High Temperature Ceramic Matrix Composites 8

High Temperature Ceramic Matrix Composites 8

Ceramic Transactions, Volume 248

A Collection of Papers Presented at the HTCMC-8 Conference

September 22-26, 2013 Xi'an, Shaanxi, China

Edited by Litong Zhang

Dongliang Jiang

American Ceramic Society

W I L E Y

The

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Contents

Introduction xiii

Preface xv

Symposia Organizers xvii

CERAMIC GENOME, COMPUTATIONAL MODELING, AND DESIGN

Design of New Gradient Cemented Carbides and Hard Coatings 3 through Ceramic Genome

Weibin Zhang, Yong Du, Li Chen, Yingbiao Peng, Peng Zhou, Weimin Chen, Kaiming Cheng, Lijun Zhang, Wen Xie, Guanghua Wen, and Shequan Wang

The Effects of Nesting and Stacking Sequence on the Structural and 15 Gas Transport Properties of Plain Woven Composites during Chemical Vapor Infiltration Process

Kang Guan, Laifei Cheng, Qingfeng Zeng, Yunfang Liu, Haitao Ren, and Litong Zhang

An Efficient Approach to Determine the Effective Properties of 23 Random Heterogeneous Materials

Yatao Wu and Yufeng Nie

Contribution of Image Processing Techniques to the Simulation of 29 Chemical Vapor Infiltration of SiC in CMCs

G. L. Vignoles, C. ChapoullIé, W. Ros, C. Mulat, G. Couégnat, C. Germain, J.-P. Da Costa, M. Cataldi, and C. Descamps

Image-Based Numerical Simulation of Thermal Expansion in C/C 39 Composites

Olivier Caty, Guillaume Couégnat, Morgan Charron, Thomas Agulhon, and Gerard Louis Vignoles

v

Analysis and Molecular Modeling of Pyrolytic Carbons 45 Nanotextures

Jean-Marc Leyssale, Baptiste Farbos, Jean-Pierre Da Costa, Patrick Weisbecker, Georges Chollon, and Gerard Louis Vignoles

A New Kinetic Monte-CarloA/olume-of-Fluid Solver for the 55 Anisotropic Surface Recession of C/C Composites by Ablation

A. Delehouzé, G. L. Vignoles, J.-F. Epherre, and F. Rebillat

Numerical Simulation of Oxidation-Assisted Failure of CMC-SiC at 65 Intermediate Temperature

Yingjie Xu and Weihong Zhang

ADVANCED CERAMIC FIBERS, INTERFACES, AND INTERPHASES

Suppression of a-AI203 Formation from Alumina Gel Fibers by 79 Urea-Catalyzed TEOS-Derived Silica

Jing He and Lifu Chen

Ceramix Matrix Microcomposites Prepared by P-RCVD within the 91 (Ti-Si-B-C) System

Sylvain Jacques

Fabrication and Properties of Zr/SiC and Zr/Si3N4 Laminated 99 Composites

Liangjun Li, Laifei Cheng, Shangwu Fan, YuPeng Xie, and Litong Zhang

Silicon Carbide Fibers Made from Nano-Powders 105 Antoine Malinge, Yann Le Petitcorps, and Rene Pailler

Composition and Reactivity of Various Silicon Carbide Fibers 113 S. Mazerat, G. Puyoo, G. Chollon, F. Teyssandier, and R. Pailler

The Investigation of Pyrolytic Coating on Carbon Monofilament by 125 Cold Wall CVD using Ethanol as Precursor

Song Zhao, Yonghui Zhang, Zhichao Xiao, Junming Su, and Lang Liu

NANOCOMPOSITE MATERIALS AND SYSTEMS

Carbon Nanotube-Reinforced Ceramic Matrix Composites: 133 Processing and Properties

Konstantinos G. Dassios

Fabrication of ZAO Ceramic Target and Effect on the Photoelectric 159 Properties of Its Film

Meikang Han, Jueming Yang, Xiaowei Yin, and Jianping Li

vi High Temperature Ceramic Matrix Composites 8

Mechanical Properties of Carbon Nanotube Reinforced Composites: 167 A Review

Qianglai Bai, Hui Mei, Tianming Ji, Yuyao Sun, Haiqing Li, and Laifei Cheng

Effect of the Electrodeposition Parameters on Deposition 179 Morphologies of CNTs on Carbon Fibers

Hui Mei, Huwei Wang, Haiqing Li, Hui Ding, Nan Zhang, Yuetang Wang, Qianglai Bai, and Laifei Cheng

Microstructure and Growth Mechanism of SiC Whiskers Synthesized 185 by Carbothermal Reduction of Silicon Nitride

Ying Zhang, Junzhan Zhang, Mingxue Jiang, and Minsheng Liu

POLYMER DERIVED CERAMICS AND COMPOSITES

High Temperature Dielectric and Microwave Absorption Properties 195 of Polymer Derived SiCN Ceramic in X Band

