Characterization of Minerals, Metals, and Materials 2014

Cover Photographs: Back-scattered electron image of a copper sulfide ore particle. Further details can be found in "Characterization of Particle Damage and Surface Exposure of a Copper Ore Processed by Jaw Crusher, HPGR and Electro-dynamic Fragmentation" by O. da F. M. Gomes, D. M. de Oliveira, L. G. S. Sobral, and E. Pirard

New proceedings volumes from the TMS2014 Annual Meeting, available from publisher John Wiley & Sons:

www.wiley.com

www.tms.org

Proceedings of a symposium sponsored bythe Materials Characterization Committee of

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

Held during

Characterization of Minerals, Metals, and Materials 2014

Edited by

John S. CarpenterChenguang Bai

Jiann-Yang HwangShadia Ikhmayies

Bowen LiSergio Neves Monteiro

Zhiwei PengMingming Zhang

February 16-20, 2014San Diego Convention Center

San Diego, California, USA

Copyright © 2014 by The Minerals, Metals & Materials Society. All rights reserved.

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10 9 8 7 6 5 4 3 2 1

v

TABLE OF CONTENTSCharacterization of Minerals, Metals, and

Materials 2014

Preface .............................................................................................................. xiii About the Editors................................................................................................xv

Characterization of Ceramics and Clays

FTIR and Raman Spectroscopic Investigation on the Structure of CaO-SiO2-TiO2 Ternary Slags.......................................................................... 3 L. Wang, L. Wen, J. Tu, S. Zhang, and C. Bai

Characterization of Heavy Clay Ceramic Mixed with Red Mud Waste .............11 C. Vieira, M. Babisk, U. da Silva Prado, and S. Monteiro

High-temperature Exposure of Oil Well Cements ..............................................17 B. Iverson, B. Waugh, and J. Maxson

Determination of Temperature and Time Calcination of Clays for Production of Metakaolin Based on Pozzolanic Activity ...................................25 J. Alexandre, G. Xavier, A. Azevedo, S. Monteiro, and C. Vieira

PBT/Brazilian Clay Nanocomposites Prepared by Melt Intercalation: Effects of Organophilic Clay Content and Ionizing Radiation Treatment ..........33 M. Sartori, M. Ferreira, F. Díaz, V. Rangari, S. Jeelani, and E. Moura

Modification of Si3N4-SiC Heat Absorption Ceramic Material Using for Tower Type Solar Thermal Power Plant.......................................................45 M. Liu, X. Xu, J. Wu, G. Xu, G. Xue, and J. Liu

Microstructural and Electrical Properties of 0.5 mol% Al2O3–0.1 mol%B2O3–doped ZnO Ceramics ................................................................................55 B. Yüksel and G. Hardal

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vi

Characterization of Composites

A Kinetic Analysis of a Thermal Curing Reaction of a Silicon Resin in SolidState ....................................................................................................................65 F. Vivier, D. Santamaria, D. Pellerej, P. Buonfico, and M. Sangermano

Halogen Free Flame Retardant for ABS Composite with Oxide Nanoparticles ......................................................................................................73 P. Martins, T. Valera, J. Bartoli, and J. Tenório

Investigation on the Thermal Conductivity of Resin Composite Materials ........81 K. Monden

Polypropylene Nanocomposites Reinforced with Organophilic Clay andBrazilian Nut Fibers............................................................................................89 L. da Rocha-Gomes, D. Fermino, E. Moura, M. Valenzuela, and F. Valenzuela-Diaz

Interfacial Evolution of Al/Cu Laminated Composite Produced by Asymmetrical Roll Bonding and Annealing..................................................97 X. Li, G. Zu, and P. Wang

Characterization of Environmental Materials

Subsurface De-alloying during SCW Exposure................................................105 J. Li, Y. Zeng, O. Woo, W. Zheng, P. Liu, and C. Bibby

Characterization of Clay Brick Incorporated with Ash from the Incineration of Urban Garbage .............................................................................................113 N. Coutinho, S. Monteiro, and C. Vieira

