5, reaching the maximum at pH  5, which were verified by means of zeta potential tests. This work can provide a better understanding of the adsorption between humic acid and Zn2+ at the microscopic scale. Keywords Humic acid · Zn2+ · Adsorption · Molecular dynamic simulations

Introduction Zinc is a typical widespread heavy metal pollutant in natural water environment, which is considered to enter the environments due to human activities such as mining, steel production, coal burning, etc. [1]. Unlike organic contaminants, zinc ions cannot be biodegraded but tend to accumulate in living organisms, and even do harm to human’s health. Hence, zinc ions should be removed from the wastewater to protect the people and the environment. Numerous methods that have been used to remove S. Su · Y. Huang · G. Han (B) · Z. Guo · F. Liu School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, People’s Republic of China e-mail: [email protected] © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_4

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zinc ions include chemical precipitation, membrane filtration, ions flotation, etc. [2]. Nevertheless, these methods are often either expensive or inefficient, especially when very low residual concentrations are required [3]. Heavy metals sorption by organic and inorganic soil components has been considered as a promising alternative for this purpose [4]. Humic acid (HA), the major extractable fraction of humic substances, is ubiquitous in soil, sediment and aquatic environments. It contains numerous chemically functional groups, such as carboxyls, phenolic hydroxyls and aromatic units, which play a critical role in controlling the physicochemical behavior of heavy metals [5]. The acidic functional groups, especially the carboxylic groups of HA, are regarded as the predominant binding sites with metal ions [6]. A significant positive linear relationship between the adsorption capacity of Zn2+ and the carboxylic group contents of HA has been reported in previous studies [7]. However, to our best knowledge, there are few reports that HA interacts with Zn2+ at the molecular level. In this work, the adsorption between HA and Zn2+ was investigated by combining molecular dynamic simulations and experiments. The effect of the number of dissociated carboxylic groups on the adsorption was inspected. Besides, the computational results were further confirmed by adsorption experiments. This work provides an understanding deeply for the adsorption of HA with Zn2+ by computational and experimental study.

Materials and Methods Materials and Characterizations Concentrated stock solutions of Zn2+ were prepared from their sulfates using deionized water and were further diluted to the required concentrations before being used. The concentration of metals was detected by atomic absorption spectrophotometer (TAS-990, Beijing Purkinje General Instrument Co. Ltd., China). The adsorption capacity, namely, qt (mg/g), was calculated by the difference between the initial and equilibrium concentrations of Zn2+ per gram of adsorbent. Commercial HA used in the experiments was obtained from Tianjin Zhiyuan Chemical Reagent Co. Ltd., China, and was further purified using the method proposed by the International Humic Substance Society [8]. All reagents used in our experiments were of analytical grade and used without further purification. Zeta potentials of humic acid particles before and after adsorption by Zn2+ were tested using a JS94k2 zeta meter (Powereach.com, China); each sample was repeated four times and the average values were reported.

Study of the Adsorption of Humic Acid with Zn2+ …

35

A MC

MD C

D

B Fig. 1 Modeling workflow for obtaining equilibration configurations of HA with Zn2+ ; a 2+ Zn(H2 O)2+ 6 , b HA, c preliminary structures of HA-Zn , d equilibration configurations of HAZn2+ ; (Color codes: red  O, gray  C, white  H, beige  Zn)

Molecular Dynamic Simulations MD simulations were conducted by COMPASS force field as implemented in the Forcite module of the Materials Studio 2017 (Accelrys Software Inc. (2016)). Previous researches indicated that the COMPASS force field can provide accurate simulations of structural properties of hydrated metal cations and metal chelating [9−11]. The modeling workflow was presented in Fig. 1. For each case, the initial configuration of the complexes (MC) was obtained by adsorbing the Zn2+ to the HA surface using the adsorption locator module. Then, the system was subsequently subjected to molecular dynamics equilibration for 100 ns at 298 K using a canonical NVT ensemble [10]. The frames in last 20 ns dynamics simulation were used to compute statistics for the adsorption energies between HA and Zn2+ . The adsorption energies are calculated using the following expression [12]: E  E total − E HA − E zinc ions

(1)

where E total is the total energy of the complexes. E HA , E zinc ions are the total energy of the HA and zinc ions, respectively. It is noticeable that more negative values demonstrate more favorable interactions between HA and Zn2+ .

Adsorption Experiments Adsorption experiments were carried out at 25 °C under certain concentration and pH of solutions. During kinetic study, an accurate mass of 0.1 g of HA was added into a series of 100 mL Erlenmeyer flasks filled with 25 mL of 200 mg/L ZnSO4 · 7H2 O solutions. Then, it was shaken in a thermostatic rotary shaker, operating at 150 rpm. The adsorption time was set to 0, 5, 10, 20, 30, 60, 120, 180, and 240 min,

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respectively. For pH experiments, the initial pH of solutions varied from 2 to 7 adjusted by adding either 0.1 M HCl or 0.1 M NaOH. The solution pH was tested using a pH meter. At predetermined time intervals, the suspension was centrifuged at 3500 rpm for 10 min. The final suspensions were filtered by 0.45 µm membrane filter to detect the residual concentration of Zn2+ by atomic absorption spectrophotometer. All experiments were performed in triplicate under identical conditions and the average values were reported.

Results and Discussion Molecular Dynamic Simulations The adsorption energies between HA and Zn2+ were presented in Fig. 2. As shown in Fig. 2, the adsorption energies increase gradually with the increase of the number of dissociated carboxylic groups, because the negative charges on HA surface increase, resulting in the enhancement of the electrostatic interactions between Zn2+ and HA [13]. Besides, the adsorption energies between HA and the hydrated zinc + ions in decreasing order are Zn(H2 O)2+ 6 > Zn(OH)(H2 O)5 > Zn(OH)2 (H2 O)4 in Fig. 4, which could be attributed to the hydroxylation of zinc ions, reducing the electrostatic attraction of HA with Zn2+ .

Fig. 2 Adsorption energies between HA and Zn2+ Adsorption Energy (kcal/mol)

0 -200 -400 -600 2+ Zn

-800

+ Zn(OH) 2 Zn(OH)

-1000 -1200

0

1

2

3

4

5

Numbers of carboxyl groups dissociated

6

Study of the Adsorption of Humic Acid with Zn2+ …

37

Adsorption Kinetics In order to well investigate the adsorption of Zn2+ onto HA surfaces, three kinetic models including pseudo-first-order rate equation [14], the pseudo-second-order rate equation [15] and Elovich model [16] were selected to fit the experimental data. The linear forms of the pseudo-first-order kinetic model, pseudo-second-order model and Elovich model were expressed as Eqs. (2)–(3), respectively. ln(qe − qt )  lnqe − k1 t 1 1 t  + qt k2 qe2 qe

(2)

qt  b ln(ab) + blnt

(4)

(3)

where qe and qt (mg/g) are the adsorption amount of Cu2+ for adsorbent at equilibrium and time t (min), k 1 (min−1 ) and k 2 (g/(mg min)) are the rate constants of pseudofirst-order and pseudo-second-order kinetic model, respectively. And a and b which represent the initial adsorption rate (mg/(g min)) and the desorption constant (g/mg) are Elovich parameters. Adsorption kinetics of Zn2+ onto HA surface was plotted in Fig. 3. It is observed that there is an increase rapidly during starting stage of adsorption, and then followed by a slow adsorption until equilibrium adsorption amount qe which is 8.384 mg/g is reached after approximate 60 min. It is worth emphasizing that the steep sloped within initial parts of the curves demonstrate prompt, dynamic adsorption on the large uncovered reactive sites, while the following stage with a slower adsorption rate may be probably controlled by chemical reaction rate of HA surfaces [17]. The adsorption kinetic parameters and correlation coefficients (R2 ) obtained from the three models were summarized in Table 1. As shown in Table 1, it was found that

10

qt (mg/g) 8 30

6

25 20

4

t/qt

qt(mg/g)

Fig. 3 Effect of contact time and the fitting of the pseudo-second-order kinetic models for Zn2+ adsorbed onto HA surfaces

15 t/qt

10

2

Linear Fit of t/qt

5 0 0

0

50

100

150

200

250

t/min

0

50

100

150

t/min

200

250

S. Su et al.

qt (mg/g)

Fig. 4 Effect of solution pH on adsorption amounts of Zn2+ onto HA surface

8

-20

7

-25

6

-30

5

-35

4

-40

3

-45

2

-50

1

Zeta potential (mv)

38

-55 2

3

4

5

6

7

pH

the value of the correlation coefficients (R2 ) of the pseudo-second-order kinetic model is higher than that for pseudo-first-order and Elovich equation under the experimental conditions, which indicates that the pseudo-second-order kinetic model may be the best one to describe the adsorption process. Meanwhile, the calculated qe value is close to the experimental ones, showing a good linearity with R2 above 0.998. It also confirms the suitability of the pseudo-second-order kinetic equation for adsorption process.

Effect of Solution pH on Zn2+ Adsorption It is believed that the pH value of the solution has a key influence on the adsorption due to its influence on the degree of ionization, the speciation of zinc ions, and the state of functional groups on the HA surface [18–20]. In order to explore the effect of solution pH on Zn2+ adsorbed onto HA surface, the equilibrium adsorption experiments with initial pH ranging from 2 to 7 were performed, and the results of which were depicted in Fig. 4. As presented in Fig. 4, it is evident that the adsorption amount of Zn2+ onto HA surfaces increases abruptly with the increase of pH at pH < 5, reaching the maximum at pH  5. However, it is noticeable that the adsorption amount qt is unreasonable at pH  7, which may be ascribed to the formation of Zn(OH)2 precipitate. In order to confirm the above results, the zeta potential before and after Zn2+ adsorbed was analyzed, and the results of which were depicted in Fig. 4. As can be seen from Fig. 4, the zeta potentials of HA surfaces become more negative with the increase of pH of the solutions. As the solution pH increases from 2 to 5, the zeta potentials raise gradually due to the adsorption of positively charged Zn2+ , which is consistent with the adsorption experimental results.

HA

8.34

qe , exp (mg/g)

5.611

qe (mg/g)

0.02947

k 1 (min−1 )

Pseudo-first-order equation

0.7479

R2 8.032

qe (mg/g) 0.216

k 2 (g/(mg min)) 0.9985

R2

Pseudo-second-order equation

Table 1 Kinetic parameters and correlation coefficients (R2 ) obtained from the three models

–

a

R2 0.1566

b −0.109

Elovich equation

Study of the Adsorption of Humic Acid with Zn2+ … 39

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Conclusions Molecular dynamic simulations and adsorption experiments were performed to investigate the adsorption of humic acid with Zn2+ . The results demonstrate that the adsorption energies between humic acid and Zn2+ rose gradually with the increase of the number of carboxyl dissociated. Besides, the adsorption energies between humic acid and zinc species in decreasing order were Zn(H2 O)+6 > Zn(OH)(H2 O)+6 > Zn(OH)2 (H2 O)4 . From the results of the adsorption experiments, it is found that the pseudo-second-order kinetic model may be the best one to describe the adsorption process of Zn2+ onto humic acid surface. The pH-dependent experimental results indicate that the amount of Zn2+ adsorbed rise abruptly with the increase of pH at pH < 5, reaching the maximum at pH  5, which are further confirmed by means of zeta potential tests. Acknowledgements The authors acknowledge the financial support provided by the National Science Fund of China (No. 51674225, No. 51774252), and the Supercomputer Center in Zhengzhou University.

References 1. Tang X, Li Z, Chen Y (2009) Adsorption behavior of Zn(II) on calcinated Chinese loess. J Hazard Mater 161:824–834 2. Fu F, Wang Q (2011) Removal of heavy metal ions from wastewaters: a review. J Environ Manag 92:407–418 3. Havelcova M, Mizera J, Sykorova I, Pekar M (2009) Sorption of metal ions on lignite and the derived humic substances. J Hazard Mater 161:559–564 4. Bradl HB (2004) Adsorption of heavy metal ions on soils and soils constituents. J Colloid Interf Sci 277:1–18 5. Li Y, Yue Q, Gao B (2010) Adsorption kinetics and desorption of Cu(II) and Zn(II) from aqueous solution onto humic acid. J Hazard Mater 178:455–461 6. Croué JP, Benedetti MF, Violleau D, Leenheer JA (2003) Characterization and copper binding of humic and nonhumic organic matter isolated from the South Platte River: evidence for the presence of nitrogenous binding site. Environ Sci Technol 37:328–336 7. Prado AG, Torres JD, Martins PC, Pertusatti J, Bolzon LB, Faria EA (2006) Studies on copper(II)- and zinc(II)-mixed ligand complexes of humic acid. J Hazard Mater 136:585–588 8. Qi G, Yue D, Fukushima M, Fukuchi S, Nie Y (2012) Enhanced humification by carbonated basic oxygen furnace steel slag–I. Characterization of humic-like acids produced from humic precursors. Bioresour Technol 104:497–502 9. Aristilde L, Sposito G (2010) Molecular modeling of metal complexation by a fluoroquinolone antibiotic. Environ Toxicol Chem 27:2304–2310 10. Pochodylo AL, Aristilde L (2017) Molecular dynamics of stability and structures in phytochelatin complexes with Zn, Cu, Fe, Mg, and Ca: implications for metal detoxification. Environ Chem Lett 15:495–500 11. Pochodylo AL, Klein AR, Aristilde L (2017) Metal-binding selectivity and coordination dynamics for cyanobacterial microcystins with Zn, Cu, Fe, Mg, and Ca. Environ Chem Lett 15:695–701 12. Han G (2018) An insight into flotation chemistry of pyrite with isomeric xanthates: a combined experimental and computational study. Minerals 8:2–16

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13. Spark KM, Wells JD, Johnson BB (1997) The interaction of a humic acid with heavy metals. Soil Res 35:89–101 14. Aksu Z (2001) Biosorption of reactive dyes by dried activated sludge: equilibrium and kinetic modelling. Biochem Eng J 7:79–84 15. Benaïssa H, Elouchdi MA (2007) Removal of copper ions from aqueous solutions by dried sunflower leaves. Chem Eng Process Int 46:614–622 16. And RSJ, Chen ML (1997) Application of the Elovich equation to the kinetics of metal sorption with solvent-impregnated resins. Ind Eng Chem Res 36:813–820 17. Town RM, Duval JF, Buffle J, van Leeuwen HP (2012) Chemodynamics of metal complexation by natural soft colloids: Cu(II) binding by humic acid. J Phys Chem A 116:6489–6496 18. Hao YM, Man C, Hu ZB (2010) Effective removal of Cu(II) ions from aqueous solution by amino-functionalized magnetic nanoparticles. J Hazard Mater 184:392–399 19. Liu Y, Chen M, Hao Y (2013) Study on the adsorption of Cu(II) by EDTA functionalized Fe3 O4 magnetic nano-particles. Chem Eng J 218:46–54 20. Hasan S, Ghosh TK, Viswanath DS, Boddu VM (2008) Dispersion of chitosan on perlite for enhancement of copper(II) adsorption capacity. J Hazard Mater 152:826–837

Part II

Process and Characteristics of Advanced Ceramics and Glasses

Structure, Phase Composition, and Properties of Ceramics Based on AlMgB14 , Obtained from Various Powders Ilia Zhukov, Pavel Nikitin and Alexander Vorozhtsov

Abstract Ceramics based on AlMgB14 were obtained by the methods of mechanical activation (MA) and subsequent hot pressing. Structure, phase composition and properties of materials based on AlMgB14 were studied. The time of mechanical activation was 1–5 h. The synthesis temperature was 1400 °C under a pressure of 50 MPa. The effect of the mechanical activation of powder mixtures was examined. Particle size distribution was obtained for each powder mixture. The minimum particle size was observed for the powder after 4 h of MA and was 0.8 μm. The increase in the particle size from 0.8 to 9.8 μm after 5 h of MA is due to the agglomeration of nanoparticles under the action of Van der Waals forces. The hardness of the sample synthesized from the powder mixture after 5 h of mechanical activation was approximately 14 GPa. The density of the sample was 2.3 g/cm3 . Keywords AlMgB14 · Ceramic · Ultra-hard materials · Hot pressing Mechanical activation · Hardness · Al–Mg–B system

Introduction Materials based on AlMgB14 (so-called BAM) are of great interest in recent decades. BAM materials have a high hardness, low friction coefficient, and excellent wear resistance [1–3], which make it possible to use these materials as additional coatings for parts of mechanisms (bearing parts, engines, turbines, etc.) and cutting tools. Also in the work of Putrolaynen et al. [4], they carried out research on the deposition of the boride AlMgB14 to the substrates of glass. This greatly expands the use of materials based on AlMgB14 as additional coatings. The bulk BAM materials have been prepared by several methods [1–6]. Cook et al. [1] reported the principle possibility of producing materials based on AlMgB14 by the methods of mechanical activation (MA) and subsequent hot pressing of powder I. Zhukov (B) · P. Nikitin · A. Vorozhtsov National Research Tomsk State University, Tomsk 634050, Russia e-mail: [email protected] © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_5

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mixtures Al–Mg–B in an argon atmosphere. In the work of Roberts et al. [5], authors used the method of pulsed electric current (PECS) for synthesis of raw powders of aluminum, magnesium and boron after milling in a planetary mill. The products with AlMgB14 phase content of ~93 wt% were obtained. Takeda et al. [6] studied thermoelectric properties of BAM obtained by PECS. Mechanical activation methods of mixed aluminum, magnesium and boron powders are used to intensify the process of obtaining materials based on AlMgB14 . The disadvantage of this method is that during mechanical activation the powders are contaminated by various impurities that degrade the properties of products during the synthesis, influencing their structure and properties. The purpose of this work is to study the structure, phase composition, and properties of ceramics based on AlMgB14 , obtained from various powders after mechanical activation and subsequent hot pressing.