Quan Li, Xiaowei Yin, Luo Kong, Wenyan Duan, Litong Zhang, and Laifei Cheng

SiCN-Nanowhiskers Self-Reinforcing CMC Quasi-3D Structure 203 Forming by PIP

I. A. Timofeev, O. G. Ryzhova, P. A. Timofeev, S. V. Zhukova, and K. V. Mikhailovski

Ablation Behavior of C/C-ZrB2-SiC Carbon-Ceramic Composites 209 Xiang-Li Meng, Lian-Sheng Yan, Hong Cui, Xing Yang, and Qiang Zhang

FIBER REINFORCED CERAMIC MATRIX COMPOSITES

Effect of Heat Exposure on the Flexural Strength of Reinforced 219 Carbon and Glass Fibers Geopolymer Matrix Composites

Sotya Astutiningsih, Yulianto Sulistyo Nugroho, Shankar M. L. Sastry, and Dwi Marta Nurjaya

Reaction Mechanism of Titanium with Carbon during Reactive Melt 227 Infiltration of a Carbon Fiber Reinforced TiC and Carbon Composite

Shuxin Bai, Yonggang Tong, Hong Zhang, and Yicong Ye

Modelling the Behavior of CMC using Damage Mechanics 237 Emmanuel Baranger

MMS Technology: First Results and Prospects 243 Evgeniy Bogachev, Anton Lakhin, and Anatoly Timofeev

Effect of Oxidation Damage on the Total Emissivity of 2D C/SiC 255 Composites

Fuyuan Wang, Laifei Cheng, and Litong Zhang

vii High Temperature Ceramic Matrix Composites 8

Effect of Water Vapor on the Oxidation Behavior of CVD-BCX 261 Weihua Zhang, Laifei Cheng, Yongsheng Liu, and Xin'gang Luan

Microstructure and Mechanical Properties of the 2D C/SiC/TC4 271 Joints Brazed with Cu-Ti + Mo

Hongmei Yang, Shangwu Fan, Xing Wang, LaiFei Cheng, and Litong Zhang

Uniaxial Macro-Mechanical Property and Failure Analysis of a 279 2D-Woven SiC/SiC Composite

Hongbao Guo, Bo Wang, and Chengpeng Yang

A Biaxial Flexural Test for Short Carbon Fiber-Reinforced 287 SiC-Matrix Composites

Shuqi Guo

C/C-SiC Materials based on Melt Infiltration —Manufacturing 295 Methods and Experiences from Serial Production

Bemhard Heidenreich, Severin Hofmann, Markus Keck, Raouf Jemmali, Martin FrieB, and Dietmar Koch

Internal Friction Behavior of SiC Ceramics Subjected to Water 311 Vapor Corrosion

Zhiliang Hong, Laifei Cheng, Chunnian Zhao, Xiufeng Han, Litong Zhang, and Yiguang Wang

Fatigue Behavior of C/SiC Ceramic Matrix Composites at Room 317 and Elevated Temperatures

Longbiao Li and Yingdong Song

The Effects Originated from Low Earth Orbit Thermal Cycling and 327 Atomic Oxygen on C/SiC Composites

Bi-feng Zhang, Song Wang, Wei Li, and Zhao-hui Chen

Processing and Properties of the C/SiBCN Ceramic Matrix 335 Composites Prepared by PIP

Wei Liu, Lamei Cao, Caihong Xu, Ling Wang, and Xiaosu Yi

Analysis and Characterization of Amorphous Boron Carbide 345 Coatings Deposited from BCI3-CH4-H2 Mixtures

Yongsheng Liu, Nan Chai, Litong Zhang, and Laifei Cheng

Chemical Vapor Deposition of Boron-Doped Carbon Coating from 357 BCI3-C3H6-H2-Ar Gas Mixture

Yongsheng Liu, JiaJia Wan, Litong Zhang, and Laifei Cheng

Preparation and Mechanical Properties of 3D-Cf/Mullite Composites 371 Fabricated by Sol-Gel Process

Kewei Dai, Haijun Peng, Qingsong Ma, and Haitao Liu

viii High Temperature Ceramic Matrix Composites 8

An Alternative to Ceramic Matrix Composites 377 S. T. Mileiko, N.I. Novokhatskaya, Yu. N. Shmotin, D.V. Karelin, and S.A. Grlshikhin

Fabrication of Short Fiber Reinforced SiCN by Injection Molding of 381 Preceramic Polymers

A. Muller-Kohn, J. Janik, A. Neubrand, H. Klemm, T. Morltz, and A. Michaelis

X-CVI (with X = I or P), a Unique Process for the Engineering and 391 Infiltration of the Interphase in SiC-Matrix Composites: An Overview

R. Naslain, R. Pailler, F. Langlais, A. Guette, and S. Jacques

Temperature Effect on C/SiC Composite with SiC Nanowires Grown 403 In Situ

Bingbing Pei, Yunzhou Zhu, and Zhengren Huang

Evaluation of Different Carbon Precursors for the Liquid Silicon 409 Infiltration Process

Kristina Roder, Andreas Todt, Daisy Nestler, and Bernhard Wielage

Microstructure and Mechanical Properties of C/C-SiC Composites 417 Reinforced with Fibers Treated at Elevated Temperatures

