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  • Characterization of Minerals, Metals, and Materials 2013

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  • Proceedings of a symposium sponsored bythe Materials Characterization Committee of

    the Extraction and Processing Division ofTMS (The Minerals, Metals & Materials Society)

    Held during the TMS 2013 Annual Meeting & Exhibition

    San Antonio, Texas, USAMarch 3-7, 2013

    Edited by

    Jiann-Yang HwangChengguang BaiJohn Carpenter

    Shadia J IkhmayiesBowen Li

    Sergio Neves MonteiroZhiwei Peng

    Mingming Zhang

    A John Wiley & Sons, Inc., Publication

    Characterization of Minerals, Metals, and Materials 2013

  • A John Wiley & Sons, Inc., Publication

    Copyright © 2013 by The Minerals, Metals & Materials Society. All rights reserved.

    Published by John Wiley & Sons, Inc., Hoboken, New Jersey.Published simultaneously in Canada.

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  • xi

    TABLE OF CONTENTS Characterization of Minerals, Metals, and

    Materials 2013

    Preface ................................................................................................................ xiAbout the Editors .............................................................................................. xiii

    Characterization of Ferrous Metals

    Application of Thermoelectric Power Technique to Study the Static Strain Ageing of Heavily Cold Drawn Steel ...................................................................3

    A. Lamontagne, X. Kleber, V. Massardier, and D. Mari

    Analysis of the Welded 100-Meter Heavy Rails for Passenger Dedicated Lines Being Broken during the Straightening Process .......................................11

    R. Chao, J Yu, and Z Min

    Effect of Continuous Cooling Rate on Microstructural Transformation of 60Si2CrVAT Spring Steel ...................................................................................21

    B. Zhou, Y. Liang, Q. Luo, J. Zhang, Q. Li, and K. Chou

    Effect of Centrifugal and Gravity Casting Technique over Metallographic and Mechanical Properties of Spheroidal Graphite Iron .....................................29

    D. Gowda H S, M. Pudukottah, and M. Herbert

    Inclusions Removal by Gas Bubbles in Steel Continuous Casting Tundish .......37M. Zhu, F. Xiong, G. Wen, S. Cao, and J. Li

    Strength and Ductility of Ultrafine Grained 304SS Prepared by Accumulative Rolling and Annealing ........................................................................................45

    W. Xue, Y. Shen, D. Liu, Z. Liu, and Y. Wang

    Characterization of Nonferrous Metal and Alloys

    Characterization of AA5754 Alloy for Identification of Barlat’s YLD2000-2dYield Criterion ....................................................................................................55

    O. Dion-Martin, M. Fafard, R. Ahmed, and G. D'Amours

    v

  • xii

    Characterization Technologies

    Automated Quantification of SiC-Particles in Solidified A356 Aluminum Using Imagepro® Plus 7.0 ...................................................................................69

    R. Fritzsch, B. Mirzaei, M. Kennedy, and R. Aune

    Quantitative X-Ray Fluorescence Determination of Elemental Composition of Micro-Constituents Smaller than the Electron Probe Volume .......................79

    A. Gesing, P. Marchwica, S. Lackie, and J. Sokolowski

    Three-Dimensional Duplex Morphology of MnS-AlN and Thermodynamic Analysis ..............................................................................................................91

    Y. Gong, C. Cai, J. Chen, S. Zheng, and H. Li

    Characterization of Inorganic Materials

    Dissolution Mechanism of Lime in FeOx-SiO2-V2O3-TiO2 Slag ......................101R. Tang, Y. Wang, S. Wang, K. Wen, H. Li, and B. Xie

    Estimation of Slag in Ferrochromium ...............................................................109R. Kozicki, G. Wrightson, and E. Graham

    Improved Thermal Shock Resistance of Shaped Alumina-Chromia Products ............................................................................................................119

    S. Breyner, T. Prietl, and K. Santowski

    Solidification Characteristics of Fe-Mn Alloy during Near-Rapid Solidification ....................................................................................................127

    Y. Guo, K. Xie, W. Xia, S. Zhao, C. Song, and Q. Zhai

    The Effect of Work-Hardening and Heat Treatment of Mild-Carbon Steel on Cyclic Deformation Behavior ......................................................................135