Methods and Materials The aluminum, magnesium and amorphous black boron powders with corresponding average particle sizes 10 μm, 80 μm and 1 μm, respectively, were mixed in an atomic ratio 1:1:14. The obtained powder mixture was mechanically activated in a planetary mill with rotation frequency of 14 Hz. The mass ratio of milling ball to powder mixtures was 2:1. The diameter of ball was 8.7 mm. The time of mechanical processing was 4–5 h. To reduce oxidation of powders during mechanical activation, the box with powder mixture was filled with argon. The average particle size was measured using analyzer ANALYSETTE 22 MicroTec plus. From powder mixtures after mechanical activation, the synthesized products were obtained by hot pressing method. The synthesis temperature was 1400 °C, and the maximum pressure was 50 MPa. XRD analysis was performed using a diffractometer Shimadzu XRD 6000 with Cu Kα radiation. The hardness of sintered bulk samples was measured using Vickers hardness tester Duramin 5. The density of the samples was calculated by the Archimedes method.

Results and Discussion The histograms of the particle size distribution are presented in Fig. 1. Unimodal particle distribution is observed for the powder mixture after 4 h of mechanical activation, and the average particle size is 0.8 μm. For the powder mixture before mechanical activation (average particle size is 10.9 μm) and the powder mixture after 5 h of mechanical activation ( ~ 9.8 μm), the particle distribution is bimodal. The increase in the particle size from 0.8 to 9.8 μm after 5 h of MA is due to the agglomeration of nanoparticles under the action of Van der Waals forces.

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Fig. 1 Particle size distribution

Figure 2 shows XRD patterns of the powder mixture after 5 h of mechanical activation (b) and the synthesized sample from this powder mixture by hot pressing (a). The phase composition of the Al–Mg–B powder mixture after 5 h of mechanical activation does not change and is represented by phases of aluminum and magnesium, despite the active change in the average particle size. A high X-ray background at small diffraction angles indicates the presence of an amorphous boron phase. XRD pattern of synthesized sample (a) is largely represented by the AlMgB14 phase with content of 95 wt%. The presence of the spinel phase is connected with the oxidation of raw powders, especially boron powder. The sample obtained by hot pressing from a powder mixture before mechanical activation has a similar phase composition. The content of the AlMgB14 phase is 96 wt%. Despite the lower content of the impurity phase of MgAl2 O4 , the sample obtained from the unmilled powder mixture had an extremely high porosity. The density of the sample synthesized from the powder mixture after 5 h of mechanical activation was 2.3 g/cm3 , while the density of the sample synthesized from the unmilled powder mixture was 1.4 g/cm3 . The hardness of the sample synthesized from the powder mixture after 5 h of mechanical activation was approximately 14 GPa. In the areas contaminated with the spinel phase, the hardness was 8 GPa.

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Fig. 2 XRD patterns of synthesized sample (a) and powder mixture after 5 h of mechanical activation (b)

Conclusions The structure, phase composition, and properties of ceramics based on AlMgB14 obtained by methods of mechanical activation and subsequent hot pressing were investigated. The effect of the mechanical activation of powder mixtures was examined. After 5 h of mechanical activation, the particles agglomerate with each other under the action of Van der Waals forces. The average particle size of powder mixture after 5 h of mechanical activation is 9.8 μm. The sample synthesized from the unmilled powder mixture has a similar phase composition in comparison with the sample synthesized from the powder mixture after 5 h of mechanical activation, but has an extremely high porosity. The hardness of the sample synthesized from the powder mixture after 5 h of MA was 14 GPa. Acknowledgements Studies were funded by Russia Science Foundation (Project No. 17-7910272).

References 1. Cook BA, Harringa JL, Lewis TL, Russell AM (2000) New class of ultra-hard materials based on AlMgB14 . Scripta Mater 42:597–602 2. Ahmed A, Bahadur S, Cook BA, Peters J (2006) Mechanical properties and scratch test studies of new ultra-hard AlMgB14 modified by TiB2 . Tribol Int 39:129–137 3. Ahmed A, Bahadur S, Russell AM, Cook BA (2009) Belt abrasion resistance and cutting tool studies on new ultra-hard boride materials. Tribol Int 42:706–713

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4. Putrolaynen VV, Grishin AM, Rigoev IV (2017) Anti-scratch AlMgB14 Gorilla Glass coating. Tech Phys Lett 43(10):871–874 5. Roberts DJ, Zhao J, Munir ZA (2009) Mechanism of reactive sintering of MgAlB14 by pulse electric current. Int J Refract Metals Hard Mater 27(3):556–563 6. Takeda M, Fukuda T, Domingo F, Miura T (2004) Thermoelectric properties of some metal borides. J Solid State Chem 177:471–475

Characterization of Modified Nickel Silicate Anode Material for Lithium–Ion Batteries Yunyun Wei, Guihong Han, Yanfang Huang and Duo Zhang

Abstract Ni2 SiO4 , as a new anode material for lithium–ion batteries, was prepared by the high-temperature calcination method in this work. The MgO-coated NSO was prepared by melt injection method. Electrochemical properties, including voltammogram (CV), electrochemical impedance spectroscopy (EIS), charge/discharge curves and cycle performance were tested. The structure and morphology of materials were further characterized by XRD and SEM. The results demonstrated that the MgO-coated Ni2 SiO4 materials exhibited higher cycle charge capacity and coulombic efficiency than that of Ni2 SiO4 . When the MgO coating amount is 1%, the first cycle charge capacity and coulombic efficiency were 584.2 mAh/g and 66.25%, respectively. After 50 cycles, the charge capacity was still maintained at 359.7 mAh/g when the current density was 100 mAh/g, which was 162.7 mAh/g higher than the NSO. The crystal structure of the materials belongs to an orthorhombic system, and the morphological structure presented cubic particles. Therefore, the NSO anode material has a better cycle stability and high capacity when the MgO coating amount is 1%. Keywords MgO-coated Ni2 SiO4 · Electrochemical properties · Anode material Lithium–ion batteries

Introduction There has been increasing demand for high specific capacity and long-life lithium–ion batteries to address pressing needs for the field of chemical power supply, such as devices for portable electronic products and electric vehicles [1–3]. The anode and cathode materials that are regarded as the most important components of lithium–ion battery determine directly the electrochemical performance of the Y. Wei · G. Han · Y. Huang (B) · D. Zhang School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, People’s Republic of China e-mail: [email protected] © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_6

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battery system. It is found that lithium–ion anode materials have evolved from carbon materials to alloys, metal oxides, tin- or silicon-based anode materials, etc. [4–7]. Because of the fast capacity attenuation and poor safety performance of conventional anode materials, exploring anode materials with high safety performance and long life is necessary [8, 9]. Therefore, it is particularly important to find anode materials with high safety performance and long life. Attention has been gradually attracted by transition metal oxides, transition metal compounds, metal simple substances, and organic compounds [10, 11]. Lithium–ion battery silicate anode materials, which have high theoretical capacity, good safety performance, low cost and environmental friendliness, have been studied [12]. Because of low conductivity and fast capacity decay of silicate, its practical application as an anode material for lithium–ion batteries is limited. Transition metal silicates that have always been studied in mineralogy and materials science [13, 14] are rarely considered a potential candidate for novel anode materials. After the reversible conversion of transition metal silicates reported, it is gradually being applied to lithium–ion battery anode materials. Nickel orthosilicate anode materials prepared by chemical precipitation method have a high capacity for first charge and discharge. However, its capacity decays rapidly with repeated cycles. In this work, nickel orthosilicate (Ni2 SiO4 , NSO), as a novel anode, is synthesized by chemical precipitation method. Although it has a high first charge and discharge capacity, its capacity decays rapidly with multiple cycles. This disadvantage is effectively overcome by surface modification of the metal oxide. Surface MgO modification of NSO was studied by melt injection method. The optimum value of the amount of MgO modification was explored.

Experiments Synthesis and Modification of Ni2 SiO4 First of all, the dark green NSO powder was obtained by chemical precipitation. In order to obtain a gray-green powder, the sample was dissolved in a 500 ml 2 M NaOH and reacted in a water bath at 60 °C for 30 h to remove SiO2 impurities. Then, the pure NSO anode materials were uniformly mixed with Mg(NO3 )2 · 9H2 O, which was accounted for 0%, 3.22%, 6.48%, 9.76%, and 13.00%, respectively. The mixtures were calcined in an air atmosphere at 500 °C for 2 h with a heating rate of 5 °C min−1 to decompose Mg(NO3 )2 into MgO. Finally, MgO-modified NSO anode materials were obtained with a mass fraction of 0%, 0.50%, 1.00%, 1.50%, and 2.00%, respectively.

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Physical Characteristics The crystal structure and phase purity of NSO/MgO were examined by X-ray diffraction analysis operating at 45 kV and 40 mA at room temperature. The X-ray patterns were recorded in the range of 10°–80° at a scan rate of 0.3°/s. The particle morphology was observed at 5.0 kV by a field emission scanning electron microscope.

Assembly and Measurement of Electrochemical Cells Working electrodes (WE) were prepared by mixing active material (NSO), conductive agent (acetylene black), and binder (sodium carboxymethylcellulose: CMC) with distilled water which have a weight ratio of 8:1:1. Copper disk substrate (1 cm2 area) was coated with the resulting slurry to form WE, which dried in a 60 °C vacuum oven with an active material mass loading between 0.7 and 1.7 mg. The electrodes were assembled into coin-like electricity (CR2032) in an argon-filled glove box with oxygen and water vapor pressures less than 0.1 ppm. Cyclic voltammetry (0.05–3.00 V, 0.3 mV/s) was tested using an electrochemical workstation. In addition, a constant current cycle was achieved with respect to Li/Li+ in a voltage window of 0.05–3.0 V at a current rate of 100 mA/g using LAND-2001A. All electrochemical tests were performed at room temperature.

Results and Discussion Characterization of Materials The patterns of NSO anode materials modified with different MgO contents were presented in Fig. 1. The orthogonal Ni2 SiO4 (JCPDS card number 84-1408) pattern that has a Pbnm space group is a. Sample b can be considered as a Ni2 SiO4 singlephase material in the XRD detected range. c, d, e, and f are MgO-modified NSO anode materials with a mass fraction of 0.50%, 1.00%, 1.50%, and 2.00%, respectively. The peak of MgO is not existed in the XRD pattern, mainly because the amount is too low and below the detection limit. However, when the coated amount reaches 2.00%, a weak peak of MgO is observed in the pattern, indicating the presence of MgO. In addition, no other peaks are seen, showing that no other chemical reactions occurred during the coating process to form impurities. SEM micrographs of different MgO-coated NSOs are shown in Fig. 2. The pure phase NSO anode material that has small cubes with clear boundaries of the particles was depicted in Fig. 2a. When the amount coated is 1.5%, MgO forms a thin coating only on the surface of the material without significant agglomeration in Fig. 2b. However, when the amount coated reached 2%, it was obvious that cubes and flakes

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Fig. 1 XRD patterns of NSO anode materials modified with different MgO contents

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were appeared in Fig. 2c, and the flakes were likely to be excessive MgO. In addition, the clear boundaries of the particles disappear.

The Electrochemical Performances The first charge–discharge curves and cycle performances coated NSO at a current density of 100 mA g−1 are shown in Fig. 3. During the first constant current charging and discharging process, the discharge platform and charging platform can be observed at positions of approximately 0.8 V and 2.4 V, respectively. The platform with MgO coated at 1 and 1.5% is longer than the rest of the platform. The first discharge capacities of NSO/0%MgO, NSO/0.5%MgO, NSO/1%MgO, NSO/1.5%MgO and NSO/2%MgO were 716 mAh/g, 743.4 mAh/g, 881.9 mAh/g, 915.4 mAh/g, 562.1 mAh/g, respectively. As the amount of MgO coated increases, the first discharge capacity of the material increases first and then decreases. The reason is that a small amount of MgO is coated on the surface of the NSO, which makes the NSO particles more uniform. However, when the coated amount of MgO reaches 2%, MgO impurities appear, resulting in a decrease in the capacity of the material, which is consistent with the aforementioned results. It can be seen that the

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capacity of the battery decreases slowly with the cycle in Fig. 3b, which may be that the coated of MgO can improve effectively the cycle stability of the NSO anode material. According to the results obtained, when the MgO coating amount is 1%, the NSO anode material has a better cycle stability and high capacity. The cyclic voltammetry tests were used to further investigate the MgO-coated anode material. The results are depicted in Fig. 4. Figure 4a and b shows the first three cycles of voltammetry of the uncoated NSO anode material and the NSO anode material coated in 1% amount, respectively. Both of the first curves have a reduction peak around 0.5 V, indicating that only one reduction reaction occurred on the electrode during the first discharge, and lithium is embedded inside the lattice of the material to form Lix Ni2 SiO4 without causing the changes of lattice [15]. Then, material conversion reaction produces metal Ni and Li2 O accompanied by alloying between Si and Li [16]. The formation of a solid electrolyte interface (SEI) film also occurs during this discharge process. The first charging curve has an oxidation peak only around 2.5 V, mainly involving oxidation of nickel and reversible dealloying reaction [17]. It was found that the coated material had a stronger and sharper oxidation peak at about 2.5 V than that of the uncoated sample in the second cycle, indicating that the coated material subjected to a certain polarization process. On the one hand, the MgO-coated layer acts as a protective layer, protecting the active material, preventing side reactions with the electrolyte, reducing the dissolution of the surface high-state transition metal ions, and improving effectively the cycle stability of the material. On the other hand, the removal of lithium ions in the bulk phase of the material is inhibited to some extent. Therefore, the capacity of the coated material is slightly decreased.

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(b) 1.0 Specific current(A g-1)

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Conclusions In summary, the nano-sized NSO materials were prepared by chemical precipitation method. XRD and SEM results demonstrate that the synthesized cubic particles have better crystallinity. The cubic particle distribution of the NSO material is more uniform by MgO-coated modification. It has been observed that the electrodes prepared from NSO exhibit MgO impurities when the coated amount of MgO is 2%. The charge–discharge experiments reveal that the initial discharge capacity of the NSO/1% MgO battery is 881.9 mAh/g at 100 mA/g rate at room temperature, which increases by 165.9 mAh/g than NSO. In addition, the electrochemical performance decays slowly after 50 cycles. Therefore, the NSO anode material has better cycle stability and high capacity when the MgO-coated amount is 1%. Acknowledgements The authors acknowledge the financial support provided by the National Science Fund of China (No. 51674225, No. 51774252), the Innovative Talents Foundation in Universities in Henan Province (No. 18HASTIT011), the Educational Commission of Henan Province of China (No. 17A450001, 18A450001), and the China Postdoctoral Science Foundation (No. 2017M622375).