J. J. Sha, J. X. Dai, Z. F. Zhang, Z. Q. Wei, J. Li, J-M. Hausherr, and W. Krenkel

Oxidation Behavior of C/C-SiC Composites with Varied Matrix 425 Composition

J. X. Dai, J. J. Sha, Z. F. Zhang, J-M. Hausherr, and W. Krenkel

Evaluation and Validation of Elastic Properties and a Failure Criterion 433 for an Oxide Wound Ceramic Composite Material

Yuan Shi, Severin Hofmann, Stefan Hackemann, and Dietmar Koch

Mechanical and Ablation Properties of Ultra-High Temperature 443 Composites with a Variable Matrix-Composition

Chenglong Hu, Shengyang Pang, Sufang Tang, Shijun Wang, and Hongtao Huang

CARBON-CARBON COMPOSITES: MATERIALS, SYSTEMS, AND APPLICATIONS

Effects of Preform Structures on Rhenium Coating Prepared on C/C 453 Composites by Chemical Vapor Deposition

Jiangfan Wang, Shuxin Bai, Hong Zhang, and Yicong Ye

Application Status of C/C Composites for Thermal Protection 461 System in Re-Entry Spacecraft

Sun Guoling and Zhou Ji

ix High Temperature Ceramic Matrix Composites 8

Techniques about Fabrication of Thin-Wall Preforms with Complex 465 Shape for Ceramic Composites

Lingling Ji, Alin Ji, Xia Bai, and Lingling Wang

Carbon/Carbon Greenbodies for Space Mirrors and Their Thermal 473 Performance

Jin Li, Hong Cui, and Ruizhen Li

Oxidation Behavior of SiC Reinforced ZrB2 Composite Coating 481 Prepared by Low Pressure Plasma Spray

Cui Hu, Yaran Niu, Hong Li, Xuebin Zheng, Chuanxian Ding, and Jinliang Sun

Structural Analysis of Carbon-Fiber/Pyrolytic Carbon Matrix 487 Composites

Boris Reznik

Preparation of p-Sialon Anti-Oxidation Ceramic Coating for C/C 491 Composites and Infrared Stealthy Characteristic

Yang Wang and Zhaofeng Chen

ULTRA HIGH TEMPERATURE CERAMICS AND MAX PHASE MATERIALS

Effect of Carbon Content on the Formation of Ti3SiC2 in the Liquid 501 Silicon Infiltration Process

Xiaomeng Fan, Xiaowei Yin, Lei Wang, Litong Zhang, and Laifei Cheng

Modification of Titanium Carbide Powders by Silicidation with 509 Gaseous SiO

Elena Istomina, Pavel Istomin, Alexander Nadutkin, and Vladislav Grass

Combustion Synthesis of Ti3SiC2-Based Ceramic Matrix 515 Composites Using Non-Powder Reactant Solids

Pavel Istomin, Alexander Nadutkin, and Vladislav Grass

Microstructure Evolution of a-SiC in the Liquid Phase Sintering 523 Process

Hanqin Liang, Xiumin Yao, Xuejian Liu, and Zhengren Huang

Mechanical Properties and Thermal Shock Resistance of 529 Anisotropic ZrB2-SiC-Graphite Ceramic

Lingling Wang, Jun Liang, and Xiaoyang Wan

Ablation Behavior of ZrB2/SiC Composite by Oxyacetylene Flame 535 Mingfu Wang, Facheng Liu, Qin Wang, and Xuesong Ma

x High Temperature Ceramic Matrix Composites 8

Synthesis of ZrC-ZrB2 Composite Powders by PIRAC Method Shoujun Wu, Yiguang Wang, and Danming Gui

541

THERMAL AND ENVIRONMENTAL BARRIER COATINGS

Formation of Fine Ceramics Layer and Intermetallics Network by 549 Thermal Nanoparticles Spraying and Pattering

Soshu Kirihara

Formation of Inter-splat Bonding and Intra-splat Microstructure 557 during Plasma Spraying of Ceramic Coating

Chang-Jiu Li, Er-Juan Yang, Guan-Jun Yang, and Cheng-Xin Li

Preparation and Ablation Properties of ZrC-TaC Co-Deposition 569 Coating for Carbon-Carbon Composites

Guo-dong Li, Min Wu, Xiang Xiong, Ya-lei Wang, and Gang-yi Yang

Phase Stabilities and Corrosion/Recession Properties of Rare Earth 579 Silicates under High Speed Steam Jet

Shunkichi Ueno, Hua-Tay Lin, and Tatsuki Ohji

INTEGRATION TECHNOLOGIES, COMPONENT TESTING, AND EVALUATION

Wettability in Joining of Advanced Ceramics and Composites: 591 Issues and Challenges

Rajiv Asthana, and Natalia Sobczak

Study on the Ablation Behavior of 3D Needled C/SiC in the Rocket 601 Combustion Environments

Chao Chen, Bo Chen, Litong Zhang, Laifei Cheng, and Xiaoying Liu

The Degradation of Hi-Nicalon Monofilament after Proton Irradiation 607 Xiaochong Liu, Laifei Cheng, Litong Zhang, Xiaowei Yin, Bo Chen, Qing Zhang, and Ning Dong

Damage Evaluation in Glass-Ceramic Matrix Composites Via 615 Combined Infrared Thermography and Acoustic Emission