Concrete of Steel Slag Composite for Paved Road and Its HydrationMicrostructure...................................................................................................121 H. Fang, J. Hwang, G. Xue, L. Lu, and Y. Liu

Method for Removal of Mercury from Oil Field Brine with Calcium Carbonate Co-precipitation...............................................................................131 F. Fazlollahi, M. Zarei, M. Habashi, and L. Baxter

Optical Parameters of Thermally Evaporated CdTe Thin Films.......................139 S. Ikhmayies

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vii

Obtaining the Polystyrene-bentonite Nanocomposite as a Method forPolystyrene Recycling ......................................................................................147 M. Machado, H. Wiebeck, F. Valenzuela-Diaz, M. Valenzuela, and V. Justo

Modified Hydrotalcites as Desulfurization Adsorbents: Preparation,Characterization, and Performance Test ...........................................................157 A. Gomes, M. Mozumder, D. Cocke, T. Benson, H. McWhinney, and T. Grady

Thermal Analysis and Characterization of Elephant Grass Ash (Pennisetum Purupureums Shaum) Incorporated into Clay Matrix ..................165 R. Faria Jr., A. Silva, R. Toledo, S. Monteiro, and C. Vieira

Characterization of High-arsenic Sludge in Copper Metallurgy Plant..............173 X. Zhu, X. Qi, H. Wang, Y. Shi, T. Liao, Y. Li, C. Liu, and X. Wang

Characterization of Ferrous Metals

In-Situ EBSD Investigation of Carbides during Annealing of AISI M42 Steel..........................................................................................................187 M. Godec, B. Bati , and T. Pirtovšek

Effects of Heat Treatment on Transverse and Longitudinal MechanicalProperties of Engineering Machinery Steel WQ960.........................................191 S. Tao, F. Wang, G. Sun, C. Li, and Q. Yan

Ultrasonic Non-Destructive Characterization of Power Plant Steel .................199 M. El Rayes, E. El-Danaf, and A. Almajid

Study on Modification of Anti-oxidation Coating for Steel Billet....................209 H. Chen, H. Gu, K. Lei, X. Chen, M. He, and G. Xue

Method Development in Characterization

Experimental Estimation of J Integral from Load-front Face DisplacementRecord for Compact Tension Specimens..........................................................219 K. Shi, L. Cai, Y. Hu, and D. Salmon

Structure Characterization of Sn-based and Ce-based Alloys Treated byUltrafast Scanning ............................................................................................227 B. Zhao, L. Li, Q. Zhai, and Y. Gao

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x

Anisotropic Finite Element Modeling of the Fused Deposition Modeling Process..............................................................................................235 S. Ogden and S. Kessler

Characterization of Material Processing

Characterization of Particle Damage and Surface Exposure of a Copper OreProcessed by Jaw Crusher, HPGR and Electro-dynamic Fragmentation..........247 O. Gomes, D. de Oliveira, L. Sobral, and E. Pirard

Effect of Friction Stir Welding Speed and Post Weld Heat Treatment on theMicrostructure and Hardness of AA7020 .........................................................253 M. Ahmed, E. Ahmed, and A. Mahdy

Study on Reactivity between Mould Fluxes and High-Al Molten Steel ...........265 T. Wu, S. He, Y. Guo, and Q. Wang

Grinding Kinetics of Vanadium-titanium Magnetite Concentrate in a Ball Mill.....................................................................................................271 R. Zhang, X. Lv, C. Ji, and X. Zheng

Arc Welding of Advanced High Strength Steels for Car-body Components....277 P. Spena, F. D'Aiuto, P. Matteis, and G. Scavino

Forging Hot and Cold: Development through the Ages ...................................285 H. McQueen and E. Evangelista

Load Carrying Capacity and Microstructure of Resistance Spot Welded Dual-phase (DP600) Steel ................................................................................297 S. Ataya