References 1. Zhang WM, Hu JS, Guo YG, Zheng SF, Zhong LS, Song WG, Wan LJ (2010) Tin-nanoparticles encapsulated in elastic hollow carbon spheres for high-performance anode material in lithiumion batteries. Adv Mater 20:1160–1165 2. Jung HG, Jang MW, Hassoun J, Sun YK, Scrosati B (2011) A high-rate long-life Li4 Ti5 O12 /Li[Ni0.45 Co0.1 Mn1.45 ]O4 lithium-ion battery. Nat Commun 2:516 3. Etacheri V, Marom R, Ran E, Salitra G, Aurbach D (2011) Challenges in the development of advanced Li-ion batteries: a review. Energy Environ Sci 4:3243–3262 4. Tarascon JM, Armand M (2001) Issues and challenges facing rechargeable lithium batteries. Nature 414:359–367

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5. Sun Y, Zhao L, Pan H, Lu X, Gu L, Hu YS, Li H, Armand M, Ikuhara Y, Chen L (2013) Direct atomic-scale confirmation of three-phase storage mechanism in Li4 Ti5 O12 anodes for room-temperature sodium-ion batteries. Nat Commun 4:1870 6. Aricò AS, Bruce P, Scrosati B, Tarascon JM, Schalkwijk WV (2005) Nanostructured materials for advanced energy conversion and storage devices. Nat Mater 4:366–377 7. Zhang F, An Y, Zhai W, Gao X, Feng J, Ci L, Xiong S (2015) Nanotubes within transition metal silicate hollow spheres: facile preparation and superior lithium storage performances. Mater Res Bull 70:573–578 8. Yang S, Huang Y, Han G, Liu J, Cao Y (2017) Synthesis and electrochemical performance of double shell SnO2 @amorphous TiO2 spheres for lithium ion battery application. Powder Technol 322 9. Quinzeni I, Ferrari S, Quartarone E, Capsoni D, Caputo M, Goldoni A, Mustarelli P, Bini M (2014) Fabrication and electrochemical characterization of amorphous lithium iron silicate thin films as positive electrodes for lithium batteries. J Power Sources 266:179–185 10. Tao P, Shao M, Song C, Li C, Yin Y, Wu S, Cheng M, Cui Z (2015) Morphologically controlled synthesis of porous Mn2 O3 microspheres and their catalytic applications on the degradation of methylene blue. Desalin Water Treat 57:1–6 11. Kiener J, Tosheva L, Parmentier J (2017) Carbide, nitride and sulfide transition metal-based macrospheres. J Eur Ceram Soc 37:1127–1130 12. Hassoun J, Panero S, Reale P, Scrosati B (2009) A new, safe, high-rate and high-energy polymer lithium-ion battery. Adv Mater 21:4807–4810 13. Mysen B (2007) Partitioning of calcium, magnesium, and transition metals between olivine and melt governed by the structure of the silicate melt at ambient pressure. Am Miner 92:844–862 14. Tang Q, Dieckmann R (2012) Orientation, oxygen activity and temperature dependencies of the diffusion of cobalt in cobalt orthosilicate, Co2SiO4. Solid State Ion 228:70–79 15. Wang X, Wu XL, Guo YG, Zhong Y, Cao X, Ma Y, Yao J (2010) Synthesis and lithium storage properties of Co3O4 nanosheet-assembled multishelled hollow spheres. Adv Func Mater 20:1680–1686 16. Poizot P, Laruelle S, Grugeon S, Dupont L, Tarascon JM (2010) ChemInform abstract: nanosized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature 407:496–499 17. Varghese B, Reddy MV, Zhu Y, Chang SL, Hoong TC, Rao GVS, Chowdari BVR, Wee ATS, Lim CT, Sow CH (2008) Fabrication of NiO nanowall electrodes for high performance lithium ion battery. Chem Mater 20:3360–3367

Sinterability of Y-Doped BaZrO3 with Micro- and Nano-CaO Additives and Its Interaction with Titanium Alloy Juyun Kang, Guangyao Chen, Baobao Lan, Shihua Wang, Xionggang Lu and Chonghe Li

Abstract The effects of micro- and nano-CaO additive on the sinterability of Ydoped BaZrO3 and its interface reaction with titanium alloys were investigated. The 10 mol% micro- and nano-CaO is doped into BaZr0.97 Y0.03 O3 (BZY), respectively. The sinterability of BZY with micro- and nano-CaO was investigated by density analyzer, SEM and XRD. The relative density of BZY pellets with micro- and nanoCaO addition improved from 88% to 97.5% and 98% at 1750 °C for 6 h, respectively. XRD and SEM(BSE) show no secondary phase in the two sintered ceramics, which indicates that a single phase of cubic perovskite-type structure of Ca-modified BZY can be obtained. After melted titanium alloys, the erosion layer is 70 μm with nano-CaO addition, while a 310 μm erosion layer with micro-CaO addition. This shows that nano-CaO can be used as an appropriate sintering aid and can prevent the Y-doped BaZrO3 refractory from erosion. Keywords Sinterability · Y-doped BaZrO3 · CaO additive · Interface reaction Titanium alloy

J. Kang · G. Chen · B. Lan · X. Lu · C. Li (B) State Key Laboratory of Advanced Special Steel, Shanghai Key Laboratory of Advanced Ferro Metallurgy, School of Materials Science and Engineering, Shanghai University, Shanghai 200072, China e-mail: [email protected] G. Chen Materials Genome Institute of Shanghai University, Shanghai 201900, China S. Wang Shanghai University Library, Shanghai, China X. Lu · C. Li Shanghai Special Casting Engineering Technology Research Center, Shanghai 201605, China © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_7

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Introduction Titanium alloys are promising candidate materials for high-temperature structural applications due to their low density, good oxidation resistance and high-temperature strength and for biomedical applications because of their good biological performance [1–3]. However, titanium melt has high activity and reacts with almost all commercially known ceramic crucibles, such as graphite [4], BN [5–7] and Al2 O3 [8, 9] refractory which in melting process [4–9]. For example, the traditional graphite crucible will increase the carbon content of the alloy after melting. BN crucible will react with titanium and produce Ti-N, Ti-B compounds. Some Al2 O3 inclusions will introduce in melt and increase the oxygen content in titanium alloys and influence the properties of the alloys. Erb et al. [10] indicated that BaZrO3 has high stability for preparation of single-crystal YB2 Cu3 O7-δ (YBCO), and no interaction was observed between BaZrO3 crucible and YBCO single crystal. And BaZrO3 has high chemical stability and thermal shock resistance. In our previous study, no obvious interfacial reaction between BaZrO3 and TiNi and TiAl alloys were found [11, 12]. However, in our further research [13], the interface reaction was observed between titanium-rich alloys and BaZrO3 crucible, namely, the stability of BaZrO3 is not enough to melt titanium-rich alloys. Y-doped BaZrO3 (BZY) exhibits excellent chemical stability and has been proposed as the high ionic conductivity [14, 15]; therefore, many researchers paid attention to this material, for instance, the ternary of BaO-ZrO2 -YO1.5 thermodynamic system was evaluated by Lin [16]; theoretically, it provides a high thermodynamic stability composite oxide refractory and theoretical basis about Y-doped BaZrO3 refractory for induction melting titanium alloys. Y-doped BaZrO3 compounds were used to prepare TiAl alloy by directional solidification, and no interface reaction was found after long time contact between shell mold and TiAl melt [17]. However, Y-doped BaZrO3 refractory material is rarely to be sintered, and a high sintering temperature (1700–2100 °C) and long sintering time (24 h) are required [18]. Adding sintering aids are the effective ways to enhance the sinterability. So many researchers attempt to improve the sintering performance of Y-doped BaZrO3 by suitable sintering aids, such as ZnO, CuO, NiO and P2 O5 . They can improve the sinterability and enhance the electrochemical property of Y-doped BaZrO3 [19–23], but they all can react with titanium melt. CaO is also a refractory for melting titanium alloys, and it is cheaper and has better thermo-chemical inertness [24]. Nobuo [25] used CaO crucible-melted TiAl alloys; no reaction layer was found and obtained a lower oxygen content metal materials. However, poor hydration resistance limits its practical applications [26, 27]. CaO also can act as sintering aid and improves the ceramics sintering behavior [28–30]. Therefore, in order to enhance the sintering performance of Y-doped BaZrO3 , micro- and nano-CaO are all selected as sintering additives due to the influence of their activity on sintering results. In this study, the effect of micro-CaO and nano-CaO as sintering additives for Y-doped BaZrO3 sintering performance and its interaction with titanium alloys were

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Table 1 The mole ratio of Y-doped BaZrO3 powders with micro- and nano-CaO additives prepared by solid-phase reaction synthesis method Powder no. n(BaCO3 ) n(ZrO2 ) n(YO1.5 ) n(CaO) BZY-MC BZY-NC

0.5 0.5

0.485 0.485

0.015 0.015

0.1 0.1

also investigated to evaluate the stability of Y-doped BaZrO3 with micro-CaO by comparing it with nano-CaO.

Experimental First, raw materials were industrial-grade BaCO3 (purity > 98%), ZrO2 (purity > 99.2%), Y2 O3 (purity > 99.8%), micro-CaO (AR, purity > 99.9%) and nano-CaO from calcined nano-CaCO3 powders, according to the stoichiometric proportion in Table 1, which were used to prepare Y-doped BaZrO3 (BaZr0.97 Y0.03 O3 denoted as BZY) powders by traditional solid-state method. These powders were put in the closed polytetrafluoroethylene (PTFE) pot with absolute alcohol as medium and Y-stabilized zirconia balls for mixing. The mass ratio of powders, zirconia balls and alcohol were 2:3:0.4. Then, the mixtures were dried and pound to powders. Second, calcination was done in high-purity Al2 O3 crucible in a conventional furnace in air atmosphere for 12 h at 1400 °C. Third, micro- and nano-CaO additives were added into BZY powders, and the addition amount is 10 mol%, and then ball-milled in absolute ethanol with zirconia balls for 8 h and a speed of 250 rotation per minute (rpm), and the final powders were labeled as BZY-MC, BZY-NC, respectively. Next, two components of crucibles were prepared by using these two kinds of powders, and the cold isostatic pressing with a pressure of 140 Mpa for 3 min, the U-shape green crucibles were 54 mm height and 46 mm diameter, which were then sintered at 1750 °C for 6 h. The master alloys Ti2 Ni (with 66 mol% Ti), which were melted by a watercooled copper crucible induction furnace, and the raw materials were titanium sponge (purity > 99.9%) and nickel plate (purity > 99.9%). Then, the two crucibles BZY-MC and BZY-NC were melted with Ti2 Ni alloys, respectively. Before melting, the crucible was fixed in the center of vacuum induction coil, and then filled with magnesite sand around the crucible to prevent damaging the induction coil. Next, put about 65 g alloy in the crucible and evacuated to 10−3 mbar of the furnace, then proceeded to fill high-purity argon gas to the furnace chamber up to 0.6 MPa, and repeated vacuuming and filled gas for three times. Then, the melting was carried out under the high vacuum. When observed the melt, the argon gas is filled to 600 Pa at once, and the temperature is increased to 1500 °C quickly, and held for 3 min and cooled down with the crucible.

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Fig. 1 XRD patterns of Y-doped BaZrO3 powders and sintered crucibles with micro- and nano-CaO additives

Sample Characterization The densities of the crucibles with micro- and nano-CaO additives were determined by full automatics density analyzer (ACCUPYC II 1340). The microstructure of the crucibles and the interface reaction between crucibles and Ti2 Ni alloys were investigated by scanning electron microscopy (SEM). Phase analysis of the powders and ceramics was conducted by the XRD machine (Bruker D8 Advance). The contaminations of the melted alloy from the crucible were investigated by ICP-AES and LECO TC600 O/N analyzer.

Results and Discussion The XRD patterns of Y-doped BaZrO3 powders and crucibles with micro-CaO additive and nano-CaO additive are shown in Fig. 1. For comparison, the XRD pattern of Y-doped BaZrO3 without CaO additive is also conducted, as shown in Fig. 1. According to the XRD patterns of both micro- and nano-CaO-doped BZY, no secondary phases of the powders and sintered crucibles were observed. It can be indicated that the Ca2+ ions might have been dissolved in the solid solution.

Sintering Behavior In order to investigate the sinterability of BZY with micro- and nano-CaO additive, the densities of the ceramics were measured by full automatic density analyzer and

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Table 2 The density of BZY-MC and BZY-NC crucibles after sintered at 1750 °C for 6 h Sample#

Holding temperature (°C)

Holding time (h)

Density (g/cm3 )

Relative density (%)

BZY-MC BZY-NC

1750 1750

6 6

5.92 5.95

97.5 98.0

the theoretical density (6.07 g/cm3 ) of Y-doped BaZrO3 with CaO calculated by the weighted average method [31]. It can be seen that the density of BZY with micro-CaO additive is lower than that of nano-CaO additive at the 1750 °C for 6 h (Table 2). Figure 2 represents that the microstructures and backscattered electron (BSE) images of Y-doped BaZrO3 with micro- and nano-CaO additives. The microstructures of Y-doped BaZrO3 with micro- and nano-CaO additives are shown in Fig. 2a, b; the grain’s arrangements of both ceramics are dense, while the grain sizes of BZY with nano-CaO (8–10 μm) additive are greater than that of BZY with micro-CaO (3–5 μm) additive; this further illustrates that the grain boundaries of BZY-MC are more than that of BZY-NC under the same areas. Figure 2c, d shows the backscattered electron images of BZY-MC and BZY-NC. No secondary phase can be found in the images; this is in accordance with the XRD patterns in Fig. 1, which further indicates that CaO-modified Y-doped BaZrO3 can be obtained in a single-phase perovskite structure. Figure 3 shows the polished cross-sectional image of Y-doped BaZrO3 with microand nano-CaO additives. It can be seen that the pores of BZY with micro-CaO additive are more than that of BZY with nano-CaO additive. It can also be observed that BZY with nano-CaO additive is much denser than that of BZY with micro-CaO additive. According to the mechanism of solid-state sintering, the reason can be explained that the densification process of sintering depends on the mass diffusion and migration. While the activity of nano-CaO is greater than that of micro-CaO, doping nanoCaO into Y-doped BaZrO3 powders will increase the specific surface area, and the contacted areas between Y-doped BaZrO3 particles to a certain extent in the sintering process, which is in favor with the mass diffusion and transfer in solid-state sintering. Meanwhile, the driving force of sintering process is also increased because of the higher activity for nano-CaO. This phenomenon is in agreement with the effects of nano-TiO2 [32] and nano-Al2 O3 [33] on Al2 O3 ceramics. It can be seen that highdensity Y-doped BaZrO3 ceramic can be obtained by doping nano-CaO additive.

Interface Reaction Figure 4 shows the SEM pictures of interfacial reaction between Y-doped BaZrO3 with micro- and nano-CaO crucibles and Ti2 Ni alloys. It is shown that the erosion layer of Y-doped BaZrO3 with micro-CaO refractory is approximately 310 μm after melting Ti2 Ni alloy, while the thickness of Y-doped BaZrO3 with

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Fig. 2 Microstructures and backscattered electron images of Y-doped BaZrO3 with micro- and nano-CaO additives at 1750 °C for 6 h. a, c BZY with micro-CaO, b, d BZY with nano-CaO

Fig. 3 Polished cross-sectional image of Y-doped BaZrO3 with micro- and nano-CaO additives at 1750 °C for 6 h. a Y-doped BaZrO3 with micro-CaO additive, b Y-doped BaZrO3 with nano-CaO additive

nano-CaO refractory is just about 70 μm. From the elements distribution of the SEM pictures, almost no refractory elements and alloy elements diffusion were observed. This indicates that nano-CaO can not only enhance the sinterability of Y-doped BaZrO3 ceramic but also improve the stability of Y-doped BaZrO3 and prevent the erosion from titanium melts.