Konstantinos G. Dassios, Evangelos Z. Kordatos, Dimitris G. Aggelis, and Theodore E. Matikas

Hybrid Ceramic—Metallic Composite Pipes for High Temperature 633 Power Plant Application

Min Huang, Karl Berreth, and Karl Maile

An Experimental Investigation on Shear Behaviors of Single-Lap 639 Four-Pin 2D C/SiC Joints

Yi Zhang, Litong Zhang, Xiaoying Liu, Yongsheng Liu, and Bo Chen

High Temperature Ceramic Matrix Composites 8 • xi

The Effect of Dimension Parameters on the Tensile Properties of a 645 C/SiC Pipe

Hui Mei, Lidong Zhang, Zhenye Xu, and Laifei Cheng

The Application Research of New Testing Technique on Mechanical 653 Experiment for Large-Size CMC Structure

Zhiyong Tan, Xujun Zhan, and Xu Han

Joining of Glassy Carbon with a C/C-SiC Composite by Brazing for 661 an Innovative High Temperature Sensor

Andreas Todt, Kristina Roder, Daisy Nestler, and Bernhard Wielage

Strengthening/Toughening of Laminated (SiCw+SiCp)/SiC Ceramic 669 Composites

Yupeng Xie, Laifei Cheng, Jie Jian, Yanan Xie, and Litong Zhang

Mechanical Properties of Carbon/Silicon Carbide Composites 675 Materials Bolts

Donglin Zhao, Litong Zhang, Laifei Cheng, and Xiang Chen

Development of Full Scale Ramjet Nozzle with C/SiC Ceramic 681 Matrix Composite

Riheng Zheng, Zhiyong Li, Jingmin Chen, Lihan Li, Jianmei Li, Litong Zhang, Laifei Cheng, Xiaoying Liu, Chao Chen, and Hui Mei

Author Index 695

xii High Temperature Ceramic Matrix Composites 8

Introduction

Ceramic matrix composites (CMCs) are becoming a set of indispensable materials for a number of applications in aerospace, power generation, ground transportation, nuclear, environmental and chemical industries involving high temperatures and extreme environments. In China, there has been tremendous progress in CMCs in the areas of scientific research, technological development, and commercialization.

The HTCMC conference was introduced by Prof. Roger Naslain in 1993 and takes place every three years at alternating locations around the globe: Bordeaux (France, 1993), Santa Barbara (USA, 1995), Osaka (Japan, 1998), Munich (Ger-many, 2001), Seattle (USA, 2004), New Delhi (India, 2007), and Bayreuth (Ger-many, 2010).

HTCMC-8, held September 22-26,2013 in Xi'an, Shaanxi, China was a success-ful platform for the community of high temperature ceramics and composites to share innovative ideas in research and development as well as up-to-date applica-tions of CMCs. We would like to gratefully thank the symposium organizers (see page xvii) for their hard work and dedication for making HTCMC-8 a success.

Prof. Litong Zhang Academician, CAE Northwestern Polytechnical University Xi'an, China

Prof. Dongliang Jiang Academician, CAE Shanghai Institute of Ceramics Shanghai, China

xiii

Preface

The High Temperature Ceramic Matrix Composites (HTCMC) conference series was initiated by Prof. Roger Naslain, Honorary professor of University of Bor-deaux, in 1993 in Bordeaux (France), and then in Santa Barbara (USA, 1995), Osa-ka (Japan, 1998), Munich (Germany, 2001), Seattle (USA, 2004), New Delhi (In-dia, 2007) and Bayreuth (Germany, 2010). HTCMC-8 conference was hold in Xian (China, 2013).

In 2013, HT-CMC conference series comes to its 20th year. Over the past two decades, ceramic matrix composites (CMCs) are becoming a set of indispensable materials for a number of applications in aerospace, power generation, ground transportation, nuclear, environmental and chemical industries involving high tem-peratures and extreme environments. Tremendous progress in CMCs has been made in scientific research, technological development, and commercialization.

With the rapid development of related new materials, simulation and process methods, the HTCMC-8 conference has been expanded to comprise nine symposia, and more and more participants have been involved in this conference. In HTCMC-8, there were 320 participants from 18 countries, in which 210 participants came from China and 110 from the other countries. There were 260 oral talks, including 36 keynotes and 52 invited talks, and 75 posters. The HTCMC conference is be-coming an influential conference and an excellent platform for academic communi-cation.

Facing the challenges of harsh service environments, novel high-temperature ce-ramic composite materials for functional/structural-integrated applications have been developed by means of designing the phase composition and microstructure of fiber, interface, matrix and coating. These kinds of research are very attractive and challengeable, which provide great opportunities for discovery of new materials. We believe the development and the application of CMCs would be promoted by effective international exchange and cooperation.

After a peer-review process, 78 papers are accepted for inclusion in this proceed-ings. We acknowledge all the authors' dedications, and appreciate the symposium editors, Jing-Yang Wang, Gregory Morscher, Hui Mei, Peter Greil, Tatsuki Ohji, He-Jun Li, Yan-Chun Zhou, Hua-Tay Lin, and Lai-Fei Cheng for their contribu-

xv

tions during the entire evaluating and reviewing process. We also appreciate Greg Geiger of The American Ceramic Society for his great work on the publication of this proceedings.