Optimization on Refining Slag and Tapping Deoxidation System for CarbonStructure Steel without Calcium Treatment......................................................305 S. Zhao, Q. Wang, G. Chen, S. He, and M. Peng

Characterization in Material Extraction

Effects of Iron and Manganese Ions on Potentiostatic Current Transients forCopper Electrodeposition .................................................................................315 A. Chen, J. Hwang, Z. Peng, Y. Ma, X. Liu, and X. Chen

viii

xi

Determination of Leaching Reaction Mechanism of Synthetic CaMoO4 inH2C2O4 Solutions..............................................................................................325 S. Ilhan, A. Kalpakli, and I. Yusufoglu

Effect of V2O3 and TiO2 on the Dissolution of Lime in FeO-SiO2-V2O3-TiO2 Slag................................................................................335 R. Tang, Y. Wang, S. Wang, B. Xie, and J. Diao

Characterization of Wastes Generated during Stainless Steel Production ........343 X. Liu, J. Zhang, Q. Xiao, and Q. Li

Investigation of Reaction Stoichiometry of Leaching of Synthetic CaWO4 in H2C2O4 Solutions..........................................................................................351 A. Kalpakli, S. Ilhan, and I. Yusufoglu

Study on Extraction of Titanium from Titanium-bearing Blast Furnace Slags....................................................................................................361 Q. Xiao, J. Zhang, Y. Feng, and Q. Li

Characterization of Minerals

Microwave Permittivity, Permeability, and Penetration Depth of Pyrite..........371 Z. Peng, J. Hwang, B. Kim, J. Kim, and X. Wang

Characterization of Waste from Ornamental Stones for Use in Mortar............379 A. Azevedo, J. Alexandre, G. Xavier, S. Monteiro, and C. Vieira

Titanomagnetite Properties and Microstructures ..............................................387 X. Liu, W. Schoenthal, T. Cox, A. Wise, D. Laughlin, and M. McHenry

Characterization of Clays Using for Formulations of Detergents.....................395 M. da Silva-Valenzuela, F. de Souza Carvalho, and F. Valenzuela-Díaz

Differential Characterization of Ikperejere Iron Shale and Iron Sandstone ......401 O. Martin, O. Gerald, O. Kelechi, and B. Li

A New Process of Fluosilicic Acid Leaching for Recovering Bismuth fromMaterials Containing Bismuth Oxide ...............................................................413 C. Zhang, X. Zhang, and J. Zhan

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xii

Fundamental Research on the Characteristics of Sierra Leone Iron Ore for Sintering......................................................................................................425 J. Dong, G. Wang, M. Zuo, H. Li, and Q. Xue

Characterization of Soft Materials I

Flexural Mechanical Characterization of Polyester Composites Reinforced with Continuous Banana Fibers ........................................................................435 F. de Assis, F. Margem, R. Loiola, and S. Monteiro

Thermal Characterization of Epoxy Matrix Reinforced with Buriti Fibers by the Photoacoustic Technique .......................................................................441 G. Altoé, F. Margem, S. Monteiro, R. Faria Jr., and T. Cordeiro

Characterization of Thermal Properties of Polyester Matrix Reinforced with Sisal Fibers by Photoacoustic Technique .................................................449 A. Pereira, F. Margem, S. Monteiro, R. Faria Jr., and T. Cordeiro

Characterization of Thermal Properties of Curaua Fibers Incorporated in Epoxy Matrix by Photothermal and Photoacoustic Techniques ...................457 N. Simonassi, F. Margem, S. Monteiro, R. Faria Jr., and T. Cordeiro

Bending Tests in Polyester Composites Reinforced with Bamboo Fibers of the Specimen Dendrocalmus Giganteus .......................................................465 L. Martins, F. Margem, S. Monteiro, R. Loyola, and J. Margem

Characterization of Soft Materials II

Comparison between Bio-composite Based on Green HDPE/Brazil Nut Shell Fiber (BNSF) Treated and Non Treated by Electron-beam Radiation.....475 R. Campos, M. Hosur, S. Jeelani, F. Díaz, E. Moura, and E. Seo