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Fig. 4 SEM pictures of interfacial reaction and elements distribution between Y-doped BaZrO3 with micro- and nano-CaO crucibles and Ti2 Ni alloys. a BZY-MC crucible and Ti2 Ni alloy, b BZY-NC and Ti2 Ni alloy

Conclusions (1) Y-doped BaZrO3 is hardly to be dense without sintering additives, and microCaO and nano-CaO are as sintering aids; the relative density of Y-doped BaZrO3 ceramic with micro-CaO is about 97.5%, while the relative density of Y-doped BaZrO3 ceramic with nano-CaO is 98%. No secondary phase is observed of these two refractories by XRD and SEM (BSE), which shows that CaO-modified Y-doped BaZrO3 is a single cubic perovskite structure. (2) After melting Ti2 Ni alloys with the two crucibles which are Y-doped BaZrO3 with micro- and nano-CaO additives, the thickness of erosion layer is about 310 μm and 70 μm, respectively; it demonstrates that nano-CaO can be as a suitable sintering aid to improve the sintering performance of Y-doped BaZrO3 and can prevent the titanium melt erosion the crucible effectively. Acknowledgements The authors thank the National Natural Science Foundation of China (No.: 51574164, U1760109); Basic Major Research Program of Science and Technology Commission Foundation of Shanghai (No.: 14JC1491400). China Postdoctoral Science Foundation funded project (2018M632081).

References 1. Wu X (2006) Review of alloy and process development of TiAl alloys. Intermetallics 14(10):1114–1122 2. Boyerr RR (1996) An overview on the use of titanium in the aerospace industry. Mater Sci Eng, A 213(1–2):103–114 3. Niinomi M, Boehlert CJ (2006) Titanium alloys for biomedical applications. Mater Sci Eng C 26(8):1269–1277

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29. Chen GH (2008) Sintering, crystallization, and properties of CaO doped cordierite-based glass–ceramics. J Alloy Compd 455(1):298–302 30. Lai YQ, Zhang Y, Zhang G et al (2008) Effect of CaO doping on densification of 10NiONiFe2 O4 composite ceramics. Chin J Nonferrous Metals 18(5):851–855 31. Chen GY, Kang JY, Gao PY et al (2018) Effect of CaO additive on the interfacial reaction between the BaZrO3 refractory and titanium enrichment melt. Rare metal technology 2018. The minerals, metals & materials series. https://doi.org/10.1007/978-3-319-72350-1_22 32. Zhang XP, Chen SJ, Li GH et al (2008) Effect of nanosized TiO2 additive on the microstructure and sintering characteristics of Al2 O3 ceramics. J Chin Ceram Soc 36(4):494–497 33. Liu Y, Wu CL, Huang WZ et al (2006) Effect of nano-Al2 O3 powder additive on sintering behaviors of alumina ceramics. J Anhui Univ Sci Technol (Nat Sci) 26(01):41–44

The Influence of Microstructure and Emissivity of NiO-Doped Fe3 O4 Spinel Structure on Near- and Middle-Infrared Radiation Jian Zhang, Bai Hao, Xu Zhang, Huanmei Yuan, Zefei Zhang and Liyun Yang

Abstract The ferrites of spinel structure have high-infrared emissivity performance at high temperature, which make it possible to be used in metallurgical industry. Based on the preparation of the materials, microstructure and ions distribution of spinel structure Fe3 O4 with Ni-ion doping was investigated. Further, the emissivity was measured as 0.97 in the 3–5 μm waveband at 500 °C, which presented excellent radiation performance. The first-principle calculation was conducted to explain the mechanism of emissivity variation with Ni-ion doping. The calculation results show that Ni doping makes the forbidden band increase, leading to a decrease of free carrier absorption in NiFe2 O4 system, and this indicates that the Ni2+ doping would enhance the energy of electron transition from valence band to conduction band which is formed due to the hybridization of the 3d orbital electrons of the Ni ions and the 2p orbital electrons of the oxygen atoms. Keywords Microstructure · NiFe2 O4 spinel · Infrared emissivity · First principle

Introduction Spinel ferrites exhibit high-infrared emissivity, good thermal and chemical stability; therefore, they can be considered as the promising infrared radiation materials to improve heat exchange in industrial furnaces. Moreover, the radiant energy in 3–5 μm J. Zhang · B. Hao (B) · X. Zhang · H. Yuan · Z. Zhang · L. Yang School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, 30# Xueyuan Road, Beijing 100083, China e-mail: [email protected] © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_8

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and 8–14 μm wavebands which is involved in the furnace accounts for more than 76% of the whole infrared radiation energy since the temperature of most industrial furnaces is higher than 1000 °C [1, 2]. The previous researches mainly focused on the emissivity of spinel ferrites at 8–14 μm waveband and found that the emissivity values can reach above 0.9. For instance, Zhang and Wen [3] discussed the emissivity of Co–Zn ferrites with different rare earth ions and found that doping La, Nd and Gd ions could make the highest emissivity about 0.96–0.97 in 8–14 μm band. Wu et al. [4] reported that the emissivity of CoFe2-x Cex O4 spinel could reach the 0.92 ± 0.01 in 8–14 μm band. However, compared with the high values of emissivity in 8–14 μm, the emissivity of spinel ferrites in 3–5 μm waveband is only approximately 0.8 [5, 6]. Thus, it is necessary to study more in order to enhance the emissivity in 3–5 μm waveband. According to the previous studies, it has been proved that the mechanism of emissivity of 8–14 μm waveband is related to the lattice vibration [7–9]. However, the emissivity in 3–5 μm waveband was mainly discussed through experimental findings. For instance, Ding et al. [10] synthesized NiCr spinel coatings and found that the prepared coatings can reach a high emissivity about 0.917 in the wavelength range of 2.5–25 μm at 1000 °C. They discussed the structure of NiCr spinel and inferred that Ni2+ in the octahedral space can increase the concentration of free carriers and break the electronic valence balance. However, they did not present evidence of the free carriers concentration increase. Hou et al. [11] obtained the highest infrared emission value of nanoscale CuFe2 O4 about 0.965 in 3–5 μm when the sintering temperature was 1000 °C. In this paper, they discussed the emissivity in 3–5 μm at different sintering temperatures and explained that the emissivity at different sintering temperatures may be related to the electron transition from the valence band to the conduction band. However, Hou et al. [11] did not give any evidence of the electron transition from the valence band to the conduction band. According to the above studies, the researchers mainly considered that the electron transitions do have effect on 3–5 μm emissivity, but they did not explain how the electron transition works. Meanwhile, some authors also think the doping metal ions can enhance the emissivity in the near- and middle-infrared waveband, but the effect of doping metal ions on the enhancement of the emissivity still needs to be further studied [3, 4, 7]. Therefore, it is necessary to study more on the process of electronic transformation from orbital hybridization which is significant to explain the emissivity of spinel structure in 3–5 μm waveband. In this work, we studied the infrared properties of Fe3 O4 and NiFe2 O4 ferrites by using the first-principle calculation. The first-principle calculation is used to predict the optical properties of spinel structure since the theoretical calculations for spinel structure would be significant for the further explanation of the experimental results and predict the infrared radiation properties of spinel structures. Therefore, the aim of this study is to further explain the micro-mechanism of 3–5 μm waveband.

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Material and Method Materials Preparation The analytical grades of NiO and Fe2 O3 were used to prepare NiFe2 O4 . The raw materials were dried for 24 h at 110 °C and then mixed in an agate mortar for 3 h to make sure the composition uniformity. The mixed mass ratio of NiO and Fe2 O3 is obtained on the mole ratio of Ni:Fe as 1:2. Then the sample was heated for 1.5 h in alumina crucibles, with the heating rate of 10 °C/min in air atmosphere at 1100 °C and then cooled to room temperature in the furnace.

Experimental Analysis An X-ray diffractometer (XRD, Rigaku Smartlab) was used to verify the crystal structure based on the elemental composition of materials. The Cu Kα radiation (k  1.54) was used at a step size of 2θ  0.02°, and the scan range angle was from 10° to 120° at a scan speed of 10°/min. A dual-band radiation emissivity measuring metre (IR-2) was applied to measure the emissivity in the waveband of 3–5 μm and 8–14 μm.

Results and Discussion XRD Analysis The XRD diffraction patterns of two samples are shown in Fig. 1, and the characteristic peaks of (111), (220), (311), (222), (400), (422), (511), (440), (533) and (731) of crystal structure are in accordance with the Joint Committee Powder Diffraction Standard (PDF# 22-1086). This means that the pure spinel structure was prepared successfully for NiFe2 O4 ferrite. The spinel structure has a closed-packed FCC with metal ion in the center of the A site (tetrahedron position) and B site (octahedral position) which can be seen in Fig. 2.

Emissivity Properties The infrared emissivity of the samples in 3–5 μm and 8–14 μm wavebands were measured, and the results are shown in Fig. 3. The results in Fig. 3a show that Fe3 O4 sample had a higher emissivity on 3–5 μm from 0.969 to 0.973 than NiFe2 O4 sample

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Fig. 1 The XRD patterns of Fe3 O4 and NiFe2 O4 samples

Fig. 2 The structures of spinel ferrite

from 0.542 to 0.611 as the temperature increases to 500 °C. This suggests that the Fe3 O4 powder has a strong optical absorption. A slight decrease of infrared emissivity from 0.979 to 0.973 on 3–5 μm waveband was observed for Fe3 O4 sample with the temperature increase from 300 to 500 °C. In Fig. 3b, the Fe3 O4 sample reached the highest emissivity about 0.996 at 300 °C and then decreased to 0.976 with the temperature increase to 500 °C on 8–14 μm. The emissivity of NiFe2 O4 sample on 8–14 μm increased from 0.934 to 0.972 with the temperature increased from 25 to 500 °C and the increased trend of emissivity decreased when the temperature exceeds 300 °C.

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(a)

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(b)

Fig. 3 a 3–5 μm and b 8–14 μm emissivity of Fe3 O4 and NiFe2 O4 samples

Electronic Properties The plane-wave-pseudo-potential (PWPP) which is an approach within the framework of the DFT was used in the calculation [12]. The Perdew–Burke–Ernzerhof (PBE) functional of generalized gradient approximation (GGA) was used to describe the exchange-correlation energy of the electrons. The valence electrons of O: 2s2 2p4 , Fe: 3d6 4s2 , and Ni: 3d8 4s2 were determined by the potential function in this study. Due to the strong correlation feature of the 3d electrons for the transition metal, the Coulomb interaction of local electrons should be revised by parameters U (LDA + U) to calculate the system energy and crystal structure. The calculation of Ueff was based on the previous reports of similar systems and the accuracy testing in which the Fe 3d orbital is 2–6 eV and Ni is 7 eV [13–15]. The primitive cells of Fe3 O4 and NiFe2 O4 are shown in Fig. 4. The two crystal structures consist of 14 atoms with metal ion in tetrahedron and octahedral position. A cutoff energy of 490 eV was used to truncate the plane-wave expansion for optimizing the crystal structure with a 5 × 5 × 5 k-mesh applied. The iteration was stopped until the energy is less than 2.0 × 10−6 eV/atom and the Hellmann–Feynman force was less than 10−2 eV/Å. According to the Hund rules and the magnetic super-exchange interaction, the Fe3 O4 and NiFe2 O4 are magnetic particles, and the electrons of the spins in tetrahedron and octahedron site have the opposite directions [16]. Figure 5 shows the partial density of Ni (s, d), Fe (p, d), O (s, p) and total orbitals from GGA calculation. As shown in Fig. 5a, the valence bands near the Fermi level (about 0–2.0 eV) were mainly donated by Fe 3d and O 2p orbitals. In this respect, the interaction between Fe2+ and Fe3+ should be accomplished via the electronic transform of O2− . In Fig. 5a, the Fermi level crossed the valence bands which were donated only by the spin-up orbitals of O 2p orbitals. This proved that the Fe3 O4 was semimetal [17]. In Fig. 5b, there was an obvious band gap about 1.21 eV for NiFe2 O4 spinel which is underestimated compared with the experimental results [18]. The valence bands of NiFe2 O4 near Fermi level were donated by Ni 3d, Fe 3d and O 2p orbitals, and the conduction bands near Fermi level were Fe 3d and O 2p

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Fig. 4 The calculated structures of a Fe3 O4 and b NiFe2 O4

orbitals. In the infrared wavelength of 3–5 μm (about 0.25–0.41 eV), there have been several evidences showing that the emissivity is related to the electronic transition from valence band to conduction band [6, 10, 11, 19]. Compared to the total PDOS near the Fermi level, the electronic transition from semimetal (Fe3 O4 ) is much easier than that in semiconductor (NiFe2 O4 ). This means that the Fe3 O4 has a strong optical absorption on 3–5 μm waveband compared to NiFe2 O4 . These results are in good agreement with the results shown in Fig. 3a.

Optical Properties According to previous literature, the optical properties can be described by the electromagnetic theory, and the Kramas–Kronig relation is applied to describe the complex dielectric function [20]. The dielectric function is ε(ω)  ε1 (ω) + iε2 (ω), where ε1 (ω) is the real part of the dielectric function and ε2 (ω) is the imaginary part. The formulas involved are as follows [20, 21]: E1  1 +

E2 

|e · MC V (K )|2 E3 8π 2  3 2   ∫ × d × κ m 2 ω2 V,C 2π E C (K ) − E V (K ) E C (K ) − E V (K ) − E 2 ω2 2

4π m 2 ω2

(1)



d 3κ

V,C B Z

2 × |e · MC V (K )|2 × δ[E C (K ) − E V (K ) − Eω] 2π

α(ω) 

√

 2

(2)

1/2 ε12 (ω)

+

ε22 (ω)

− ε1 (ω)

(3)

where ω is the frequency of light, α(ω) is the absorbance, BZ is the first Brillouin Zone, the subscripts of C and V are the conduction band and valence band, κ is the reciprocal lattice vector, |MC V (K )|2 is the momentum matrix element, and E C (K ) and E V (K ) are the intrinsic energy levels of conduction band and valence band.

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Fig. 5 The partial density of states of Ni (s, d), Fe (p, d), O (s, p) orbitals. a Fe3 O4 , b NiFe2 O4

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Fig. 6 The calculated absorption coefficient of Fe3 O4 and NiFe2 O4

Without considering the intra-band transition, the calculated absorption coefficients of Fe3 O4 and NiFe2 O4 systems are shown in Fig. 6. It is seen that the calculated absorption coefficient around 0–1.2 eV has a peak for Fe3 O4 system and for NiFe2 O4 is almost zero. For Fe3 O4 system, the electronic transition between Fe 3d and O 2p orbitals only needs small energy from valence band to conduction band. However, for NiFe2 O4 system, the electronic energy from valence band to conduction band must overcome the forbidden band. This means the electrons of valence band could be excited to conduction band easily for Fe3 O4 system compared with the NiFe2 O4 system, which increases the energy absorption in short waveband.

Conclusion (1) The NiFe2 O4 sample was prepared by sintering process and the XRD diffraction pattern showed that the spinel structure had already formed at 1100 °C. (2) The infrared emissivity in 3–5 μm shows that Fe3 O4 sample has a higher emissivity from 0.969 to 0.973 than NiFe2 O4 sample from 0.542 to 0.611 with the temperature increased from 25 to 500 °C. (3) The first-principle calculation indicates that the electron transition is much easier from valence band to conduction band than that in semiconductor (means NiFe2 O4 ). The Fe3 O4 has a strong optical absorption on 3–5 μm waveband.