PROF. LITONG ZHANG

Academician, CAE Northwestern Polytechnical University Xi'an, China

PROF. DONGLIANG JIANG

Academician, CAE Shanghai Institute of Ceramics Shanghai, China

xvi High Temperature Ceramic Matrix Composites 8

Symposia Organizers

Symposium 1: Ceramic Genome, Computational Modeling, and Design • Jingyang Wang, China • Yong Du, China • Zhiqiang Feng, France • Weihong Zhang, China • Gerard Vignoles, France Symposium 2: Advanced Ceramic Fibers, Interfaces, and Interphases • Gregory Morscher, USA • Lifu Chen, China • Yongcai Song, China • Hubert Jager, Germany • Yutaka Kagawa, Japan Symposium 3: Nanocomposite Materials and Systems • Sanjay Mathur, Germany • Hisayuki Suematsu, Japan • Soshu Kirihara, Japan • Zhengwei Pan, USA • Wei-Hsing Tuan, Taiwan • Yubai Pan, China • Lalit M. Manocha, India Symposium 4: Polymer Derived Ceramics and Composites • Peter Greil, Germany • Paolo Colombo, Italy • Raj Bordia, USA • Linan An, USA • Giinter Motz, Germany • Yiguang Wang, China • Dong-Pyo Kim, Korea • Ralf Riedel, Germany Symposium 5: Fiber Reinforced Ceramic Matrix Composites • Shaoming Dong, China

xvii

• Tatsuki Ohji, Japan • Walter Krenkel, Germany • Jacques Lamon, France • Gilbert Fantozzi, France • Dietmar Koch, Germany • Laifei Cheng, China • Xiaowei Yin, China • Frank Zok, USA • David Marshall, USA Symposium 6: Carbon-Carbon Composites: Materials, Systems, and Applications • Hejun Li, China • Hong Cui, China • Xiang Xiong, China • Walter Krenkel, Germany • Hiroshi Hatta, Japan • Lalit M. Manocha, India • Gerard Vignoles, France Symposium 7: Ultra High Temperature Ceramics and MAX Phase Materials • Guojun Zhang, China • Yanchun Zhou, China • Sylvia Johnson, USA • Alida Bellosi, Italy • Yoshio Sakka, Japan • Xinghong Zhang, China • Shibo Li, China Symposium 8: Thermal and Environmental Barrier Coatings • Hua-Tay Lin, USA • Wei Pan, China • Hagen Klemm, Germany • Yiguang Wang, China • Dileep Singh, USA Symposium 9: Integration Technologies, Component Testing, and Evaluation • Laifei Cheng, China • Mrityunjay Singh, USA • Monica Ferraris, Italy • Roland WeiG, Germany • Rajiv Asthana, USA • Martin Friel3, Germany

xviii High Temperature Ceramic Matrix Composites 8

Ceramic Genome, Computational Modeling,

and Design

DESIGN OF NEW GRADIENT CEMENTED CARBIDES AND HARD COATINGS THROUGH CERAMIC GENOME

Weibin Zhanga, Yong Dua\ Li Chena, Yingbiao Penga, Peng Zhoua, Weimin Chen8, Kaiming Cheng8, Lijun Zhang8, Wen Xieb, Guanghua Wenb, and Shequan Wangb

B State Key Lab of Powder Metallurgy, Central South University, Hunan, 410083, China b Zhuzhou cemented carbide cutting tools limited company, Zhuzhou, Hunan, 412007, China

ABSTRACT The concept of ceramic genome is briefly introduced, and its combination with CALPHAD

(CALculation of PHAse Diagrams) method is a powerful tool for materials process optimization and alloy design. The quality of CALPHAD-type calculations is strongly dependent on the quality of the thermodynamic and diffusivity databases. The development of thermodynamic and diffusivity databases for cemented carbides is described. Several gradient cemented carbides sintered under vacuum and various partial pressures of N2 have been studied via experiment and simulation. Examples of ceramic genome applications in design and manufacture for different kinds of cemented carbides are shown using the databases and comparing where possible against experimental data, thereby validating their accuracies. Metastable Ti-Al-N coatings have been well acknowledged as protective layer for industrial applications due to their excellent mechanical, chemical and thermal properties. Here, we study the effect of Zr addition on structure and thermal properties of Tii.xAlxN based coatings under the guidance of ab initio calculations. The preparation of Tii.x.2AlxZrzN by magnetron sputtering verifies the suggested cubic (NaCl-type) structure for x below 0.6-0.7 and z < 0.4. Alloying with Zr also promotes the formation of cubic domains but retards the formation of stable wurtzite A1N during thermal annealing.

INTRODUCTION Cemented carbides have long been used in applications such as cutting, grinding, and drilling1.