Dynamic-mechanical Behaviour of Epoxy Composites Reinforced with Jute Fiber ..................................................................................................483 I. da Silva, A. Bevitori, C. de Oliveira, F. Margem, and S. Monteiro

Investigation on Mechanical and Morphological Behaviours ofCopolyester/Starch Blend Reinforced with Rice Husk Ash .............................491 E. de Oliveira, V. Silva, R. Oliveira, A. Teran, A. Castillo, J. Harada, F. Diaz, and E. Moura

Charpy Toughness Behavior of Continuous Banana Fiber Reinforced Epoxy Matrix Composites ................................................................................499 F. Assis, S. Monteiro, F. Margem, and R. Loiola

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xi

Thermal Photoacoustic Characterization of Polyester Composites Reinforced Ramie Fibers ..................................................................................507 C. de Oliveira, A. Bevitori, I. da Silva, F. Margem, G. Altoé, R. Faria Jr., T. Cordeiro, and S. Monteiro

Weibull Analysis of the Density of Ramie Fibers with Different Diameters ...515 A. Bevitori, I. da Silva, C. de Oliveira, F. Margem, and S. Monteiro

Poster Session

Brazilian Bentonite Submitted to Mild Acid Treatment ...................................525 C. Andrade, V. Justo, F. Mondelo, M. Valenzuela, C. Volzone, and F. Valenzuela-Diaz

Characterization of Different Clays for the Manufacture of Artifacts Ceramic Red .....................................................................................................533 J. Alexandre, A. Azevedo, E. Zanelato, G. Xavier, S. Monteiro, and C. Vieira

Characterization of Laterite Nickel Ore............................................................541 T. Li, X. Chen, B. Zhang, and X. Hong

Characterization of Sisal Fibers Thermal Properties by Photoacoustic Technique .........................................................................................................549 A. Pereira, F. Margem, S. Monteiro, R. Faria Jr., and T. Cordeiro

Friction Stir Welding of Polycarbonate Sheets.................................................555 M. Shazly, M. Ahmed, and M. El-Raey

In-Situ High Temperature X-ray Analysis of a Supermartensitic Stainless Steel ...................................................................................................565 T. dos Santos, A. Rocha, R. de Carvalho, and V. Buono

Izod Impact Resistance of Jute Fiber Reinforced Polyester Matrix ..................573 I. da Silva, A. Bevitori, C. de Oliveira, F. Margem, and S. Monteiro

Izod Impact Tests of Polyester Composites Reinforced with Bamboo Fibers of the Specimen Dendrocalmus Giganteus .......................................................581 L. Martins, F. Margem, S. Monteiro, R. Loyola, and J. Margem

Obtaining Nanocapsules from PHBEG/MMT Composite................................589 M. da Silva-Valenzuela, C. Matos, I. Sayeg, A. Moreira, H. Wiebeck, F. Valenzuela-Díaz, and W. Hui

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Photoacoustic Characterization of Polyester Matrix Reinforced with CurauaFibers ................................................................................................................595 N. Simonassi, F. Margem, S. Monteiro, R. Faria Jr., and T. Cordeiro

Photoacoustic Thermal Characterization of Buriti Fibers................................. 603 G. Altoé, F. Margem, S. Monteiro, R. Faria Jr., and T. Cordeiro

Preparation and Characterization of Polypropylene Nanocomposites with Organoclay and Discarded Bond ..............................................................611 D. Fermino, M. Valenzuela, E. Moura, D. Parra, and F. Diaz

Research on Preparation and Properties of Inorganic Gelling Materials for Sand Fixation ..............................................................................................619 M. He, J. Li, G. Xue, and F. Hao

Synthesis and Characterization of Ammonium Jarosite with Arsenic ..............627 F. Patiño, M. Flores, I. Reyes, J. Méndez, M. Reyes, I. Mireles, and J. Hernández

The Grain Growth Kinetics of 0.5 mol% B2O3-1 mol% TiO2-doped ZnOCeramics ...........................................................................................................637 G. Hardal and B. Yüksel