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References 1. Liu HZ, Liu ZG, Liu Ouyang JH, Wang YM (2011) Thermo-optical properties of LaMg1−x Nix Al11 O19 (0 ≤ x≤1) hexaaluminates for metallic thermal protection system. Mater Lett 65(17):2614–2617 2. Lu L, Fan XA, Zhang JY, Hu XM, Li GQ, Zhang Z (2014) Evolution of structure and infrared radiation properties for ferrite-based amorphous coating. Appl Surf Sci 316:82–87 3. Zhang Y, Wen DJ (2012) Infrared emission properties of RE (RE  La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) and Mn co-doped Co0.6 Zn0.4 Fe2 O4 ferrites. Mater Chem Phys 131(3):575–580 4. Wu XY, Yu HB, Dong H, Geng LJ (2014) Enhanced infrared radiation properties of CoFe2 O4 by single Ce3+ -doping with energy-efficient preparation. Ceram Int 40(4):5905–5911 5. Zhang JY, Fan XA, Lu L, Hu XM (2015) Ferrites based infrared radiation coatings with high emissivity and high thermal shock resistance and their application on energy-saving kettle. Appl Surf Sci 344:223–229 6. Hou HL, Xu GY, Tan SJ, Zhu YM (2017) A facile sol-gel strategy for the scalable synthesis of CuFe2 O4 nanoparticles with enhanced infrared radiation property: influence of the synthesis conditions. Infrared Phys Technol 85:261–265 7. Wu XY, Yu HB, Dong H (2014) Enhanced infrared radiation properties of CoFe2 O4 by doping with Y3+ via sol-gel auto-combustion. Ceram Int 40(8):12883–12889 8. Wang YM, Tian H, Guo LX, Ouyang JH, Zhou Y, Jia DC (2014) Amorphous AlPO4 coating formed on titanium alloy for high temperature oxidation protection: oxidation kinetics and microstructure. Surf Coat Tech 252:134–141 9. Wang D, Han MK, Li M, Yin XW (2016) Effect of strontium doping on dielectric and infrared emission properties of barium aluminosilicate ceramics. Mater Lett 83:223–226 10. Ding SY, Mao JW, Zeng X, Cheng XD (2018) Enhanced infrared emission property of NiCr spinel coating doped with MnO2 and rare-earth oxides. Surf Coat Tech 344:418–422 11. Hou HL, Xu GY, Tan SJ, Xiang SS (2018) A facile hydrothermal synthesis of nanoscale CuFe2 O4 spinels with enhanced infrared radiation performance. J Alloy Compd 735:2205–2211 12. Chen QY, Xu M, Zhou HP, Duan MY, Zhu WJ, He HL (2008) First-principle calculation of electronic structures and optical properties of wurtzite Inx Al1-x N alloys. Phys B 403:1666–1672 13. Hou YH, Zhao YJ, Liu ZW, Yu HY, Zhong XC, Qiu WQ, Zeng DC, Wen LS (2010) Structural, electronic and magnetic properties of partially inverse spinel CoFe2 O4 : a first-principles study. J Phys D Appl Phys 43(44):1–7 14. Anisimov VI, Aryasetiawan F, Lichtenstein AI (1997) First-principle calculations of the electronic structure and spectra of strongly correlated system: the LDA + U method. Phys Condens Matter 9(4):767–808 15. Rák Z, O’Brien CJ, Brenner DW (2014) First-principles investigation of boron defects in nickel ferrite spinel. J Nucl Mater 452:446–452 16. Atacan Keziban, Özacar Münteha, Özacar Mahmut (2014) Investigation of antibacterial properties of novel papain immobilized on tannic acid modified Ag/CuFe2 O4 magnetic nanoparticles. Int J Biol Macromol 109:720–731 17. Fu ZM, Yang BW, Zhang Y, Zhang N, Yang ZX (2018) Dopant segregation and CO adsorption on doped Fe3 O4 (111) surfaces: a first-principle study. J Catal 364:291–296 18. Pottker WE, Ono R, Cobos MA, Hernando A, Araujo JFDF, Bruno ACO, Lourenço SA, Longo E, La Porta FA (2018) Influence of order-disorder effects on the magnetic and optical properties of NiFe2 O4 nanoparticles. Ceram Int 44(14):17290–17297 19. Liu QS, Chang Q, Li JL, You Z, Peng JQ, Chen JG (2018) Infrared radiation performance and calculation of B-site doped lanthanum aluminate from first principles. Ceram Int 44(10):11570–11575 20. Guo SQ, Hou QY, Xu ZC, Zhao CW (2016) First principles study of magneto-optical properties of Fe-doped ZnO. Phys B 503:93–99 21. Du FL, Wang N, Zhang DM, Shen YZ (2010) Preparation, characterization and infrared emissivity study of Ce-doped ZnO films. J Rare Earth 1(28):391–395

Incorporation of Silver Nanoparticles in Zinc Oxide Matrix in Polyester Thermoplastic Elastomer (TPE-E) Aiming Antibacterial Activity Leonardo Guedes Marchini, Duclerc Fernandes Parra and Vijaya Kumar Rangari

Abstract The purpose of present study is to evaluate the antimicrobial potential of Thermoplastic Polyester Elastomer (TPE-E) incorporated with zinc oxide added with colloidal dispersion of metallic silver adsorbed on pyrogenic silica (AgNPs_ZnO). A combination of single screw extruder and hot press technique was used to fabricate these polymer nanocomposite films. These polymer nanocomposite films were prepared by mechanical mixing of 1% (w/w) of oil, anti-oxidant 0.05% (w/w), TPE-E granules 0.5% (w/w) and followed by single screw extruder to produce the pellets. As-prepared pellets were further melted for films in hot press technique. Antimicrobial activity was evaluated according to Japan Industrial Standard—JIS Z 2801 in TPE-E compounds against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). TPE-E samples containing additives 0.05 and 0.5% AgNPs_ZnO presented 75 and 93% bactericidal reduction for Gram-negative bacteria Escherichia coli (E. coli) and 76 and 92% bactericidal activity reduction for Gram-positive bacteria Staphylococcus aureus (S. aureus), respectively. Keywords AgNPs · Antimicrobial activity · TPE-E · Characterization

L. G. Marchini · D. F. Parra (B) Nuclear and Energy Research Institute, IPEN, CNEN/SP, Av. Professor Lineu Prestes, 2242, Cidade Universitária, São Paulo, SP CEP 05508-000, Brazil e-mail: [email protected] V. K. Rangari Center for Advanced Materials Science and Engineering, Tuskegee University, Tuskegee, AL 36088, USA © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_9

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Introduction Silver nanoparticles are well known as potent antimicrobial agents. Although the significant progress has been made in elucidating the antimicrobial mechanism of silver nanoparticles, the exact mechanism of action is not yet fully understood. The literature reports discussion of topics including the release of silver ions and silver nanoparticles, cell membrane damage, DNA interaction, free radical generation, bacterial resistance and the relationship of resistance to silver ions versus resistance to silver nanoparticles [1]. The present overview incorporates recent original contributions on the progress of new materials with silver for anti-microbial performance. Several polymeric antimicrobial composites have been prepared by mixing silver nanocomposites. As for reported examples of AgNps addition: AgNPs with polyamide (PA) [2], AgNPs nanocomposites with polypropylene PP [3], and AgNPs nanocomposites with polyethylene (PE) [4]. Gamma irradiation was also applied in the production of polymers containing AgNPs [5, 6]. Silver nanoparticles applied in elastomeric thermoplastics (TPE), such as thermoplastic polyurethane (TPU) with AgNPs [7] and TPE based on styrene-ethylene butylene-styrene block copolymer (SEBS) containing several types of AgNPs [8] were studied. However, it is not found in the literature studies of the bactericide action of AgNPs in ZnO carrier in polyester elastomeric thermoplastic (TPE-E) obtained by single screw extrusion.

Materials Thermoplastic Polyester Elastomer (TPE-E) The TPE-E polymer used in the study was TPE-E 1155-201ML from the Chinese company Chang Chun Plastics Co., Ltd. The material has a hardness of 65 shore D, density of 1.19 g/cm3 , flow rate of 10 g · 10 min−1 , water absorption after 24 h of 0.4%, melting point of 200 °C, maximum point of 15 MPa, elongation at the maximum point of 28%, and tensile modulus of 30 MPa.

Silver Nanoparticle (AgNPs) The silver nanoparticles (AgNPs_ZnO) used have zinc oxide additive as carrier and metallic silver colloidal dispersion adsorbed on pyrogenic silica was purchased from the Brazilian company TNS Ltda. It is in powder form with average particle size of 15 nm, density 5 g/cm3 and insoluble in water.

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Antioxidant Irganox 1010 from BASF used in the work of the chemical name Tetrakis (pentaerythritol 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) is a sterically hindered phenolic antioxidant of molecular weight of 1178 g/mol and density of 1.15 g/ml.

Oil Oil used for processing was Alkest TW 80 from Oxiteno. It is an ethoxylated sorbitan esters oil, of liquid appearance at 25 °C, and maximum water content of 3%.

Methods Production of TPE-E_AgNPs Films by Single Screw Extrusion TPE-E containing AgNPs was obtained by single screw extruder according to the following conditions: temperature profile (feed to die), for zones in different temperatures between 180 and 210 °C with 100 rpm speed. After mixing, the material was granulated followed by blow extruder processing at temperature profile 180–210 °C, with 20 rpm speed, for film production.

Characterization of TPE-E Films Differential Scanning Calorimetry (DSC) The analyses were performed using the Mettler-Toledo DSC 822 apparatus under nitrogen atmosphere. The program used was: heating from 25 to 250 °C and isotherm of 5 min, cooling from 250 to 25 °C and isotherm of 5 min and reheating from 25 to 250 °C and isotherm of 5 min, all in the heating rate of 10 °C min−1 .

Thermogravimetric Analysis (TGA) The TGA analyses were performed on the Mettler-Toledo-TGA/ SDTA 851 equipment. The tests were programmed for nitrogen atmosphere using a temperature range between 25 and 750 °C with a 10 °C min−1 heating rate.

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X-Ray Diffraction (XRD) The diffractograms were obtained using an X-ray diffractometer with CuKα radiation source (λ = 1.54056 Å) generated at 30 kV and 20 mA. The angle variation (2θ) was 3–60° with the pitch of 0.03° and acquisition time of 1 s in the Rigaku Mine Flex II apparatus.

Transmission Electron Microscopy with Energy Dispersive Spectroscopy (TEM-EDS) The transmission electron microscope (TEM) equipment used was Jeol model JEM2100, with dispersive energy spectroscopy detector.

Antibacterial Activity—JIS Z 2801:2010 The antimicrobial activity was performed according to the JIS Z 2801:2010 procedure at the Brazilian company Controlbio. The test was used to evaluate the bactericidal activity, or the antimicrobial potential of silver incorporated TPE-E compounds against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli).

Results and Discussion Differential Scanning Calorimetry (DSC) The results of crystallinity are illustrated in Fig. 1 and reported in Table 1.

Table 1 Results of melting temperature, melting enthalpy and degree of crystallinity of two melting cycles in comparison to the pure TPE-E Samples Melting point 1st Hm (J/g) 1st Xc (%) 2nd Hm 2nd Xc (%) (°C) (J/g) TPE-E_neat

199

27

11

25

10

TPE-E_0.05% 199 AgNPs_ZnO

23

9

23

9

TPE-E_0.5% AgNPs_ZnO

27

11

25

10

200

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Fig. 1 DSC curve of TPE-E pure TPE-E with 0.05 and 0.5% AgNPs_ZnO in N2 atmosphere

It was possible to observe any change that occurred in the melting point and in the degree of crystallinity of the first and second heating cycles with increasing the percentage of AgNPs_ZnO. The incorporation of the silver nanoparticle did not change the crystallinity of the polymeric film in the concentration range analyzed. The melting point and level of crystallinity were studied due to the importance of both in silver release and bactericidal effect. According to the Kumar et al., 2005, the bactericidal efficiency and silver release are related to the level of crystallinity of the polymer as also the potential of polymer to absorb moisture. High level of crystallinity decreases the silver release and in consequence decreases the bactericidal effect of silver. This occurs because silver tends to be in the amorphous phase so when a high level of crystal is present, the diffusion decreases and nanosilver or silver ions do not came to the surface to act against bacteria. TPE-E presents low level of crystallinity that justify it performance for bactericidal efficiency. Water (H2 O) and Ag+ have affinity to the amorphous phase so when crystallinity increases, more difficult will be the H2 O and nanosilver diffusion to permits the ion formation according to Ag0 + H2 O ↔ Ag+ .

Thermogravimetric Analysis (TGA) The influence of nanoparticles in the stability of the composites can be observed in the displacement of TGA events as concentration function, Fig. 2. The temperature of decomposition is associated to the initial temperature Tonset of the event according to Table 2. It was shown a displacement in the decomposition onset temperature of TPE-E with increase of concentration, 0.05 and 0.5% AgNPs_ZnO. The concentration of 0.5% AgNPs_ZnO showed a significant decrease in the decomposition

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Fig. 2 TGA curve of TPE-E pure, TPE-E with 0.05 and 0.5% AgNPs_ZnO in N2 atmosphere

Table 2 Results of degradation temperature (Tonset) of TPE-E pure, TPE-E with 0.05 and 0.5% AgNPs-ZnO

Samples

TOnset (°C)

TPE-E_neat

362.4

TPE-E_0.05% AgNPs_ZnO

362.6

TPE-E_0.5% AgNPs_ZnO

329.5

onset temperature at about 35.1 °C when compared to the decomposition onset temperature of pure TPE-E_. Although the concentration of 0.5% AgNPs_ZnO was not sufficient to increase crystallinity by nucleation phenomena, it was enough to decrease the stability of the nanocomposite.

X-Ray Diffraction (XRD) Diffractograms are presented in Fig. 3 and compare the nanocomposites with the pure thermoplastic elastomer. The β-phase related peaks at 29° and 31° are absent with increasing % AgNPs-ZnO in the TPE-E polymer matrix. The 7° and 24.5 ° peak became absent in the compound containing AgNPs-ZnO. The appearance of a peak between 21.1° and 23.8° was associated with the peak of the amorphous SiO2 phase present in the AgNPs-ZnO composition. In the sample containing 0.5%, it was possible to observe the presence of ZnO peaks at around 31.80; 34.40 and 36.29° assigned to the respective crystalline planes [100], [002], [101]. With the addition of the additive, there was a decrease in peak intensity in relation to the TPE-E pure.

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Fig. 3 Diffractogram of TPE-E_pure, TPE-E with 0.05 and 0.5% AgNPs_ZnO

Fig. 4 Transmission microscopy image of AgNPs_ZnO powder. Zinc is indicated by long arrow and silver by short arrow

Transmission Electron Microscopy with Energy Dispersive Spectroscopy (TEM-EDS) Images of microscopy, Figs. 4 and 5, of AgNPs_ZnO powder and TPEE_AgNPs_ZnO films were obtained at 100 nm and 20 nm scales respectively. In the TEM image (Fig. 4) of AgNPs_ZnO powder was possible to observe particles with stick-shaped of ZnO and spherical darker associated to spherical nanoparticles of Ag°. In the films, it was possible to observe nanoparticles at around 20 nm as shown in Fig. 5. The darker particles represent the spherical Ag° nanoparticles indicated by short arrow. Kumar et al., 2005 studied the difference of filled type on silver release and showed that silver bactericidal efficiency depends on silver particle shape. It was observed that silver spherical shape presented better bactericidal results

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Fig. 5 Transmission microscopy image of TPE-E_AgNPs_ZnO films. silver indicated by short arrow

Table 3 Bactericidal activity results of sample TPE-E_0,5% AgNPs_ZnO and TPE-E_0,05% AgNPs_ZnO Condition and reduction TPE-E_0.5% AgNPs_ZnO TPE-E_0.05% AgNPs_ZnO Bacterial count at time zero S. aureus ATCC 6538

2.1 × 105

1.8 × 105

Bacterial count after 24 h contact S. aureus ATCC 6538 Logarithmic reduction

5.0 × 104

1.4 × 104

0.62

1.11

% Reduction

76.2

92.2

Bacterial count at time zero E. 2.3 × 105 coli ATCC 8739

2.0 × 105

Bacterial count after 24 h contact E. coli ATCC 8739 Logarithmic reduction

5.7 × 104

1.3 × 104

0.60

1.19

% Reduction

75.2

93.5

comparing with rod and triangular shape. As Ag, Zn either has bactericidal effect when added in the polymer. The combination of action of both reveals favorable performance for the bactericidal application.

Bactericidal Test—JIS Z 2801:201 In Table 3 are compared the results of the microbial tests with Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli).

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The TPE-E pure sample showed no bactericidal activity, as expected, for either of the two types of bacteria tested. TPE-E with AgNPs_ZnO presented bactericidal activity. TPE-E with 0.05% AgNPs_ZnO presented better results than TPE-E with 0.5% AgNPs_ZnO. This effect in TPE-E film can be related to saturation and high level of agglomeration when compounded in concentration of 0.5% of additive AgNPs_ZnO.