Cemented carbides2 are hard and tough tool materials consisting of micrometer-sized tungsten carbide embedded in a metal binder phase, usually rich in Co. Cubic carbides or carbonitrides based on Ta, Ti, and Nb are often added in cemented carbides to increase the resistance to plastic deformation or as gradient formers1. Some grain growth inhibitors such as Cr and V may also be added in small amounts. In order to increase cutting performance of the cemented carbide inserts, the wear surface are usually coated with a thin layer of hard material3. Due to the high deposition temperature and a large difference in thermal expansion coefficients between the coating and substrate, cracks would be introduced into the coating unavoidably4. And the formed cracks might easily propagate into the substrate to cause failure when coating tools are employed in metal machining5. In order to prevent crack propagation from the coating into the substrate, a gradient layer, which is free of cubic phases and enriched in binder phase, is introduced between coating and substrate3.

In the past decades, cemented carbides were mainly developed through a large degree of testing. However, there are numerous factors influencing the microstructure and properties of cemented carbides, such as alloy composition, sintering temperature, time and partial pressure and so on. These factors can only be varied in an infinite number of ways through experimental method. In order to shorten

3

Design of New Gradient Cemented Carbides and Hard Coatings through Ceramic Genome

development time, reduce the cost and improve outcome, the concept of materials genome has been proposed. Computation, experimentation, and database are identified as three major components of materials genome. The ceramic genome can describe the interaction of the various process conditions, which presents the opportunity to design and produce new kinds of cemented carbides more efficiently. CALPHAD (CALculation of PHAse Diagrams) method is a powerful tool to establish the database of various properties in the ceramic genome. Computational thermodynamics, using, e.g. the Thermo-Calc and DICTRA packages, has shown to be a powerful tool for processing advanced materials in cemented carbides, which is more efficient on composition and process parameters optimization compared with expensive and time consuming experimental methods. With the development of thermodynamic and diffusivity databases, it is possible to make technical calculations on commercial products which are multicomponent alloys. On the basis of thermodynamic database, thermodynamic calculations can give an easy access to what phases form at different temperatures and alloy concentrations during the manufacture process. By combining CSUTDCC1 and CSUDDCC1 databases, DICTRA6 permits simulations of the gradient process, which is a major advance in the understanding of the gradient zone formation in the cemented carbides.

Ti-Al-N hard coatings with cubic (c) NaCl structure, where A1 substitutes for Ti in the TiN-based structure (i.e., c-Tii.xAlxN), are widely used in cutting tools because of their high hardness and wear resistance as well as good thermal properties7. Because of the spinodal decomposition of c-Tii^AlxN into nano-size cubic Ti-rich and Al-rich domains at elevated temperatures, the age-hardening abilities of Ti-Al-N coatings can improve the mechanical properties of coatings8. Due to solid solution strengthening, alloying Zr to Ti-Al-N coating can improve the hardness. Unfortunately, a huge amount of work is needed to find appropriate elements by using experimental method, while first-principles calculations on the investigation of structural and mechanical properties can reduce the workload effectively and provide the reasonable explanation for the experimental observation.

This paper is devoted to 1) describe the development of the thermodynamic and diffusion databases in cemented carbides, 2) design experiments to investigate the gradient zone formation under different sintering environments, 3) validate the accuracy and reliability of the presently established databases in ceramic genome by comparing the experimental and simulation results, 4)investigate the structural and thermal properties of Ti-Al-Zr-N hard coatings by first-principles calculations and experiment, and 5) present the schematical ceramic genome strategy for the development of new cemented carbides and hard coating.

ESTABLISHMENT OF THE CERAMIC GENOME

Development of Thermodynamic and Diffusivity Databases The development of thermodynamic and diffusivity databases in cemented carbides has started

from the major elements in gradient cemented carbides C-Co-Cr-W-Ta-Ti-Nb-N. The usage of ceramic genome in industry will necessarily require that thermodynamic and diffusivity databases provide data that is not only of high quality, but relevant to industrially complex materials.

Developed using the CALPHAD approach, the thermodynamic database, CSUTDCC1, is based on critical evaluations of binary, ternary and even higher order systems which enable making predictions

4 • High Temperature Ceramic Matrix Composites 8

Design of New Gradient Cemented Carbides and Hard Coatings through Ceramic Genome

for multicomponent systems and alloys of industrial importance. Six important phases in cemented carbides, e.g. liquid, WC, carbides or carbonitrides, binder (Co), and eta (MeC or M12C) phases, are the main focus during the modeling. A large number of additional phases are also included in CSUTDCC1, because many of the binary and ternary systems in CSUTDCC1 have been assessed over their entire composition and temperature ranges. It is important to have reliable descriptions for all the stable phases in the system when developing new alloys and exploring new composition ranges. The thermodynamic models describe the thermodynamic properties of various types of phases depending on the crystallography, order-disorder transitions, and magnetic properties of the phases. With parameters stored in database, many different models9, including the substitution solution model, sublattice model, order-disorder model, have been adopted for the phases in cemented carbide systems. The thermodynamic models for Gibbs energy of a phase can be represented by a general equation:

Gi=refGi+idGi+EGdm+

m^G»m (1)

Here refGem represents the Gibbs energy of the pure elements of the phase and ,dG°m represents the

contribution due to the ideal mixing. The term EG^ represents the excess energy and masnGem the

magnetic contribution.