Thermal Decomposition Reaction Mechanisms and Kinetics of AmmoniumParatungstate Tetrahydrate ...............................................................................645 A. Eser, C. Kahruman, and I. Yusufoglu

Author Index.....................................................................................................655

xii

Subject Index ....................................................................................................659

PREFACEThe relationships between processing, microstructure, and properties form the basis

the use of characterization across the entire life cycle of materials, from extraction to

to cover characterization across the spectrum of science and engineering consistent

The Materials Characterization Committee of TMS sponsors a symposium on Characterization of Minerals, Metals, and Materials as a major event during the TMS

Metals, and Materials symposium at TMS is not only one of the largest and most broad

Focused sections within this book will include those centered on ferrous metals, non-

sections will focus exclusively on characterization concerns in the extraction,

soft materials), the editors encourage readers to view the entire book as potentially

grateful to the publishers, TMS and John Wiley & Sons, for their help in producing

TMS for providing the Materials Characterization Committee with the opportunity to

xiii

publish a stand-alone volume, which illustrates the importance and interest level in

and chairs of the committee for their desire to serve the greater materials science

Chenguang BaiJiann-Yang Hwang

Bowen LiSergio Neves MonteiroZhiwei PengMingming Zhang

xiv

EDITORSJohn S. Carpenter is a technical staff member in

-

after performing his undergraduate studies at Vir--

acterization, processing, and mechanical testing of metallic composites fabricated via severe plastic

Currently, his work focuses on understanding the relationship between plastic strain, texture, and the mechanical properties of bimetallic nanocom-posites fabricated via accumulative roll bonding and joined using friction stir

Mechanical testing for this work includes methods such as micropillar compres-

-mittee of TMS and is a participating member of the Mechanical Behavior of Materials, Nanomechanical Behavior, and the Advanced Characterization, Test-

Metallurgical and Materials Transactions A and has co-edited special sections in JOM related to neutron characterization and coherent x-ray diffraction imaging

-

xv

Chenguang Bai of Metallurgical Engineering, School of Materials

Metals, and Member of the Advisory Committee of -

-

-

Jiann-Yang (Jim) Hwang -partment of Materials Science and Engineering at

Chief Energy and Environment Advisor of the Wu-

the Editor-in-Chief of the Journal of Minerals and Materials Characterization and Engineering since

---

-

materials and their applications, and he has been actively involved in the areas of separation technologies, pyrometallurgy, microwaves, hydrogen storages, ceram-ics, recycling, water treatment, environmental protection, biomaterials, and en-

xvi

-tion Committee and the Pyrometallurgy Committee in TMS and has organized

Shadia Ikhmayies -

-

-

-search is focused on producing and characterizing

characterizing different compounds by computa-

--

Physics Express for Simplex Academic Publishers and is now an associate editor of the Journal of Physical and Environmental Science ResearchShe is a member of the editorial board of the International Journal of Materials and Chemistry -view book project titled Advances in the II-VI Compounds Suitable for Solar Cell Applications

JOM as a represen-

xvii

Bowen Li is a research associate professor in the

-clude materials characterization, metals extraction, ceramic processing, antimicrobial additives, and

-

Science and Engineering from Michigan Techno-

Sergio Neves Monteiro graduated as metallurgical

-lowed by a course in Energy at the Brazilian War

--

professor of post-graduation program in engineer-

---

xviii

Zhiwei Peng is a research assistant professor in the

-

and Engineering from Michigan Technological

such as Metallurgical and Materials Transactions A, JOM, Energy & Fuels, Applied Physics Express, Ceramics International, IEEE Transactions on Instrumentation and Measurement, IEEE Transactions on Mag-netics, and ISIJ International -crowave heating, dielectric characterization of materials, non-thermal microwave effects, ferrous metallurgy, computational electromagnetics, and microwave ab-

JOM and has been on the editorial board of the Journal of Minerals and Materials Characterization and Engineer-ing -