Conclusion The polymer nanocomposite films containing AgNPs_ZnO showed bactericidal activity in different percentage of nanoparticles. Sample with 0.05% presented better results when compared with sample containing 0.5%. Samples with AgNPs_ZnO did not show changes in melting point and degree of crystallinity when compared with TPE-E neat. Sample with 0.5% of AgNPs_ZnO showed decrease in degradation onset temperature when compared to sample with 0.05% AgNPs_ZnO and TPE-E pure. The microbiological results of TPE-E_ AgNPs_ZnO proved it efficiency against Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). The higher activity was achieved for TPE-E_0.05% AgNPs_ZnO against Escherichia coli (E. coli). Acknowledgements The authors are thankful to CCTM/IPEN for the TEM images, to the Mr. Eleosmar Gaspar for the DSC and TGA analysis, and Vinicius Juvino dos Santos and Camilla Bassetti for the extrusion experiments. To project CAPES 08881068030/2014-10.

References 1. Durán N, Durán M, de Jesus MB, Seabra AB, Fávaro WJ, Nakazato G (2016) Silver nanoparticles: a new view on mechanistic aspects on antimicrobial activity. Nanomed Nanotechnol Biol Med 789–799 2. Kumar R, Howdle S, Münstedt H (2005) Polyamide/silver antimicrobials: effect of filler types on the silver ion release. J Biomed Mater Res Part B Appl Biomater 311–319 3. Kumar R, Münstedt H (2005) Silver ion release from antimicrobial polyamide/silver composites. Biomaterials 2081–2088 4. Becaro AA, Puti FC, Correa DS, Paris EC, Marconcini JM, Ferreira MD (2018) Characterization and antibacterial properties of nanosilver-applied polyethylene and polypropylene composite films for food packaging applications. Food Biosci 83–90 5. Oliani WL, Parra DF, Komatsu LGH, Lincopan N, Rangari VK, Lugao AB (2016) Fabrication of gamma-irradiated polypropylene and AgNPs nanocomposite films and their antimicrobial activity. In: TMS annual meeting, pp 143–150 6. Rao YN, Banerjee D, Datta A, Das SK, Guin R, Saha A (2010) Gamma irradiation route to synthesis of highly re-dispersible natural polymer capped silver nanoparticles. Radiat Phys Chem 1240–1246 7. Triebel C, Vasylyev S, Damm C, Stará H, Özpinar C, Hausmann S, Peukert W, Münstedt H (2011) Polyurethane/silver-nanocomposites with enhanced silver ion release using multifunctional invertible polyesters. J Mater Chem 4377

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8. Tomacheski D, Pittol M, Ribeiro VF, Santana RMC (2016) Efficiency of silver-based antibacterial additives and its influence in thermoplastic elastomers. J Appl Polym Sci

Part III

Non-ferrous Metals and Processes

Adsorption Behavior of Cu(II) to Silica-Humics Composite Aerogels Guihong Han, Pengfei Tang, Hongyang Wu, Jun Ma, Xiaomeng Yang and Yongsheng Zhang

Abstract Silica aerogel is a kind of nanoscale amorphous solid mesoporous material made by agglomerating colloidal particles with gas as dispersion medium, providing silica aerogel with high surface area and absorptive performance. The humics contain a large number of carboxyl which brings a strong adsorption behavior for Cu(II). The morphology and structure of the as-prepared silica-humics composite aerogels were prepared via sol-gel method. In this paper, the adsorption behavior of 10 mg/L Cu(II) to silica-humics composite aerogels was studied. The adsorption parameters such as pH, temperature and the amount of silica-humics composite aerogels were studied to achieve the optimal conditions. This work opens a new perspective for the Cu(II) removal from contaminated water. Keywords Silica · Humics · Composite aerogels · Adsorption

Introduction The pollution of water resources with heavy metals has been causing worldwide concern in the last few decades. Namely, some metals can have toxic or harmful effects on many forms of life. Although the country has advocated green industry in recent years, there are still many industrial enterprises that discharge three wastes in violation of regulations, and the wastewater is particularly serious, which has caused the pollution of water bodies to increase. Water weight metal ions include about 45 kinds of mercury (Hg), copper (Cu), nickel (Ni) and manganese (Mn), etc. Copper has been reported to cause neurotoxicity commonly known as “Wilson’s disease” due to the deposition of copper in the lenticular nucleus of the brain and kidney failure [1]. Because of all these reasons and some definite regulation measures of

G. Han · P. Tang · H. Wu · J. Ma · X. Yang · Y. Zhang (B) School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, People’s Republic of China e-mail: [email protected] © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_10

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precaution, it becomes necessary to remove these heavy metals from wastewater by an appropriate treatment before releasing them into the environment. Conventional methods for the removal of heavy metals include precipitation, adsorption, flocculation, ion exchange, reverse osmosis, complexation/sequestration [2, 3], electrochemical operation and biological treatment [4, 5]. Compared with other methods, the adsorption method has attracted much attention due to its advantages such as the wide source of raw materials, easy availability of products, simple operation of equipment, high efficiency, high selectivity, high recovery and utilization rate, and low secondary pollution. The choice of adsorbent is critical during the adsorption process. Adsorbents are solid materials that are effective in adsorbing some of these components from gases or liquids. Adsorbents generally have the following characteristics: large specific surface, suitable pore structure and surface structure; strong adsorption capacity to adsorbate; generally do not chemically react with adsorbate and medium; easy to manufacture, easy to regenerate; good mechanical strength, etc. Pore size, pore distribution and surface area, as well as pore surface chemistry, are the major factors in the adsorption process [6, 7]. Silica aerogels meet these conditions because they are extremely porous (up to 99%) nanostructured materials with high specific surface areas (500–1000 m2 g−1 ), low density (as low as 5 kg/m−3 ), large porosity (80–99.8%), low thermal conductivity(~0.01 w/m k) and they exhibit capacities which are comparable or even exceed that of commonly used adsorbents [8]. Due to the friability of the porous network skeleton structure of the aerogel, the aerogel structure collapses under heavy pressure, which seriously degrades its unique properties and limits its application. Aerogels are widely used as catalysts and catalyst carriers [9], acoustic impedance coupling materials [10], gelling agents for rocket propulsion, etc. In the practical application of silica aerogel, it needs to be combined with other materials to construct a network skeleton supporting and protecting the aerogel structure to obtain an aerogel composite [11]. Humic acid is a kind of macromolecular organic weak acid polymer formed by a series of decomposition and transformation of animal and plant remains, under the action of geophysical, chemical and microbes. Humic acid is widely found in soil, lakes, oceans, and lignite, weathered coal, and peat. The humic acid molecule has a certain adsorption capacity, and its molecule contains a large number of active groups such as carboxyl group, alcoholic hydroxyl group and phenolic hydroxyl group, which can interact with many organic and inorganic substances [12]. The removal of heavy metal ions depends on concentration, pH, adsorbent dose and temperature. That is the reason why in our research we have first determined optimal conditions for adsorption. At these conditions, the results were fitted with the first-order kinetic model and the second-order kinetic model.

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Experimental Materials The chemicals used for the preparation of silica-humics composite aerogels by solgel synthesis were Na2 SiO3 (AR), Sinopharm Chemical Reagent Co. Ltd.; DMF (AR, 99.5%), NaOH (AR, 96%), Tianjin Kermel Chemical Reagent Co. Ltd.; sulfuric acid (AR, 95–98%), Luoyang Haohua Chemical Reagent Co. Ltd.; HA (fulvic acid, FA ≥ 90%), Shanghai Aladdin Bio-Chem Technology Co., Ltd were all used as received. Other chemicals included distilled water. A mixture of heavy metal ions was prepared for selectivity test. For the following experiments to determine adsorption capacity of aerogel, the solutions for each metal ion were prepared by diluting 10 mg/L of stock solution with distilled water. The pH adjustments were made with buffer solutions (sodium hydroxide/acetic acid, disodium dihydrogen phosphate/potassium dihydrogen phosphate) of appropriate pH.

Preparation of the Composite Aerogels 8 g of sodium silicate and 120 ml of distilled water were weighed and mixed to prepare a sodium silicate solution, and N,N-dimethylformamide (DMF) was used as a drying control chemical additive [13], and the amount of DMF added was 2.54 ml. A volume of sulfuric acid is then added to the sodium silicate solution to adjust the pH to 1–2. Then, 2 g of humic acid was added to the solution, and a 1 mol/L sodium hydroxide solution was added dropwise to adjust the pH to 6, and stirring was continued while adjusting the pH, and the gel was formed after standing for a while. The gel was washed three times with distilled water, followed by freeze-drying to obtain an aerogel powder.

Adsorption Experiments The adsorption experiment explored the influence of the amount of silica humic acid composite aerogel, pH and temperature on the adsorption of 10 mg/L Cu(II) solution. The results of these studies were used to obtain the optimum conditions for adsorption capacity measurements. Atomic adsorption spectrophotometer (AAS) was used to analyze the concentration of heavy metals in water solutions. The percent of adsorbate removal was calculated using Eq. (1) E  (C0 − Ce ) × 100/C0

(1)

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Fig. 1 Effect of composite aerogels dose on the removal of Cu(II)

where E is metal ion removal in %, C0 initial metal ion concentration of test solution and Ce final equilibrium concentration of test solution.

Results and Discussion Effect of Composite Aerogels Dose and Adsorption Kinetics The samples of composite aerogels dose were prepared over the range 60–180 mg, with initial metal concentration 10 mg/L. The results for percent removal of Cu(II) with regard to composite aerogels dose are shown in Fig. 1. They show the increase of percent removal with composite aerogels dose, reaching 81% removal at composite aerogels dose of 120 mg. Percent removal of heavy metal ions increases with the increase in composite aerogels dose because of a greater number of available exchangeable sites.

Effect of pH The results of pH effect on adsorption are presented in Fig. 2. In the case of Cu(II) ions, the percentage adsorption increases with pH. The percent removal of Cu(II) ions decreases by increasing pH above 6. The reason may be partial hydrolysis of M+ , resulting in the formation of MOH+ and M(OH)2 . Higher adsorption of Cu(II) ions at higher pH values appears due to precipitation of nonsoluble metal hydroxyl complexes. The optimum pH is 6 in the case of Cu(II) ions.

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Fig. 2 Effect of pH on removal of Cu(II) by silica-humics composite aerogels

Fig. 3 Effect of temperature on removal of Cu(II) by silica-humics composite aerogels

Effect of Temperature It can be seen from Fig. 3 that the adsorption percentages at 25, 35, and 45 °C are gradually increased, and the highest adsorption percentage is reached at 60 min. After 60 min, the percent adsorption was balanced. The optimum temperature is 35 °C in the case of Cu ions.

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Conclusions In this study, silica-humics composite aerogels were prepared by sol-gel method and freeze-drying method, and the ability of silica-humics composite aerogels to remove Cu(II) ions from water was investigated. The functional groups and microstructure of the composite aerogel were characterized by FTIR and SEM analysis. Optimal conditions of adsorption on silica-humics composite aerogels were then determined. Cu(II) removal was the most efficient at pH 4 and 45 °C. The most efficient composite aerogels dose is 120 mg. The results of the present investigation illustrate that silicahumics composite aerogels could be used as an effective adsorbent for the removal of Cu(II) ions from aqueous solutions. Acknowledgements The authors acknowledge the financial support provided by the National Science Fund of China (No. 51674225, No. 51774252), the Innovative Talents Foundation in Universities in Henan Province (No. 18HASTIT011), the Educational Commission of Henan Province of China (No. 17A450001, 18A450001), and the China Postdoctoral Science Foundation (No. 2017M622375).

References 1. Bloomer JL (1982) Introduction to organic and biological chemistry. ACS Publications 2. Aptel P, Clifton M (1986) Synthetic membranes: science, engineering and applications. D Reidel Publishing Company 3. Hartinger L (1991) Handbuch der Abwasser-und Recyclingtechnik für die metallverarbeitende Industrie (Handbook of sewage-recycling techniques for the metalworking industry). Hanser Verlag, München 4. Kiffs R, Barnes C, Forster S (1987) Surveys in industrial wastewater treatment-manufacturing and chemical industries. Longman, New York 5. Namasivayam C, Ranganathan K (1995) Removal of Pb(II), Cd(II), Ni(II) and mixture of metal ions by adsorption onto ‘waste’ Fe(III)/Cr(III) hydroxide and fixed bed studies. Environ Technol 16(9):851–860 6. Yang RT (2003) Adsorbents: fundamentals and applications. Wiley 7. Ruthven DM (1984) Principles of adsorption and adsorption processes. Wiley 8. Lee C, Kim G, Hyun S (2002) Synthesis of silica aerogels from waterglass via new modified ambient drying. J Mater Sci 37(11):2237–2241 9. Pajonk G (1991) Aerogel catalysts. Appl Catal 72(2):217–266 10. Sugihara T, Bruner J, McElroy L (1991) Lawrence Livermore National Lab., CA (United States) 11. Aegerter MA, Leventis N, Koebel MM (2011) Aerogels handbook. Springer Science & Business Media 12. Ghabbour EA, Davies G (2014) Humic substances: structures, properties and uses. Woodhead Publishing 13. Lenza RF, Nunes EH, Vasconcelos DC et al (2015) Preparation of sol–gel silica samples modified with drying control chemical additives. J Non-Cryst Solids 423:35–40

Inter- and Transgranular Nucleation and Growth of Voids in Shock Loaded Copper Bicrystals Elizabeth Fortin, Benjamin Shaffer, Saul Opie, Matthew Catlett and Pedro Peralta

Abstract Understanding the evolution of dynamic deformation and damage due to spall at grain boundaries (GBs) can provide a basis for connecting micro- to macroscale failure behavior in polycrystalline metals undergoing extreme loading conditions. Bicrystal samples grown from the melt were tested using flyer-plate impacts with shock stresses from 3 to 5 GPa. Pulse duration and crystal orientation along the shock direction were varied for a fixed boundary misorientation to determine thresholds for void nucleation and coalescence in both the bulk and the boundary. Sample characterization was performed using electron backscattering diffraction (EBSD) and scanning electron microscopy (SEM) to gather microstructural information at and around the GB, with emphasis on damage at the boundary. Simulations were performed to interpret experimental results. Initial results show that the kinetics of damage growth at the boundary is strongly affected by pulse duration and stress level and that once a threshold level is reached, damage increases faster at the GB compared to the grain bulks. Keywords Spall · Bicrystal · Pulse duration · Grain boundary

Introduction Shock loading is a dynamic condition that can lead to material failure and deformation starting at the microstructural level such as cracking, void nucleation and growth, and eventually spallation, the most common failure mode [1]. The amount of spall observed in a sample can vary with loading conditions, e.g. pressure and E. Fortin (B) · B. Shaffer · P. Peralta Arizona State University, Tempe, AZ, USA e-mail: [email protected] S. Opie General Atomics, Palmdale, CA, USA M. Catlett Los Alamos National Laboratory, Los Alamos, NM, USA © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_11