In contrast to extensive efforts on the establishment of thermodynamic database for multicomponent cemented carbides, diffusivities in the multicomponent cemented carbides have received limited investigations both experimentally and theoretically. In a multicomponent system, a large number of diffusivities need to be evaluated, making a database very complex. A superior alternative is to model atomic mobility instead. In this way, the number of the stored parameters in the database is substantially reduced and the parameters are independent. A detailed description for the atomic mobility is given by Andersson and Agren10. The atomic mobility for an element B, MB, can be expressed as

MB=M0Bexp(-QjRT){l/RT) (2)

where R is the gas constant, Tthe temperature, Mjj a frequency factor and QB the activation enthalpy.

Both Ml and QB are in general dependent on composition and temperature.

The simulation of gradient zone formation is based on the model for long-range diffusion occurring in a continuous matrix with dispersed phases. Due to the presence of dispersed phases (WC, carbides and carbonitrides), the diffusion is reduced in the matrix (the liquid binder phase)11. A so-called labyrinth factor KJ), where/is the volume fraction of the matrix, was introduced to reduce the diffusion coefficient matrix.

(3)

First-principles Calculations of Hard Coatings First-principles calculation is one of the theoretical methods to study the microstructure and

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Design of New Gradient Cemented Carbides and Hard Coatings through Ceramic Genome

properties of materials. This method is based on the density functional theory (DFT) with the local density approximation (LDA)12 or generalized gradient approximation (GGA)13. In the present work, first-principles calculations are performed by Vienna ab-initio simulation package (VASP)14. The electron-ion interactions are described by the projector augmented wave (PAW) method15, and the exchange-correlation is depicted by GGA and LDA. The energy cutoff of the wave functions is taken as 1.3 times higher than the default values in the psudopotentials. The Monkhorst-Pack scheme16 of k-points sampling and the linear tetrahedron method including BlGchl corrections17 are adopted for the integration in the Brillouin zone. The total number of k-points is at least 10,000 per reciprocal atom for all the calculations. The convergence criterion for electronic self-consistency is 10"6 eV per unit cell.

The quasiharmonic approach is adopted to evaluate the finite-temperature Helmholtz energy as a function of volume V and temperature T18

F (VJ) = E(V)+ Fvih(V,T)+ Fele(V,T) (4)

where E{V) is the static energy at 0 K without the zero-point vibrational energy, Fvih(V,T) is the

vibrational contribution to Helmholtz energy with the input of phonon density of state (DOS), and

Fele(V,T) is the thermal electronic contribution to the free energy, which can be calculated by Mermin

statistics19 with input of electronic DOS from first-principles directly.

EXPERIMENTAL The alloys were prepared from a powder mixture of WC, (Ti,W)C, Ti(C,N), and metallic Co

powder provided by Zhuzhou cemented carbide cutting tools limited company. The composition of the sintered material is given in Table 1. After milling and drying, the powders were pressed into cutting tool inserts. Samples were dewaxed and sintered under different nitrogen partial pressures (0, 20 and 40 mbar) at 1723 K for 1 h. After sintering the samples were cut, embedded in resin and polished. SEM (Nova NanoSEM 230, USA) was employed to investigate the microstructure of the gradient zone, and EPMA (JXA-8230, JEPL, Japan) was used to determine the concentration profiles of the elements.

Table I. Chemical composition of the investigated cemented carbides (wt%) Alloy Ti Co C N W

WC-Ti(C,N)-Co 5 7.5 6.35 0.1 Bai.

Tii.x.zAlxZrsN films were deposited onto several substrates by unbalanced magnetron sputteringin a mixed Ar+N2 (both of 99.999% purity) glow discharge. DSC with TGA was performed in a Netzch-STA 409C from room temperature (RT) to 1500 °C with a heating rate of 20 K/min in flowing He (99.9% purity, 20 seem flow rate) .The chemical compositions of the films were determined using energy dispersive X-ray analysis (EDX) with an Oxford Instruments INCA EDX. Phase identification and structural investigations of the layers in their as deposited state and after thermal treatment with the DSC equipment in He or synthetic air were conducted by XRD with CuK« radiation using a Brucker D8 diffractometer in Bragg/Brentano mode. DFT calculations were performed using the VASP code.

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Design of New Gradient Cemented Carbides and Hard Coatings through Ceramic Genome

RESULTS AND DISCUSSION

Verification and Application of the Databases It is generally known that the graphite and eta (M6C or MI2C) phases are unexpected phases and

the carbon content in cemented carbides should be carefully controlled to avoid the formation of these phases. With the aid of thermodynamic calculations, it is easy to see how to control the carbon content and how the carbon content affects the choice of sintering temperature when developing a new alloy. Figure 1(a) shows a calculated phase equilibria closing to the sintering region of an alloy with the composition of C-W-9Co-15Ti-10Ta-2Nb-0.1N (wt.%). As can be seen, the carbon content have to be carefully located in a narrow range about 0.2 wt.% in order to avoid the appearance of unwanted phases. Figure 1(b) presents a similar calculation by adding 2 wt.%, of Cr. From Fig. 1(b), it can be seen that the melting point of binder phase is decreased substantially by Cr addition and the existence of the preferable fcc_Co + M(C, N)x + WC equilibrium is broadened. On the basis of CSUTDCC1, a similar calculation can be performed on alloys with any composition, which will be a useful guidance for

Figure 1. Calculated phase equilibria closing to the sintering region of alloys with the composition of (a) C-W-9Co-15Ti-10Ta-2Nb-0. IN (wt.%) and (b) C-W-2Cr-9Co-15Ti-10Ta-2Nb-0.1N (wt.%)

Study of Gradient Zone Formation in Cemented Carbides Figure 2 shows SEM micrograph of the cross section of alloys sintered under different nitrogen

partial pressures (0, 20 and 40 mbar) at 1450 °C for 1 h. It is obvious that the near-surface of the alloy has formed the gradient zone which is enriched in binder phase and depleted in cubic carbides. Comparing the micrographs of the cross section of the cemented carbides sintered under different low nitrogen gas pressure shows that a decreasing thickness of gradient layer with increasing nitrogen gas pressure.