    G. Tober, C. Ruback, M. Kuttig, and P. Maier

    Green Materials

    Study on the Hydraulic Ash-Slag Cementitious Composites (HA-SC) Solidification of Dredged Sludge......................................................................145

    Z. Shu Jing, and H Xinghua

    Evaluation of Sisal Fibers Components by Infrared Spectroscopy ...................153A. Camposo, F. Margem, R. Loiola, and S. N. Monteiro

    vi

  • xiii

    Tensile Behavior of Epoxy Composites Reinforced with Continuous and Thinner Buriti Fibers ........................................................................................159

    G. Altoé, R. Loiola, F. Margem, N. Simonassi, and S. Monteiro

    Influence of the Red Mud Content in Mechanical Properties of Natural Fiber-Reinforced Polymer Composites .............................................................167

    M. Oliveira, E. Cunha, J. da Silva Souza, and E. Macedo

    Flexural Mechanical Characterization of Polyester Composites Reinforced with Continuous Banana Fibers ........................................................................175

    S. Monteiro, F. Margem, F. de Assis, R. Loiola, and J. Igor Margem

    Characterization for Environmental Applications

    LaCoO3: The Efficient Catalyst to Purify Pollutant Gases...............................183F. Fazlollahi, H. Atashi, and M. Sarkari

    Characterization of the Clay Soil of the Neighborhood Codin, Located in Campos (RJ), to Produce Soil-Cement Blocks .................................................191

    J. Alexandre, A. Azevedo, and G. Xavier

    Study of Mortars Used in the Projection Mechanized ......................................199G. Xavier, J. Alexandre, and A. Azevedo

    Study on Treatment of Coking Wastewater by Three-Dimensional Fluid Bed Electrode Reactor Combined with Fenton Process ...................................209

    L. Zhang, L. Wang, P. Liu, B. Fu, G. Xue, and X. Liu

    Study on Correlation between COD and TOC of Industrial Wastewater .........217S. Liu, G. Xue, and J. Zhou

    Photocatalytic Activity of TiO2-Doped Diopside .............................................225H. Yang, D. Liu, Z. Yang, X. Xue, T. Jiang, and Y. Li

    Characterization of Advanced Materials

    A Comparison between the Properties of SnO2:F Thin Films Prepared by Using Different Doping Compounds: HF and NH4F ..................................................235

    S. Ikhmayies

    Ab-Initio Calculations of the Optical Properties of Δ-NbN Single Crystal ...............................................................................................................243

    S. Ikhmayies, B. Hamad, and J. Khalifeh

    vii

  • xiv

    Photoluminescence of n-Type CdS Thin Films ................................................251S. Ikhmayies

    Photoluminescence of P-Type CdTe Thin Films ..............................................259S. Ikhmayies

    Structural and Electronic Properties of Δ-NbN Single Crystal: First Principles Calculations .............................................................................267

    S. Ikhmayies, B. Hamad, and J. Khalifeh

    Electrochemical Characterization of Lead-Calcium Alloy in Agitated Zinc Electrowinning Electrolyte ...............................................................................275

    M. Mohammadi, F. Mohammadi, and A. Alfantzai

    Effects of Rare Earth Pr on the Mechanical and Electrochemical Properties of Pb-based Alloys ............................................................................................283

    L. Jiang, X. Yu, B. Hong, X. Zhong, J. Gui, Y. Lai, J. Li and Y. Liu

    Synthesis and Characterization of Pb Free Piezoelectric Ceramics - Barium Zirconate Titanate - Barium Calcium Titanate .................................................291

    P. Praveen, K. Kumar, T. Jayaraman, A. James, and D. Das

    Characterization of High Performance Alloys

    Characterizing Primary Dendritic Microstructures to Quantify the Processing- Structure-Property Relationship in Single Crystal Nickel-Based Superalloys..301

    M. Tschopp, A. Oppedal, J. Miller, M. Groeber, A. Rosenberger, and K. Solanki

    Creep Cavitation and Fracture in Single Crystal Superalloy ............................311J. Zhao, J. Li, and S. Liu

    SCW Corrosion Resistance of Candidate Stainless Steels ................................319J. Li, W. Zheng, S. Penttilä, P. Liu, and C. Bibby