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pulse duration [1–3]. Previous research has determined that the microstructure does play an important role in damage nucleation and growth, through parameters such as grain size [3, 4], grain boundaries [5–9], the effects of which are compounded by material anisotropy [2]. By studying the deformation patterns at and around GBs in samples where damage in its incipient or intermediate stages, we can determine preferential sites in the material’s microstructure where voids will nucleate and grow. The observation of spall damage on a material is important because if a structure is impacted at a high enough pressure for fracture to occur, there is a possibility that microstructural cracks can grow to the macroscale leading the structure to burst from the inside out. The purpose of this work is to understand the kinetics of void nucleation and growth at selected grain boundaries using copper bicrystals to have a single boundary that allows for the sole observance of the effect at the boundary without other interactions. Experiments on copper multicrystals performed by Peralta et al. [5] have proved that some grain boundaries have a stronger response to dynamic loading than others. Results showed that tips of terminated twins, which are the high energy and mobility ends of an annealing twin with an incoherent boundary [5], were the sites of damage localization in many of the copper samples. Work performed by Wayne et al. [10] found that terminated twins and grain boundaries with misorientation angles between the 25° and 60° range were preferred sites for intergranular damage nucleation. Shock loading experiments were also performed on copper samples with different thermomechanical histories (heat treated, fully recrystallized, and as received), producing grain size and plastic deformation variations in [11, 12]. Results confirmed previous findings of Wayne et al. [10] that the 25°–50° range is favorable for damage nucleation, regardless of the initial conditions, and that damage was unlikely to nucleate at {111} 3 boundaries. The work suggests that plasticity in the grain bulks is responsible for the incipient spall to nucleate at the weaker grain boundaries in the microstructure [11, 12]. Escobedo et al. [13] found in spalled tantalum samples that damage occurred at low coincidence, high angle grain boundaries. Subsequent work performed by Cerreta et al. in [7] where they concluded that 3 and low-angle boundaries were resistant to void nucleation with peak compressive stresses between 1.5 and 2.5 GPa during shock loading. This further confirmed the earlier results found by Wayne et al. [10]. The effect of pulse shape has been reported in work performed by Gray et al. [14] on 316L stainless steel using Taylor waves, or triangular-shaped, and square-topped pulse shapes. Peak shock stresses were 6.6, 10.2, and 14.5 GPa. The triangularshaped pulse showed damage only at 14.5 GPa, while results for the square pulse showed incipient spallation at 6.6 GPa. From this, it can be seen that the squareshaped pulse has a lower spall strength than the triangular pulse. Pulse duration was also explored by Gray et al. [15] using three different pulse durations, 0.84, 0.28, and 0.25 μs on Tantalum targets, reaching peak stresses of 7.4, 10.6, and 21 GPa, respectively. Different flyer thicknesses, 2.25, 2.42, and 6.25 mm, were used to vary pulse duration, while target thickness remained constant at 4.572 mm. The 21 GPa sample resulted in full spallation, with a scab being ejected from the free surface,

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with the 7.4 and 10.6 GPa samples show incipient spallation. From this, it can be seen that a longer pulse duration and higher peak shock stress create more damage. Molecular dynamic simulations have been performed Rudd and Belak [16] in order to study void nucleation and growth. Results showed that GBs are the preferential sites for void nucleation and void growth is anisotropic [16]. Molecular dynamic simulations of copper bicrystals performed by An et al. [9] found that most of the damage still takes place in the GB region due to boundary weakening. Secondary void nucleation was also found to be more pronounced in the grain that had more activated slip systems. This difference in damage is attributed to differences in plastic deformation, caused by the structural asymmetry of the grain boundary [9]. Wilkerson et al. [17] have studied the dislocation kinetics on dynamic void growth using a dislocation-based viscoplastic computational model. They discovered that dislocation kinetics and micro-inertia effects play a role in dynamic void growth. It was found that micro-inertia affected void growth once the void was larger than a micron, and the growth of smaller voids was dominated by dislocation kinetics. The authors also state that smaller grains can cause a lower spall strength by inversely following the Hall–Petch behavior. The fast nature of shock loading does not allow dislocation movement to be the dominant failure mode; instead, failure will occur at the weak point of the sample, the grain boundaries. In this study, SEM and EBSD were used alongside optical microscopy (OM) to observe the damage at the GB and grain bulks to understand the roles pulse duration and crystal orientation play in void nucleation and growth at individual boundaries.

Materials and Methods Bicrystal Growth Bicrystals were grown using a modified vertical Bridgman technique [18]. A graphite mold was constructed to fit inside a quartz tube and to hold the single crystal seeds and stock copper. The graphite mold used has reentrant corners that pinned the boundary so that it is located where both the single crystals meet (see [18]). The mold also had a bottom hole where a thermocouple is located to measure the temperature of the seed. The temperature profile of the furnace used was measured so the seeds would be placed just below the hottest zone of the furnace. This way, once the top portion of the seeds reached melting temperature, the stock copper placed on the top was already molten, allowing for the seed orientation to quickly grow upwards once the temperature in the furnace is reduced by decreasing the power. A thermolyne furnace model 21100 was used for the bicrystal growth. The system was purged with UHP Argon gas for 10 min prior to starting the experiment. The furnace was consistently ramped up by increasing the set point 300 °C at a time until the thermocouple monitoring the seed temperature approached 1080 °C. The set point of the furnace was then increased by 1° at a time until the inner thermocouple

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Fig. 1 Bicrystal boule after growth

read 1083 °C. The furnace was held at 1083 °C for 10 min to alloy for enough time to melt the full load of material inside the mold. Then, the furnace set point was increased a degree until the inner thermocouple read 1084 °C, the furnace was held there for 30 s. This process allows for the seeds to slightly melt, which results in the seed orientation growing vertically along the mold, producing a bicrystal. Then, the setpoint of the furnace was decreased by 1° a minute for the first 20° and 2° a minute for the next 40°. The resulting boule is shown in Fig. 1.

Sample Preparation Samples were sectioned from the resulting bicrystals via electro-discharge machining (EDM) and polished to their desired thicknesses. The sample surfaces were finished with 0.02 μm colloidal silica and a planarity of 0.05°. Two different configurations of bicrystal samples were studied in order to understand the effect of crystal orientation on the damage kinetics for a fixed grain boundary misorientation. Targets were fabricated from the parallel, or growth direction, and perpendicular directions on the bicrystal boule. The crystallography of both targets is shown in Fig. 2. The grains are labeled 1 and 2 in the inverse pole figures to correspond to the orientations shown in the EBSD scan for both the growth and punch out directions. Figure 3 shows where samples were extracted from the boule.

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Fig. 2 Top: EBSD scan of the undeformed growth direction, bottom: inverse pole figures for the growth and punch out directions

Fig. 3 a Growth direction cut, b punch out direction cut

Flyer-Plate Impact Flyer-plate impacts were performed on a light gas gun system at ASU. Bicrystal targets measured 10 mm in diameter and 1 mm thick, while copper polycrystals flyers were 8 mm in diameter and either 500, 385, or 225 μm thick. The flyer was attached to an ultra-high molecular-weight polyethylene sabot using epoxy. The sabot had a hole machined in the center, which gave the flyer a free surface on the backside and provided an alignment tool to place the flyer in the center of the sabot face. Targets were placed in a PMMA window with a hole machined in the center to give the backside of the target a free surface. The target and window were placed in a PMMA holder and secured in the recovery chamber of the gas gun. The sabot is

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launched down the barrel of the gas gun via a light gas, such as nitrogen. Shortly after exiting the barrel, the flyer attached to the sabot will come into contact with the target in the recovery chamber. Growth direction sample velocities began at 200 m/s and increased by 10 m/s until 240 m/s, while punch out sample velocities began at 225 m/s and increase by 5 m/s until 240 m/s. Maximum pressures ranged from 3.7 to 4.5 GPa. The velocities were chosen based off of previous experiments where incipient and intermediate, or coalescence, spallation was observed at the boundary. Intermediate spallation was seen at the boundary in both targets at 240 m/s, while incipient spall was seen at the boundary at 200 m/s for the growth direction targets and 225 m/s for the punch out direction targets. The gas gun uses a laser/photodiode/oscilloscope system to capture the velocity of the flyer before impact. A laser beam passes directly through the recovery chamber and meets the photodiode on the opposite side, which is attached to an oscilloscope, where data is captured. As the projectile leaves the barrel and crosses the laser beam, the oscilloscope is triggered to record the change of light the photodiode experiences. From the result recorded on the oscilloscope, time is measured from where the signal begins to drop to where the signal begins to rise, left to right. Then, velocity can be calculated by dividing the length of the projectile by the time spent passing the laser beam. The resulting velocity measurements are, approximately ±1.6 m/s accurate. This initial velocity data is enough information to determine the maximum shock stress experienced by the sample.

Post-Shot Characterization After the experiment, targets were soft recovered and cross-sectioned so that the boundary was perpendicular to the cut. The cross sections were then polished to EBSD quality and scanned to observe the spall damage at the boundary and within the bulk of the grains. Consecutive sectioning was also performed through the thickness of the spall zone to observe the change in the void nucleation and growth at the boundary.

Abaqus Simulations A dynamic, explicit Abaqus model and crystal plasticity subroutine based on the model described in [19] to simulate flyer-plate impact. An 8 mm in diameter flyer and a 10 mm in diameter target with the desired thicknesses were used to match the samples used in gas gun experiments. The target was partitioned in half and a separate crystallographic orientation was assigned to each half as determined from EBSD data collected on the as grown bicrystals. The flyer was assigned a predefined velocity field and set to the measured impact velocity during the experiment. Figure 4 shows the flyer-plate model.

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Fig. 4 Flyer-plate model used for simulations. The flyer is on top and the partitioned target is below

The crystal plasticity subroutine used [19] is specialized to FCC materials and uses a multiplicative decomposition of the deformation gradient that includes a volumetric component to account for damage due to void nucleation and growth, as follows: F  Fe Fv F p

(1)

where F is the total deformation gradient, Fe is the elastic part of the deformation, Fv is the volumetric part of the deformation due to void nucleation and growth, and F p is the isochoric plastic deformation [20, 21]. Damage due to void growth and nucleation is accounted for using a Gurson–Tvergaard–Needleman (GTN) model where the voids are assumed to grow isotropically and micro-inertia effects can be ignored when observing void nucleation at an incipient stage [22]. Further information about the crystal plasticity subroutine used in this work can be found in [19].

Results and Discussion Bicrystal Growth Results After the boule is recovered, the seeds are removed and a small sliver of the boule is cut to verify that only two grains exist. The boundary is naturally meandering, shown in Fig. 2, so that it makes a good surrogate for boundaries found in actual polycrystals and multicrystals, which have curvature as well. The misorientation measured 42° across the boundary, which was found to be close to the misorientation most likely to nucleate damage from results in [4, 12].

Shot Conditions Results from the flyer-plate impact experiments are shown in Tables 1 and 2 for the growth and punch out direction shots, respectively. Results are shown for the samples

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Table 1 Growth direction shot conditions Flyer Shot Velocity σmax (GPa) thickness number (m/s) (μm) 225 385

500

Right grain damage

233.7

4.29

Incipient

None

None

127

240.1

4.42

Incipient

None

Incipient

121

199.7

3.65

Incipient

Incipient

Incipient

119

230.6

4.23

Incipient

Coalesced

Incipient

117

240.3

4.42

Incipient

Coalesced

Incipient

110

223.4

4.1

Incipient

Incipient/

Incipient

Incipient

coalesced Coalesced

Incipient

Left grain damage

Boundary damage

Right grain damage Incipient

232.6

4.27

Table 2 Punch out direction shot conditions Flyer Shot Velocity σmax (GPa) thickness number (m/s) (μm)

500

Boundary damage

122

112

385

Left grain damage

148

230.7

4.24

None

Incipient

151

240.7

4.43

None

Unzipped

None

159

227.5

4.17

Incipient

Unzipped

Incipient

136

239.4

4.4

Incipient

Unzipped

Incipient

that did nucleate damage and are grouped by flyer thickness (225, 385, 500 μm) and velocity. Damage at the boundary and each bulk were also recorded.

Gas Gun Experiments From both the growth and punch out direction results, the 225 μm flyers were unable to nucleate damage at the boundary. In the growth direction shots 122 and 127, damage was observed in the bulk of the grains, indicating that the boundary was stronger than the bulks for short pulses at high velocities. However, no damage was observed in the punch out samples with similar velocities (shots 156 and 150), showing how the difference in orientation affects strength. The boundary also behaves differently between the growth and punch out samples. For the 385 μm flyer shots, the growth direction boundary shows an incipient coalescence at 213.1 m/s (shot 191), while coalescence is not observed until 240 m/s (shot 151) in the punch out direction. Taylor Factor maps for both the growth and punch out directions are shown in Figs. 5 and 6, respectively. The Taylor Factors from the figures from top to bottom are 3.24 and 3.42 for the growth direction and 2.94 and 2.37 for the punch out

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Fig. 5 Taylor factor map of the growth direction

Fig. 6 Taylor factor map of the punch out direction

direction. The punch out direction has the higher Taylor Factor mismatch between the two grains with 0.57. Previous research by Krishnan et al. [19] has indicated that a high Taylor Factor mismatch contributes to spallation and growth. However, damage begins to nucleate at higher velocities compared to the growth direction. The low-velocity damage nucleation in the growth direction samples can be explained by their overall higher Taylor Factors compared to the growth direction. The Taylor factor can indicate the spall strength of the grain based on the plasticity needed to begin void nucleation. A high Taylor Factor would suggest the grain is weaker in spall strength because it requires less plastic deformation before voids nucleate. Wilkerson et al. [23] developed a relationship between grain size and spall strength to predict the amount of voids nucleated in a sample. They define three fracture regions: intergranular, mixed-mode, and transgranular. For the bicrystalline experiments performed in this work with 5 mm grains and spall strengths between 3 and 4 GPa, the paper states that intergranular fracture would be the primary failure mode, which matches what is seen.

Abaqus Results from Flyer-Plate Impact Simulations Crystal plasticity simulations were performed for both the growth and punch out orientations. Two growth direction simulations were are shown in Figs. 7 and 8: shot 110 and shot 112. Both used a 500 μm target and showed incipient spall at the boundary at 223.4 m/s (shot 110) and coalesced at the boundary at 232.6 m/s (shot 112). Two outputs are of interest in each of the simulations: void volume fraction, or the ratio of voids to the total volume, and von Mises stress.

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Fig. 7 Result of a 500 μm flyer with an impact of 223.4 m/s (shot 110, growth direction). Top: von Mises (MPa), bottom: void volume fraction

Fig. 8 Result of a 500 μm flyer with an impact of 232.6 m/s (shot 112, growth direction). Top: von Mises (MPa), bottom: void volume fraction

The void volume fraction results for both shots correlate well with each other and with experimental results. The void volume fraction is higher at the boundary for shot 112, while lower for shot 110, matching what is seen experimentally in both samples. There is also a difference in damage and stress between the bulks that can be seen in the simulations. This effect can also be seen experimentally where one grain contains voids, while the other grain fails to nucleate any voids. For the samples shown in the simulations in Figs. 7 and 8. ImageJ was used to count the voids in the bulks. The left bulk had a lower number of voids in each sample with 105 for shot 110 and 145 for shot 112, while the right bulk contained 155 and 162, respectively. Although the difference in the void count can be relatively small, this could be related to the difference in the Taylor factor between the two grains. If one grain requires

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less stress to nucleate damage, voids will have a longer time to nucleate and grow compared to the grain at a higher initial stress. Further work in this area is needed to be able to confirm the orientation and Taylor Factor of each bulk in the sample to the simulation.

Conclusions Results from the flyer-plate impact tests show clearly that the kinetics of damage growth along the boundary is strongly affected by stress level and pulse duration, and the damage kinetics increase faster at the boundary than at the bulk of the grains. Comparisons of the boundary damage between both targets show the effect of grain orientations. The punch out direction seems to need a higher stress and velocity to nucleate voids compared to the growth direction, but fast kinetics once the voids nucleate. Since the misorientation angle across the boundary was controlled, another conclusion is that void nucleation and growth at the boundary is independent of orientation. Abaqus simulations are in agreement with experimental results. Simulation results indicate a difference in von Mises stress between the two bulks, which may be linked to their respective Taylor Factors, causing the differences in bulk damage seen experimentally.