-

-

Mingming Zhang is currently working at Arcelor-

-

number of research projects involving mineral ben--

lurgical reactions, electrochemical processing of

xix

managed a number of process improvement and upgrade projects on melting and

reviewer for a number of prestigious peer-reviewed journals, including Metallur-gical and Materials Transactions B, Journal of Phase Equilibria and Diffusion, Mineral Processing and Extractive Metallurgy, and Journal of Thermal Sciand Engineering Applications

been invited to a number of international conference committee gatherings to

-

xx

Characterization of Ceramics and Clays

Session Chairs:Benjamin Iverson

Takashi Nagai

Characterization of Minerals, Metals, and Materials 2014

FTIR and Raman Spectroscopic Investigation on the Structure ofCaO-SiO2-TiO2 Ternary Slags

WANG Long, WEN Liang-ying, TU Jia-jia , ZHANG Sheng-fu, BAI Cheng-guang

College of Materials Science and Engineering, Chongqing University, Chongqing China, 400030

Keywords: TiO2, Structure, Slag, Raman, FTIR

Abstract

The structures of CaO-SiO2-TiO2 slags with CaO/SiO2=1.1 were investigated by FTIR and Raman. Gaussian deconvolutions of the FTIR and Raman spectroscopic curves indicated the variation of the structural units inthe slags. The deconvoluted results of the Raman spectra showed that the silicate network was more depolymerized with the increase of TiO2 and octahedral Ti4+ in the slags plays a role of network modifier. The deconvolution of the FTIR spectra revealed the rate of Q3(Si-O tetrahedral with three bridging oxygens) and Q2 (Si-O tetrahedral with two bridging oxygens) decreased while the rate of Q1 (Si-O tetrahedral with onebridging oxygen) and Q0 (Si-O tetrahedral without bridging oxygen) increased when increased TiO2 from 0%to 10%. However, the rates of Q3 Q2 Q1 and Q0 changed little with the increase of TiO2 from 10% to 15%.

Introduction

There is a lot of vanadium-titanium magnetite (VTM) in Panxi region, China, in which the proven reserves is approximately 10 billion tons. The VTM is a very complex ore containing about 30.5% Fe, 10.6% TiO2 and 0.3% V2O5

[1]. In order to extract Fe, the blast furnace (BF) process is traditionally adopted to reduce the VTM, and in the process Ti is concentrated and finally enters into slag. The slag containing about 22-25% TiO2 has a higher melting temperature and higher viscosity compared with those of the conventional BF slag without Ti-bearing[2-

4]. The viscosity of the BF slag is an important parameter which not only affects the smelting process, but also metal/slag reaction kinetics, mass transfer, and the heat transfer[5,6]. Thus, viscosities of various slags have been measured by steelmakers[7-13]. Many researchers have also tried to predict the viscosity by different modeling[5,14-16].

It has been found that the structure of silicate melts is the dominant factor which influences the physicochemical properties of high temperature slag based on the research of the structures of silicate slags using Fourier Transform Infrared (FT-IR) spectroscopy and Raman spectrum.[12,13,17-19] Similarly, structure and properties of slags containing TiO2 have also been investigated in order to understand the relationship between structure and property[4,7-9,16-18,20-22].It’s reported that TiO2 can increase the viscosity of the CaO-SiO2-Al2O3-TiO2 slag under reducing atmosphere indicating that it behaves as a network-former which can increase the polymerization of the network of the slag by Ohno and Ross[3]. However, Saito et al. revealed that TiO2 decreases the viscosity in quaternary CaO-SiO2-Al2O3-TiO2 slag system[9]. Handfield et al. described industrial slags with high TiO2 content are very fluid melts once completely molten[2]. Park et al.[18], Sohn et al. [17] and Liao et al. [7] proposed that TiO2 acts as a basic oxide resulting in the depolymerization of the slags under neutral conditions in CaO-SiO2-MgO-TiO2-Al2O3 quinary slag systems with varying basicity and TiO2 contents although the content of MgO and Al2O3 are different in their systems. Park et al.[18], investigated the effect of TiO2 on the silicate structure in CaO-SiO2-17 mass% Al2O3-10 mass% MgO slags by the FT-IR and Raman spectrum contributing to the conclusion that TiO2 act as a basic oxide.