    High-Cycle Fatigue Behavior of Three Ferrite Stainless Steels at 800°C ........327T. Liu, L. Chen, H. Bi, and X. Che

    Characterization of Minerals

    A Minimum Pollution, Low Energy Process for the Recovery of Cobalt and Copper from Complex Sulphide Minerals ........................................................335

    Y. Hara

    viii

  • xv

    Characteristics and Non-Isothermal Crystallization Kinetics of Spinels in Vanadium Slag Containing High Content of Chromium ..................................345

    H. Fang, H. Li, T. Zhang, C. Liu, C. Li, and B. Xie

    Characterization and Dry High Intensity Magnetic Separation of Aswan Iron Ore.............................................................................................................355

    M. Sadawy

    Experiment Study on Sintering Process Optimization of High Chromium Vanadium-Titanium Magnetite ......................................................363

    Y. Zhang, J. Liu, G. Cheng, Z. Liu, M. Chu, and X. Xue

    Physicochemical Properties of Slags Generated during the Copper Converting Process ...........................................................................................371

    H. Zhang, X. Shi, F. Sun, X. Li, and X. Hong

    Reduction Mechanisms of Copper, Cobalt and Iron during Low Temperature Recovery from Mineral Sulphide Concentrates ................................................379

    Y. Hara

    Microwave Dielectric Characterization of Silicon Dioxide ..............................389Z. Peng, J. Hwang, B. Kim, M. Andriese, and X. Wang

    The Effect of Temperature on Dielectric Permitivity and Microwave Absorption Properties of Anthracite in Microwave Field ................................. 397

    C. Liu, L. Zhang, J. Peng, B. Liu, H. Xia, H. Chen, and K. Huang

    Recovery of High Grade SnO2 from Cassiterite Ore by Microwave Pretreatment, Leaching and Precipitation .........................................................407

    G. Onyedika, M. Ogwuegbu, E. Ejike, A. Asuwaji, and C. Nwoye

    Research on a Novel Technology of Interactive Roast of Complex Low-grade Bismuth Sulfide Ore and Pyrolusite ...............................................415

    Z. Wang, C. Zhang, C. Xia, J. Zhan, and J. Wu

    Characterization of Soft Materials

    Comparison between HDPE/Clay and HDPE/Piassava Fiber/Clay Treated by Electron-Beam Radiation .............................................................................425

    A. Ortiz, C. Escanhoela, M. Gomes, R. Oliveira, F. Díaz, and E. Moura

    ix

  • xvi

    Investigation on the Thermal Conductivity of Inorganic-Filler/Resin Composite .........................................................................................................433

    K. Monden

    Weibull Analysis of the Elastic Modulus of Bamboo Fiber of the Specimen Dendrocalmus Giganteus ..................................................................................441

    L. Martins, S. Monteiro, F. Margem, R. Loiola, A. Pereira, and J. Margem

    Characterization of Tensile Properties of Jute Fiber Reinforced Epoxy Composites .......................................................................................................449

    I. da Silva, A. Bevitori, A. Pereira, V. da Silva, F. Margem, and S. Monteiro

    Composite Based on Poly(Vinyl Alcohol), Starch and Sugarcane BagasseAshes ................................................................................................................455

    D. Jacomo, M. Gomes, J. Teixeira, V. Silva, R. Oliveira, A. Castillo, and E. Moura

    Tensile Behavior of Epoxy Composites Reinforced with Continuous and Aligned Ramie Fibers .......................................................................................465

    A. Bevitori, I. da Silva, N. Simonassi, C. Oliveyra, F. Margem, and S. Monteiro

    Tensile Strength of Epoxy Matrix Composites Reinforced with Giant Bamboo Fibers (Dendrocalmus Giganteus) ......................................................473

    L. Martins, F. Margem, S. Monteiro, R. Loiola, N. Simonassi, and J. Margem

    Surface, Joint, and Processing of Metals

    A Route to Fracture Prediction of Spot Welded Boron Steel in Automotive Applications ......................................................................................................483

    N. Raath, D. Hughes, D. Norman, I. McGregor, and R. Dashwood

    Coating Characterization in CrN Deposited by Magnetron Sputtering Method on AISI 316 Steel ................................................................................491