References 1. Meyers MA (1994) Dynamic behavior of materials. Wiley, New York 2. Minich RW, Cazamias JU, Kumar M, Schwartz AJ (2004) Effect of microstructural length scales on spall behavior of copper. Metall Mater Trans A 35A(9):2663–2673 3. Koller DD, Hixson RS, Gray GT III, Rigg PA, Addessio LB, Cerreta EK, Maestas JD, Yablinsky CA (2005) Influence of shock-wave profile shape on dynamically induced damage in highpurity copper. J Appl Phys 98:103518-1–103518-7. https://doi.org/10.1063/1.2128493 4. Buchar J, Elices M, Cortez R (1991) The influence of grain size on the spall fracture of copper. J Phys IV Col 1(C3):C3-623–C3-630. https://doi.org/10.1051/jp4:1991387 5. Peralta P, DiGiacomo S, Hashemian S, Luo SN, Paisley D, Dickerson R, Loomis E, Byler D, McClellan KJ, D’Armas H (2008) Characterization of incipient spall damage in shocked copper multicrystals. Int J Damage Mech 18:393–413. https://doi.org/10.1177/1056789508097550 6. Wayne L (2009) Three-dimensional characterization of spall damage at microstructural weak links in shock-loaded copper polycrystals. Master’s thesis, Arizona State University 7. Cerreta EK, Escobedo JP, Perez-Bergquist A, Koller DD, Trujillo CP, Gray GT III, Brandl C, Germann TC (2012) Early stage dynamic damage and the role of grain boundary type. Scripta Mater 66:638–641. https://doi.org/10.1016/j.scriptamat.2012.01.051 8. Escobedo JP, Dennis-Koller D, Cerreta EK, Patterson BM, Bronkhorst CA, Hansen BL, Tonks D, Lebensohn RA (2011) Effects of grain size and boundary structure on the dynamic tensile response of copper. J Appl Phys 110:033513-1–033513-13. https://doi.org/10.1063/1.3607294 9. An Q, Han WZ, Luo SN, Germann TC, Tonks DL, Goddard WA III (2012) Left-right loading dependence of shock response of (111)//(112) Cu bicrystals: deformation and spallation. J Appl Phys 111(5):053525-1–053525-4. https://doi.org/10.1063/1.3692079

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Alloying and Annealing Effects on Grain Boundary Character Evolution of Al-alloy 7075 Thin Films: An ACOM-TEM Analysis Prakash Parajuli, Rubén Mendoza-Cruz, Miguel José Yacamán and Arturo Ponce Abstract Since polycrystalline materials consist of a complex network of various types of grain boundaries (GBs), a detailed study on the types of the GBs, their distribution and how they are connected is crucial to further enhance the material’s performance. Herein, the GB character distribution (types and connectivity) of asdeposited Al and Al-alloy 7075 thin films, as well as annealed Al-alloy thin films, was investigated using an advanced microscopic technique: ACOM-TEM. Annealing processes up to 12 h caused a decrease in the content ratio of random high-angle GBs (r-HAGBs) and triple junctions comprised of r-HAGBs. However, there was no significant consequence of alloying in the GB type and connectivity distribution. Furthermore, our results indicate that vacuum-deposited Al or Al-alloy thin films possess a strong texture, and a characteristic GB distribution consistingof a significantly fraction high   of low  coincidence  site lattice GBs (predominant 1 followed by 13b, 7, 21a, 31a and 19b in descending order) and a minor fraction of r-HAGBs. Keywords Grain boundaries · Thin films · Alloying · Annealing · Triple junction ACOM-TEM

Introduction It is well-known and well-accepted that the type and frequency of grain boundaries (GBs), and their connectivity, are vital microstructural parameters that determine the material’s properties. Hence, the detailed knowledge of individual GBs, structural and thermodynamical relation with neighboring GBs, and their impacts on material properties is crucial to produce polycrystalline materials with optimum performance. Following this, an approach to “grain boundary engineering (GBE),” initially called P. Parajuli · R. Mendoza-Cruz · M. J. Yacamán · A. Ponce (B) Department of Physics and Astronomy, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX 78249, USA e-mail: [email protected] © The Minerals, Metals & Materials Society 2019 B. Li et al. (eds.), Characterization of Minerals, Metals, and Materials 2019, The Minerals, Metals & Materials Series, https://doi.org/10.1007/978-3-030-05749-7_12

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“grain boundary design and control” was proposed by Watanable in the early 1980s [1]. Based on the concept of GBE, some structural and functional properties, including but not limited to creep fracture [2], corrosion [3], segregation-induced embrittlement [4], and fatigue crack propagation [5] of face-centered cubic (fcc) metals and alloys are improved  and enhanced by introducing a high fraction of low CSL boundaries, particularly 3 boundaries. Despite enormous efforts and achievements in the field of GBE research, the application of GBE towards the development of high-performance thin films is not quite satisfactory [6]. The reason behind this could be the lack of precise control of the microstructures and a detailed understanding of the mechanism. The evolution of texture and grain boundary character distribution (GBCD) in polycrystalline thin films is strongly affected by the material processing and operating conditions, being quite different from the case of bulky specimens [4, 7]. After annealing, a strong texture is expected for fcc materials like gold, copper, and aluminum as a consequence of grain growth driven by the surface energy [8]. Numerous experimental [9, 10] and theoretical studies [11, 12] on Fe-6.5 mass% Si alloy illustrated the strong correlation between the degree of texture sharpness and the GBCD. These studies presented an extremely high fraction of CSL boundaries, in which the fraction of each type of CSL boundary was in the descending order of        value ( 1, 5, 13 and 25 for {100} textured specimens, and 1, 3, 9,  11, 17 and 19 for {110} textured specimens). However, earlier studies on gold films prepared by thermal evaporation  presented some contradicting results.  Singh et al. [13] reported a higher fraction of 7 CSL boundaries rather than 3 CSL in gold thin fractions  of CSL boundaries in descending order of  films,  whereas  high value ( 1, 3, 7, 13, 19 and 21) were reported by Shigeaki et al. [6] in sharp the same study, an extremely large fraction  textured gold thin  films.  In of 1 and a high fraction of 13, 7, 3 and 19 CSL boundaries were reported in Al films [13].  Recently, by using the ACOM-TEM technique, a high fraction of  low-angle GBs ( 1) and twin boundaries ( 3), followed by a notable fraction of  7 CSL boundaries, was reported for gold thin films, with a significant increment  in the 7 GBs after annealing [14]. Hence, these diverse results necessitate a more quantitative study on the GB microstructure evolution in sharp textured thin films, to further enhance the processing methods and conditions in order to control the GBs microstructure. Recent advances in the electron microscopy techniques and the understanding of interfaces have uncovered the important aspects of structure-dependent GB properties [15] and the GB segregation phenomena [16], which impacts the macroscopic behavior of alloyed materials. It has been well perceived in interface research that the GB segregation can be used as a microstructure design method, since accumulating solutes affect the structure, phase state, and atomic bonds within the decorated interface [17, 18]. For example, it has been reported that the increasing bulk concen tration of sulphur in pure nickel from 0.3 to 10 ppm reduces the portion of the 3 CSL boundaries from >90% to about 55% [19], whereas bulk concentration increment of sulphur in α-iron reduces the fraction of special GBs [20]. Similarly, early studies on the effect of the addition of Sn, Ti, and Cu to pure Al showed a drastic

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increase of the concentration of CSL boundaries in the case of Sn-added samples, while negligible or no effects in the case of using Cu or Ti [21]. Most of the GB segregation studies are concentrated on the effects in bulk properties of materials. Reports on the microstructure evolution (one of the important parameters influencing bulk properties) due to alloying multiple elements are largely inadequate. The purpose of this paper is to investigate the effects of alloying and annealing on GBCD of nanocrystalline Al thin films. Crystallographic information of the grains and boundaries were acquired using an advanced microscopic technique: automatic crystal orientation mapping in transmission electron microscopy (ACOM-TEM). In particular, the GB type and connectivity distribution of the as-deposited (pure Al and Al-alloy 7075) and annealed Al-alloy 7075 thin films were investigated. Furthermore, the microstructural features (texture, GB type, and connectivity distribution) of Al thin films were analyzed in detail.

Experimental Methods Thin Film Deposition Pure Al and Al-alloy 7075 films were grown by physical vapor deposition, following a methodology reported previously elsewhere [22]. The films were deposited on freshly cleaved commercial (100) NaCl crystals by the thermal evaporation of small pieces of a commercially available Al wire (99.99% pure) and a Al-alloy 7075 foil (chemical composition: Al 90%, Zn 5.5%, Mg 2.5%, Cu 1.5% and Si 0.5%), in high vacuum (10−5 torr). The thin films were prepared at a deposition temperature of 200 °C, and a rate of 0.5 Å/s. The final thickness of the film was ~400 Å. Following deposition, the sample was slowly cooled down to room temperature in vacuum. For annealing treatment, the Al-alloy sample was cleaved into smaller pieces, and these pieces were annealed in high vacuum (10−5 torr) at 300 °C for 6 and 12 h. The substrate was then dissolved in water to transfer the film to TEM grids for further characterization.

Electron Microscopy Characterization Microstructural features (texture, grain boundary character, and connectivity distribution) of the films were examined using the electron diffraction-assisted automated crystal orientation mapping technique provided by ASTARTM (NanoMEGAS, Brussels, Belgium) software package attached on a JEOL ARM 200F microscope operated at an accelerating voltage of 200 kV. A 10 μm condenser aperture and a precession angle of 0.6° were used. The electron diffraction patterns were recorded with an external ultrafast charge-coupled device (CCD) camera attached to the viewing screen of the microscope. These experimental diffraction patterns acquired from large areas

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Fig. 1 Schematic representation of the electron beam in the microscope column under the precession geometry, and experimental set up of the electron diffraction scanning unit showing different steps of the pre-formation, including diffraction acquisition and template matching

of the samples were stored in a computer, indexed, and analyzed using an automatic cross-correlation procedure with a database of pre-calculated theoretical templates of all the possible orientations and crystallographic structures [23]. A schematic representation of the processed electron beam and experimental set up of the unit in the JEOL ARM 200F microscope is shown in Fig. 1.

Results and Discussion Crystallographic Distribution of Al Thin Film Detailed ACOM analysis of the as-deposited Al thin film is shown in Figs. 2 and 3. Orientation maps viewed along the Z- and X-directions are shown in Fig. 2a and b, respectively, in which each color represents a crystallographic orientation viewed from a particular axis zone following the color code (a section of the stereographic projection of the different planes along [100]) (Fig. 2e). Here, the Z-direction refers to the view direction parallel to the electron beam (in which the experimental diffraction patterns were acquired), while the X-direction relies on the paper plane and provides complementary crystallographic information of the crystallites. Precession electron diffraction patterns obtained from the areas labeled as 1 and 2 in the orientation

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(d)

(f)

(g)

Fig. 2 ACOM analysis of an Al thin film. Orientation maps along Z-axis (a) and X-axis (b), respectively, overlaid with the index map. c, e electron diffraction patterns corresponding to the grains marked as 1 and 2 in Fig. (a). d Color code to identify the orientation of the crystallites. f Pole figures along , and g index map

maps are presented in Fig. 1c and d, respectively. There is no evidence of overlapped diffraction patterns, indicating that the grains are columnar and continuous through the film thickness. The maps revealed a strong texture indicating preferential growth direction of the film, as well as predominant when viewed along Xdirection. In addition to the orientation maps, the shown pole figure along [111] (Fig. 1f) clearly depicted the strong texture of the film. The grain boundary character is summarized in Fig. 3. The GB type is represented with colored contours in the GB map in Fig. 3b, and the length fraction of each GB is plotted in Fig. 3d. The connectivity distribution (as grain boundary triple junction (GBTJ)) is summarized in the inset in Fig. 3d. It should be noted that for a cubic crystal (applying possible symmetries), the misorientation between two adjacent

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(a)

(c)

(b)

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Fig. 3 ACOM analysis of an Al thin film. a Orientation-reliability map. b Grain boundary contours map (different types of GBs are marked by unique colors). c Orientation-reliability and disorientation graphs between the grains along the arrow marked in Fig. (b). d Length fraction of different types of GBs. The inset corresponds to the GB connectivity distribution. Dominant low CSL GBs and triple junction comprised of CSL GBs are shown in the GB contours map

grains is reduced to the disorientation angle of 0°–62.8° [24], and the CSL boundaries were assigned in view of the rotation axis and Deschamps’s  criteria for CSL boundaries [25]. Thereby, the different types of GBs such as   1 (low-angle GBs), random high-angle GBs (r-HAGBs), 13b (/27.79°), 21a (/21.78°),    7 (/38.21°), 31a (/17.90°), and 19b (/46.80°) are marked by red, black, lime, cyan, magenta, yellow, and blue colors, respectively. The GB length fraction graph in Fig. 3d indicates that a high fraction (50%)  of low-angle GBs ( 1, disorientation < 15°) are present in the film, followed by 13b  (12%) and 7 (11%) CSL boundaries. Additionally, the film possesses too few 19b (2%)   and an almost equal fraction of 21a (7%) and 31a (7%) GBs. This is consistent   with the high content ratio of 13b and 7 GBs reported for strong textured Al-alloy thin films in prior studies [13]. However, the fraction of each type of GBs is not identical, and we did not observe any twin boundaries. This difference can be related to the different deposition conditions. To study the GB connectivity distribution, the crucial parameter controlling mechanical properties [26], GBTJs were examined thoroughly, and they were cate-

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gorised into four groups based on the presence of r-HAGBs at the junction, namely, triple junction (TJ) without r-HAGBs (comprised of CSL GBs only) and TJ comprised of one, two, and three r-HAGBs. The GB connectivity distribution plot is shown in the inset of Fig. 3d, showing larger fraction (45%) of TJ without r-HAGBs, too low TJ containing two r-HAGBs (4%), and no TJ of three r-HAGBs, which seems reasonable considering the proportion of r-HAGBs in the whole film. Indicators of the quality of indexing, the index and orientation-reliability maps, are shown in Figs. 1g and 2a, respectively, representing the degree of matching between the theoretical templates to the experimental diffraction patterns during the indexing of the orientation maps, displayed in a scale of minimum (black color) to maximum (white color). The disorientation and reliability values along the line (marked in Fig. 3b) spanning two GBs are shown in Fig. 3c. It can be seen that reliability value is high (around 50) in the grain interior, whereas low (around 10) across the GB. Furthermore, the disorientation graph shows that the first two grains are disorientated by ~32° (r-HAGB), whereas other two grains are disorientated by  ~21° ( 21a GB). Black spots on the index, reliability maps, and a reliability value under 15 indicate poor quality and unsafe indexing [23], which is seen in the GB region where the reliability value dropped around 10. The reliability value around 50 and the intensity homogeneity containing white region along all the grains in the index and orientation-reliability maps in our study indicate the excellent quality of the experimental acquisition and the subsequent analysis. The strong texture and the abundance of CSL boundaries (dominant LAGBs) can be correlated to the consequences of the grain growth driven by the surface energy of Al-alloy crystallites, generating low surface energy planes towards the minimum energy configuration [27]. These results are consistent with the various reports on vacuum-deposited fcc metallic  thin films [13, 14, 22], except for the unobserved presence of twin boundaries ( 3 − /60°) and the high fraction of  19b GBs. The absence of twin boundaries in our films is ascribed to the combined effect of high stacking fault energy of Al [28], the absence of any external stress to create those boundaries [29], and the effect of the strong texture that restricts the formation of twin boundaries [6].

Grain Boundary Character Evolution Orientation maps and the corresponding GB contours map for the as-deposited and annealed Al-alloy thin films are shown in Fig. 4a–f, representing different types of GBs by unique colors. Extensive analyses on the Z-contrast imaging and spectroscopic results are reported in other studies [22] showing the chemical composition within the film and grain boundaries. Similar to the pure Al thin films, Al-alloy thin films possessed a strong texture and a dominant proportion of LAGBs. Following a minimum energy configuration, the film remained with a strong texture after annealing treatment.

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To gather statistical information on the GB types and connectivity distribution, three different regions of the as-deposited and annealed thin films were selected randomly from different meshes of the TEM grid and were scanned by a precession electron diffraction module attached to the TEM. The GB character and connectivity distribution for pure Al (as-deposited) and Al-alloy (as-deposited and annealed) thin films averaged over a large area (approx. 9 μm × 9 μm) are compared in Fig. 5. It should be noted that some poorly indexed GBs are excluded for comparison. A close observation of the graph of GB type distribution for the as-deposited pure Al and the Al-alloy thin films shows that the majority of the GBs are LAGBs (46 and 45%) for both films, and there are no significant differences ( F less than 0.05 indicate that the model terms were significant. In this case, X 1 , X 2 , X 3 , X 2 X 3 , X 21 , X 22 and X 23 are the significant model terms. According to MYERS et al. [11], for a good fitness of a model, the correlation coefficient should be at least

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Table 4 Zn recovery efficiency analysis of variance for response surface quadratic model Source Sum of square df Mean square F-value Prob > F Model X1

1956.29 23.14

9 1

217.37 23.14

86.81 9.24