3

Characterization of Minerals, Metals, and Materials 2014Edited by: John S. Carpenter, Chenguang Bai, Jiann-Yang Hwang, Shadia Ikhmayies,

Bowen Li, Sergio Neves Monteiro, Zhiwei Peng, and Mingming ZhangTMS (The Minerals, Metals & Materials Society), 2014

Nevertheless, there is a significant difference between the chemical composition of previous researches and that in the BF slag of actual production. In this work, the in fluence of TiO2 on the structure of calcium-silicate based slags with CaO/SiO2=1.1 would be essential in later studies to maintaining stable blast furnace operations.

Experimental method

The chemical compositions of the samples are displayed in Table 1. The four samples were discussed to reveal the effect of varying TiO2 contents (0-wt% to 15-wt%) on the slags.Analytical grade of lime, silica, and titantium dioxide were used as raw materials and mixed in an agate mortar before melting. Then the mixed raw materials with different formula were put inside a molybdenum crucible and melted in purified Ar atmosphere at 1823-K. The sampleswere preserved at 1823-K for approximately 2-hours to guarantee assure complete fusion and homogenization. After 2-hours, the homogenized slags were drawn from the furnace and quickly quenched by pouring it into a tank filled with cooling water. Subsequently, the slags were confirmed to be amorphous by XRD show in Fig.1. After each vitreous sample as obtained, compositions of all elements in several different portions of the sample were measured by X-ray fluorescence analysis, and no noticeable difference in composition of elements was detected among those portions. The samples were finally tested by a laser confocal Raman spectrometer,Jobin Y’Von U1000 to obtain the corresponding Raman spectra and the corresponding FT-IR spectra.

Table.1. Oxide compositions of experimental samples

NO.Chemical composition wt%

CaO SiO2 TiO2 C/S1# 52.4 47.6 0.0 1.102# 49.8 45.2 5.0 1.103# 47.1 42.9 10.0 1.104# 44.5 40.5 15.0 1.10

Fig.1. XRD curves of the quenched samples

4

Results and Discussion

Raman spectra of the four samples are exhibited in Fig.2. According to Mysen[23], the main envelope curve in the Raman spectra of CaO-MgO-SiO2 was observed between 800 cm-1 and 1150 cm-1. Obviously the bands composing the envelope stemmed from the three-dimensional network of silicate. In the similar ternary slags with high silicate content (more than 50 mol%) studied by Mcmillan[24], the Raman signals were mostly detected in the range of 800 cm-1 and 1200 cm-1 but with the maximum at higher frequency nearly 1050 cm-1. The Raman spectra of present samples also inherit this frequency region. The maximum of the spectral curve moved from 1054 cm-1 to 862 cm-1 which is easy to explain the concentration of SiO2 becomes smaller and the details will be given below.

Fig.2. Raman spectra of the samples

Interpretation of the acquired Raman spectral curves should be combined with the structural features of both Ti-bearing and Ti-free slags to work out all the bands comprising the integrated envelopes. Two assumptions proposed by Mysen et al. [23]were adopted throughout the fitting process. Firstly, every single characteristic peak was restricted to be symmetric and coincide with the Gaussian distribution. Secondly, bands were added and fitted to the envelope only when there were separate peaks or distinguishable shoulders indicating their existence or great deviations between the sum of pre-existing fitted bands and original spectral curve needing to beeliminated by new band. It seems not difficult to deconvolute the Raman curve of 1#(TiO2=0%)with the guidance of several shoulders beside the peak, yet more information about the high-frequency region (800cm-1 to 1200cm-1) related to silicate structure must also be considered. Mcmillan designated this region as the stretching vibration of SiO4