    I. Hilerio, M. Barrón, D. Medina, and R. Hernández

    x

  • xvii

    Characterization for Extraction Applications

    Co-Intensification of Bio-Oxidizing As-Bearing Gold Ores ............................501L. Qian, Y. Hong-Jing, Y. Yong-Bin, J. Tao, Z. Yan, and B. Guo-hua

    Effect of Copper and Ammonia on Consumption of Thiosulfate in Gold Leaching Solutions ...........................................................................................511

    J. Tao, W. Dan, Y. Yong-bin, and L. Qian

    Composition Control of the Precursor of Fibrous Ni-Co Alloy Powders by Coordinated Coprecipitation .............................................................................519

    J. Zhan, C. Zhang, and Y. Yao

    The Contrastive Studies of Microwave and Conventional Roasting CuCl Residue from Zinc Hydrometallurgy ................................................................529

    L. Shuaidan, Y. Wei, S. Ju, J. Peng, H. Chang-yuan, G. Wu, and L. Zhang

    Organophilization of a Brazilian Kaolin Clay ..................................................541C. Matos, M. Valenzuela, O. Magalhães, I. Sayeg, L. de Sant'Anna, F. Carvalho, and F. Díaz

    Indium Extraction Process from Sulfuric Pressure Leaching Solution for Vacuum Furnace Germanium Slag ...................................................................547

    H. Cao, J. Wang, B. Wu, J. Wang, and J. Li

    Research on Desilication Technology from Acid Leaching of High-Grade Silic Stone Coal ................................................................................................553

    Q. Zhao, W. Chen, S. Tang, K. Yu, X. Xing, and S. Ning

    Reformulation of a Roofing Tiles Body ...........................................................561C. Vieira, and S. N. Monteiro

    Author Index .....................................................................................................567 Subject Index ....................................................................................................571

    xi

  • PrefaceTo process minerals, metals, and materials, it is always necessary to understand the chemistries, physical properties, forms, structures, occurrences, functions, relations, etc., of the associated materials prior, during, and after the processing of materials. This type of work, which is broadly understood as characterization, is usually the ����� ����� ���� ��� ����� �� ������ ���� ��������� ����������� ���������� ��������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������������in characterization technologies and applications, the Materials Characterization Committee is formed under TMS.

    The Materials Characterization Committee of TMS sponsors the symposium on �������������� ��� !�������� !������ �� !������� ������� �� � �"��� ������ ������� ���������� ��� �������� �����!#� ����� ��������� #������� ������ ��������� �� ����symposium in conjunction with the TMS 2013 Annual Meeting in San Antonio, Texas, $#%�������������������������������

    The Characterization Symposium has grown to become one of the largest symposia in �!#������&'()����������������������������(*'��������������������������+�����Among them, 141 were selected for presentations on the symposium and more than 60 ������+������������������������������������������������������+�����������

    ����������������������+����������������������������������������������������include Characterization Technologies, Ferrous Metals, High Performance Alloys, -����������!������!������������������/5��������%������������/�������������� ������������� !�������� ��������� !�������� #���� !�������� %�����!��������#������� 7�������8�������������9�����!�������� ���������������� ������������������ ������������� �������� �� ������ ���� ���� �������� ������� ���

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  • ��� ���� ����� ������ �� ��� ������� ��� ��� �������� ������� ���� ����� ��������������������� ��� ���������� ���� ����� ���� ���� ������ ��������� �� ��� ���������������������������������������������������������������������������������������������������������������������������������������������������������� ���

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    xii

  • EditorsJiann-Yang (Jim) Hwang is a Professor in the Department of Materials Science and Engineering ��� ������� ����

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    ���� ����as a Guest Professor, including the Central South ���������'� ���������� �� ������� ��� ����

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    ���������������� ��0143�������� ���������� ����-��������� ���� ���������������������5�����������011%���%&00���������#������������#��������0146������research interests include the characterization and processing of materials and their �""����������������#�����������������������������������"����������

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    Chenguang Bai� ��� ���������"�������� ����*�����������'���������� �����������#������������� ��������������� ������� �� ��*�� ���������'�014%'�����������������������������-����������in Metallurgical Engineering there. He has published ��������06&�"�"���'�����#���1&�.�������������������������������������"�����������������������'�

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    xv

  • John Carpenter is a technical staff member in the ��������������������������������������

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    ����%����0��������3�%���������#=�������on Green Energy and Sustainability for Arid Region and Mediterranean Countries �������'���+�>����+�$�-������7617�+�03#?#���66@��

    Bowen Li is a Research Associate Professor in the Department of Materials Science and Engineering ��� 0���� �%� ��������� *��������� �� ��������������������� B�-������� F��� ��������� �������include materials characterization, metals extraction, �������� ���������+� ������������ �����-��+� ����������� ����������� � F�� ���� �-��� H6� ���������+����7��������I�"��K�������-�����*��L������������������������*��������%����3����B�-�������%�?����������I��.��� ��7@@H+������*��L��������� ��Materials Science and Engineering from Michigan ������������� B�-������ �� �66H�� F�� ���� ���� �������������������669+�������-�����������������Materials Characterization Committee and Powder Materials Committee.

    xvii

  • Sergio Neves Monteiro graduated as a metallurgical �������������

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    Dr. Monteiro is now a professor in the materials science department of the Military 1�����)������5����������&�1�5&������������������������/)(�������������&:::������������� 3�)������ ���������������/����������� ��������(������������'���� �������� �'�����including the ASM Fellowship. Dr. Monteiro is presently a top researcher (1A) of the +��,������.�)���������!������>������?�������������$�����/�����.8#@�&�#������������the Superior Council of the State of Rio de Janeiro Research Foundation (FAPERJ), ����)������������������+��,�������G$���������&��������(��������������������(�����of three international journals.

    Zhiwei Peng is a Research Assistant Professor in the Department of Materials Science and Engineering at ���������?������������� ������������ ��� ��������� ����+�5��������!��������������.�������!�)�����������������%::*�����%::2&����/��������&���������#��$���������in Materials Science and Engineering from Michigan ?������������� ����������� ��� %:�%�� ���� ������������������� ����)�������� ��������� �������'�����������&������������ ����������,������ ��� ��������&� ���0�������

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    xviii

  • ���������������������������������

    ������������������������������������Finishing Fellowship and Dean’s Award for Outstanding Scholarship from Michigan ������������� !�������"� �� #$�#%� &�� ��� �� '�'���� �(� ���� ��������� ������� ������������������"�)���*������������+��������������"�)�+�*��,���������(����������������������������������),���*���'������������"�(����������)���*�������������(���,��������������������"�)�,��*������'������-���'���������"�)�-���*%

    Mingming Zhang is currently working at ��������������������+�����������-��������,����%���%�.��������������$�"������(�������������/��������� ����0�����(�'������/����������'������������� ���materials engineering. He obtained his Ph.D. degree ������������������������� (��'� ����!�������"��(�Alabama and his Master degree in mineral processing (��'� ������ +�������� ,�������� (��� 2�3(�������Metals in China. He has conducted a number of ��������� /��4����� �������� '������ ���0��������thermodynamics and kinetics of metallurgical reactions, electrochemical processing of light '������� ����"� �(0����� ��� �����'����� �������technologies. Upon graduation with a Ph.D. degree he joined Nucor Steel Tuscaloosa and was assigned to the melting shop technical departments. He managed a number of /��������'/����'�������/������/��4�������'����������������/������%�

    &������/��������������#$����������/�/���������������������/�����(����6,78�/�����������!���/����%���%�.�����������������������������9�"���������(������'�����(� /����������� /���3�������� 4������%� ������ ������� Metallurgical Transactions B, Journal of Phase Equilibria and Diffusion, Mineral Processing and Extractive Metallurgy, and ASME Journal of Thermal Science and Engineering Applications. Dr. Zhang has made more than 10 research presentations at international conferences �� -���� ��� ���� !����� ������%� &�� ���� ���� ������� ��� �� �'���� �(� �������������(��������''�������������������'�9��/����������������������������9�"��������%���������(��������������#$���,�������������(���������������������������-�(������)���-*��#$�$�,����������&��������(���-�(������),&�-*��#$$K��� ����Annual Meeting & Exhibition, San Antonio, TX, 2006.

    xix

  • Characterization of Ferrous Metals

    Session Chairs:Donato FirraoAnchao Ren

    Characterization of Minerals, Metals, and Materials 2013

  • APPLICATION OF THERMOELECTRIC POWER TECHNIQUE TO STUDY THE STATIC STRAIN AGEING OF HEAVILY COLD DRAWN

    STEEL

    Aude Lamontagne1, Xavier Kleber1, Véronique Massardier1, Daniele Mari2

    1Université de Lyon – INSA de Lyon, MATEIS, Bât. St Exupéry, 25 avenue Jean Capelle, 69621 Villeurbanne, France

    2Ecole Polytechnique Fédérale de Lausanne, Institute of Condensed Matter Physics, Station 3, CH-1015 Lausanne, Switzerland

    [email protected]

    Keywords: Pearlite, Wire drawing, TEP, Cementite dissolution, Static strain ageing, , Carbides precipitation

    AbstractThe thermoelectric power (TEP) technique was used to determine with high accuracy the strain ageing kinetics in heavily cold drawn pearlitic steel. Because of the very high sensitivity of the TEP to solute atoms, this technique allowed the strain ageing to be followed from the very first moments. The kinetics were followed during isothermal ageings performed between 20°C and 200°C for different strains. In order to avoid any ageing at room temperature, the samples were kept at -80°C immediately after cold drawing. TEP evolution versus strain highlights cementite decomposition occurring during cold drawing. During the ageing, a redistribution of the dissolved carbon atoms in ferrite occurred. The TEP increase with the ageing time was attributed to the departure of carbon atoms from ferrite (segregation to dislocations and/or carbide precipitation). The kinetics were analysed using the Johnson-Mehl-Avrami-Kolmogorov approach which enabled to determine activation energies associated with carbon atoms redistribution.

    Introduction

    Heavily cold drawn pearlitic steel wires are commonly used as structural materials for theirhigh strength and their acceptable ductility. However, several previous studies highlight the microstructural destabilization of pearlite mainly due to cementite decomposition during the drawing process, which induces changes of mechanical properties [1, 2]. This phenomenon was detected by several experimental techniques such as Mössbauer spectroscopy [3, 4, 5],themomagnetic analyses [6, 7], TEM [8, 9, 10] or atom probe tomography [9, 10, 11]. Nevertheless, the mechanism of cementite decomposition is still unclear. Several hypotheses were proposed in the literature. The first hypothesis relies on a strong interaction energy between carbon atoms and dislocations involving higher binding energy than that betweencarbon atoms and iron atoms in cementite [3]. The second hypothesis is the increase of the free energy of the interface between cementite and ferrite due to the fragmentation of cementite during deformation (Gibbs-Thomson effect) [8]. Some authors even suggest that the dissolution of cementite occur during a post-deformation ageing [12, 13]. It is worth

    3

    Characterization of Minerals, Metals, and Materials 2013Edited by: Jiann-Yang Hwang, Chengguang Bai, John Carpenter, Shadia J Ikhmayies,

    Bowen Li, Sergio Neves Monteiro, Zhiwei Peng, and Mingming ZhangTMS (The Minerals, Metals & Materials Society), 2013

  • noticing that the disagreement between studies can be due to differences in the thermomechanical history of samples (ie. average reduction area per step, drawing speed, storage conditions after drawing…). These points could have an important influence on cementite dissolution and consequently on post-drawing ageing. Indeed, cementite dissolution could be the reason for the post-drawing ageing: destabilized microstructure tends to get back to a more stable state. This ageing has been highlighted by numerous authors [14, 15, 16] but, like the cementite dissolution mechanisms, ageing mechanisms are uncertain. Nevertheless, all authors agree on the fact that the movement of carbon atoms should be responsible for such a phenomenon. It is therefore essential to use a mean for fine and precise microstructural characterization. Due to its high sensitivity to atoms in solid solution, ThermoElectric Power measurements (TEP) technique is relevant to analyze the early stages of ageing. The aim of the study presented in this paper is to follow by thermoelectric power measurements the microstructural evolution after varying ageing times and temperatures of several wires presenting different strain levels in order to highlight and define the ageing mechanisms of pearlitic steels.