4--tetrahedra and Qn (n ranges from 0 to 4) species were reflected by the bands on the positions of ~850 cm-1, ~900 cm-1, 950–1000 cm-1, 1050–1100 cm-1, and ~1200 cm-1, respectively[24]. Analogous results were obtained at by Mysen et al. [23] with the assignments of monomer (Q0), dimer (Q1), chain (Q2), and sheet

5

(Q3) species from signals at 840–860 cm-1, 900–920 cm-1, 960–980 cm-1, and ~1050 cm-1. You et al. [25] verified the bands representing Q1, Q2, and Q3 at ~920 cm-1, 990 cm-1, and 1060 cm-1,respectively.

On the basis of the above discussion and other previous works[26,27], the high-frequency region of 1#(TiO2=0%) was deconvoluted into four symmetric bands at 862, 910, 968, and 1043 cm-1

indicating the structural units of tetrahedrally coordinated Si with different NBO/Si (Q0 to Q3)which shows at 863, 924,969,1042 cm-1 in the Raman of 2#(TiO2=5%), as shown in Fig.3.Reynard and Guyot[28] noted that the intense stretching vibrations of Ti octahedra occurs belowabout 650 cm-1 if the octahedra share corners, and above 700 cm-1 only when the octahedralshare edges such as in ilmenite structures. So the bands at 635 cm-1 and 720 cm-1 were assignedto the deformation of O-Ti-O in the Ti-octahedral. When the content of TiO2 increase from 10% to 15% the bands move to the 660 cm-1 and 770 cm-1, respectively. So Ti4+ exits in this slags with 6-coordination which plays the role of network modifier.

Fig.3. Deconvoluted results of the Raman spectra for the samples

The FTIR results of the four samples is shown in Fig .4, respectively, which further support the role of TiO2 as a basic oxide and a network modifier. FTIR spectra of silicate slags are typically focused within the wavenumber region between 1200 and 400cm-1. [29,30,31] This region representsthe symmetric stretching vibration bands of the [SiO4]-tetrahedra, the symmetric stretching vibrations of the [AlO4]-tetrahedra, and the symmetric Si–O bending vibration bands, etc. The vibration band between the wavenumbers of 1200 and 800 cm-1 is the [SiO4]-tetrahedra symmetric stretching vibration band, which are well known to be the convoluted band of the NBO/Si transmission troughs from Q0 to Q3. This characteristic stretching vibration band for thelarge silicate network structures becomes less pronounced and the depth of the convoluted band

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becomes shallower with TiO2 additions. According to Mysen et al.,[23] Qn , n assigned values from 0 to 3 are structurally defined as monomers (880 –850 cm-1), dimers (920–900 cm-1), chains (980–950 cm-1), and sheets (1100–1050 cm-1), respectively. This decrease in the depth of thetransmission trough indicates a depolymerization of the slag structure as suggested in previously published literature.[29,32]

Fig.4. FTIR results of quenched samples

Fig.5. Deconvoluted results of the FTIR spectra for the samples

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The FT-IR spectra can be deconvoluted in the same way of Gaussian deconvolution, as shown in Fig.5. And the concentrations of Qn(n=0,1,2,3) varying with TiO2 content are plotted in Fig.6,where the rate of Q0 and Q1 increase in the cost of a decreasing in Q2 and Q3 with the increase of TiO2 in the range of 0% 10%,and the rate of Q3 Q2 Q1 and Q0 change little with the increase of TiO2 from 10% to 15%. It is further reinforced that significant amounts of Ti4+ get into the silicate network as network modifier.

Fig.6. The rate of the various Si-O tetrahedrons in the slags

The rate (Xn) of Qn structural units also can be applied to deduce the degree of polymerization of silicate network by the following expression:[33]

NBO/Si=4X0+3X1+2X2+X3

The calculated NBO/Si rate is exhibited in Fig.7. The increased NBO/Si is observed throughout the studied samples due to a more depolymerized silicate network structure.

Fig.7. The NBO/Si in samples calculated from FTIR spectra

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