    Experimental Procedure

    Material

    The material used in this study is a pearlitic wire of 1.75 mm in diameter. Its composition is given in Table 1. The wire was cold-drawn up to 0.21 mm in diameter corresponding to a true ������������������he true strain is defined as ln(di2/df2), where di and df are the initial and final diameters of the wire, respectively. The average reduction of section area per step was 17.5%. As-drawn samples were taken every two dies and immediately immersed in liquid nitrogen. Then, they were kept at -80°C in order to prevent any uncontrolled ageing at room temperature before measurement.

    Table I. Composition (wt%) of the steel used in this studyC Mn Si Ni Cu Cr P S Al Mo N

    0.91 0.32 0.22

  • dislocation density also leads to a decrease of TEP decrease. Lastly, the precipitates are considered to have no important effect on the TEP, unless they are small and coherent (��ppnearly equal to 0).

    Figure 1. TEP measurement principle

    Experimental Protocol

    TEP measurements were performed at 20°C on each as-drawn sample in order to assess the initial TEP values, S(t0). Then, samples were isothermally aged for different times t at different temperatures T (with 20°C ���T ������������������������������������T, the TEP value, S(T, t), of each heat-treated sample was measured at room temperature. Thus, the TEP variation induced by the ageing at T,, �Sa=S(T, t) - S(t0), could be assessed and for each strain, it was possible to plot the TEP kinetics obtained at different ageing temperatures.

    Experimental Results

    Figure 2 shows the TEP evolution of as-drawn wires as a function of strain. TEP values ������������������������������������ �!��"������deformation, TEP values quickly fall. This evolution highlights two phenomena of microstructural evolution during cold-drawing.

    Figure 2. TEP evolution of as-drawn wires during the cold-drawing process.

    Figure 3 shows the different static ageing kinetics at temperature between 20°C and 200°C for two different true strains. As it can be seen, TEP values increase from the very beginning of the ageing treatment even at 20°C. This increase is even more significant for highly

    5

  • deformed samples. These results highlight the microstructural evolution of cold-drawn wires during static ageing and the influence of the amount of previous plastic deformation on this phenomenon.

    �������������������������������������������������������������3.05; b) ������

    Discussion

    The TEP evolution of as-drawn wires as a function of the deformation (figure 2) showed two stages of microstructural change during cold-drawing. For low strain ������� �, TEP increase can be explained by both the segregation of carbon atoms initially present in the ferritic phase of the steel [19] and the lamellar orientation induced by the deformation process [20]. Then, the increase in the deformation leads to a TEP decrease, which can be explained by two phenomena: the increase in the dislocation density and the increase in the amount of carbon atoms in solid solution. It is noteworthy that the first hypothesis alone cannot justify such a significant drop of TEP. Thus, a carbon enrichment of the ferrite should occur, induced by the cementite dissolution during heavy deformation of pearlitic steel as mentioned by several authors [3, 4, 6, 8, 10]. However, the mechanism of cementite decomposition is still a controversial subject. Gridnev et al. proposed an interpretation of this dissolution based on the interaction between carbon atoms and dislocations [3]. According to these authors, the driving force for the cementite dissolution may be the fact that the carbon-dislocation interaction energy exceeds the binding energy between carbon and iron atoms in cementite. This interpretation has been more recently used by others authors in order to explain the inhomogeneous distribution of carbon atoms after cementite dissolution observed by atom probe tomography as well as the saturation of the cementite decomposition for high strain level [11]. Nevertheless, present study contradicts this explanation: if carbon atoms from cementite were directly trapped by dislocations, no TEP variation should be observed (TEP is only sensitive to variations of the carbon content in solid solution). Moreover, no saturation of the phenomenon can be seen according to the TEP variation of as-drawn wires during deformation (Figure 2). These results are consistent with the theory of Languillaume et al. [8], which relies on thermodynamic destabilization of cementite during drawing due to the increase in the free energy of the cementite phase in the course of the thinning of cementite lamellae. Unstable cementite could dissolve into a supersaturated solid solution of carbon in ferrite.

    6

  • However, these results are in contradiction with the study of Takahashi et al. [13] which suggests that the cementite dissolution occurs during ageing treatment and not during drawing. It is worth noting that these discrepancies could be due to a difference in the initial state of wires. In fact, according to Figure 3, samples evolve quickly during ageing treatment even at 20°C (in just few hours). So, depending on the time between drawing and characterization of the sample and the temperature of storage, the results could be really different. In this study, samples of as-drawn wires were plunged in liquid nitrogen directly after drawing and kept at -80°C in order to avoid any uncontrolled ageing before measurements. The quick increase of TEP during ageing treatments can be explained by the restoration of the phase equilibrium following the cementite dissolution. It can be attributed to a departure of carbon atoms from the supersatured solid solution, since an increase of carbon atoms in solid solution lead to a decrease of TEP. One can observe that changing the ageing temperature shifts the timescale of the microstructural evolution associated with TEP variations. Therefore, a temperature-time equivalence has been performed, according to an Arrhenius law (activation energy Q), to find the “equivalent time at 20°C” (t20°C

    t20°C= tT exp �-QR

    �1T

    - 1T20°C

    �� (1)

    ) for all ageing treatments performed at temperature T:

    However, the microstructural evolution taking place within the samples could involve more than a single mechanism of ageing and therefore an activation energy per mechanism should be applied. Here, two activation energies have been used to build a unique TEP curve for the whole range of investigated ageing temperatures. Figures 4a and 4b show these curves at 20°C for ��������������������The activation energies used for each sample are reported in Table 2. The “low” temperature activation energies appear to be close to that for segregation of carbon atoms on dislocations in ferrite [21] and the “high” temperature activation energies seem to be close to that for precipitation of epsilon carbides in iron-carbon martensite [22]despite crystallographic difference between martensite crystal lattice and the supersatured ferrite crystal lattice of the study. Therefore, it appears that two mechanisms of redistribution of carbon atoms could occur during ageing depending on temperature and/or time treatment. After having determined the activation energies of the two phenomena, a Johnson-Mehl-Avrami-Kolmogorov approach was used to model the TEP master curves at 20°C shown in Figures 4a and 4b: it gives the evolution of the amount of carbon atoms in solid solution as a function of time t with two parameters k and n that describe the kinetics of the reaction:

    P(t)=Pmax���-(kt)n� (2)

    where P(t) is the evolution of TEP corresponding to the amount of carbon atoms in solid solution as a function of time, Pmax

    k= k0exp �-QRT

    � (3)

    is the value of TEP corresponding to the minimum amount of carbon atoms in solid solution, n is the Avrami coefficient and k is the rate constant given by:

    7

  • where k0

    As two mechanisms succeed during ageing of cold-drawn pearlite wires, an expression corresponding to the sum of two JMAK laws was used to fit the master curves at 20°C. The values of the Avrami coefficients have been fixed based on the values found in literature for both the mechanisms cited above. Therefore, for the “low” temperature ageing mechanism that could be attributed to segregation of carbon atoms on dislocations, the Avrami coefficient is fixed at n

    is a constant, Q is the activation energy of the process, R is the universal gas constant and T is the absolute temperature.

    1 = 2/3 [21, 23] whereas for the “high” temperature ageing mechanism that could be attributed to precipitation of epsilon carbides, the Avrami coefficient is fixed at n2 = 1/3 [24]. The parameters used to model TEP variation are reported Table 2.

    Table 2. Parameters used to obtain master curves at 20°C and to model it by a JMAK-type equation . The first mechanism refers to “low” temperature ageing mechanism and the second

    one refers to the “high” temperature ageing mechanism. True Strain

    �1st 2mechanism nd mechanism

    Q1 n k1 Q1 n2 k2 23.05 87 2/3 1.76x10 100-3 1/3 1.52x10-6

    3.81 85 1.36x10 110-3 1.51x10-7

    As can be seen in Figures 4a and 4b, the fit curves of the TEP evolutions at 20°C are quite good. However, they differ from the master curves for long ageing times at 20°C. It could exist a third mechanism of ageing for a longer time of treatment or a higher ageing temperature. This last stage of ageing could be epsilon carbides transformation into more stable carbides like cementite. Finally, it is worth noticing (Figure 4) that the amplitude of TEP variation is larger for highly deformed sample. This observation is consistent with the theory of cementite dissolution during cold-drawing. Increasing the strain level of the wires enhances the cementite dissolution phenomenon. Indeed, more carbon atoms are dissolved in supersatured ferrite and static ageing is amplified.

    Figure 4. TEP evolutions during ageing at various temperatures ranging from 20°C to 200°C as a function of the “equivalent time at 20°C”.

    8