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Design of New Gradient Cemented Carbides and Hard Coatings through Ceramic Genome

Figure 2. SEM micrograph of the cross section of alloys sintered under different nitrogen partial pressures (0, 20 and 40 mbar) at 1450 °C for 1 h.

By combining the presently established thermodynamic and diffusivity databases, DICTRA software has been used to simulate the formation of the gradient zone. Figures 3(a)-(b) illustrate the simulated elemental concentration profiles for Co and Ti in alloys after sintering for 1 h at 1450 °C under different nitrogen partial pressures (0, 20 and 40 mbar), compared with the measured data. This result indicates that the content of Ti is free in the near-surface zone and enrich inside the surface zone. At the near-surface zone, the content of Co increases sharply and reached a maximum value. Beneath the near-surface zone, a decrease of Co is observed, which leads to the minimum value. Above this minimum value, the content of Co increases slowly to its bulk value. The calculated thickness of the gradient layer decreases with the increasing of nitrogen partial pressure, which shows the similar diffusion behavior as the experimental results. As can be seen in Figs. 3(a)-(b), the presently obtained thermodynamic and diffusion databases can reasonably reproduce most of the experimental concentration profiles.

(a) (b) Figure 3. Concentration profile for (a) Co and (b) Ti in alloys: measurement (symbols) and calculation (curve).

Ti-Al-Zr-N Hard Coatings Elemental analysis by EDX reveals that our Tii.x.zAlxZrzN films are stoichiometric with N/metal

ratios of l±0.1and compositions of Tio.48Alo.52N, Ti0.40Al0.55Zr0.05N, Tio.39Alo.51Zro.joN, Tio.36Alo.47Zro.17N,

and Tio.34Alo.37Zro.29N, respectively. XRD investigations in Fig. 4 reveal a single phase cubic structure,

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Design of New Gradient Cemented Carbides and Hard Coatings through Ceramic Genome

which is in agreement with ab intio calculations. Figure 5a presents the energy of formation (Ef) of the cubic and wurtzite Tii.x.zAlxZrzN alloys with constant z - 0, 0.05 and 0.1 as a function of the A1N mole fraction x. The data suggest a transition from cubic to wurtzite structure Tii.^AlxZrzN at x -0.72, 0.70, and 0.68 for a ZrN mole fraction z of 0, 0.05, and 0.10, respectively. Since the compositional steps given by the supercell sizes are different for the cubic (1/18) and for the wurtzite (1/16) alloys, to evaluate the maximum solubility of A1N in the cubic phase we proceeded as follows. First, we fitted each set of data with constant ZrN mole fraction with a quadratic polynomial (ao + ai x + a2'X

2). For c-Tii_x.zAlxZrzN, the A1N mole fraction x was varied 19 times for z- 0, 12 times for z = 0.055, and 10 times for z = 0.111. The calculations of w-Tii.x.zAlxZrzN were obtained with 7, 6, and 5 variations in x for z - 0, 0.0625, and 0.125, respectively, in the composition range * = 0.5-1. Subsequently, for each phase (i.e. cubic or wurtzite) we fitted individually the coefficients (i.e. ao, ai, a2) of their quadratic polynomial for the three different ZrN mole fractions, z, with a linear expression in the ZrN contents. This way, two polynomial fits (one for the cubic and one for the wurtzite modification) as functions of x (A1N mole fraction) and z (ZrN mole fraction) were obtained. In the last step, we used these fits to estimate the cross-over between the formation energies of the cubic and wurtzite phases at fixed ZrN mole fractions (and thus to estimate the influence of Zr on the maximum A1N mole fraction in the cubic Ti^AUZrzN).

a c-Tio.5Alo.5N

30 40 50 60 70 80 29(deg)

Figure 4. XRD patterns of as deposited powdered Tii.x-zAlxZrzN thin films.

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Design of New Gradient Cemented Carbides and Hard Coatings through Ceramic Genome

-2,8 0 . 0 0 . 2 0 . 4 0 . 6 0 . 8 1 .0

AIN mole fraction, x —ab initio * experiments

AIN

TIN 0 . 2 5 0 . 5 0 ' 0 . 7 5

AIN mole fraction, x

Figure 5. (a) Energy of formation (Ef) for c-Tio.33Alo.39Zro.28N and cubic and wurtzite phases Tii.x.rAl*ZrzN with z = 0, 0.05 and 0.1 as functions of AIN mole fraction, (b) Overall chemical compositions of our Tii.x-.AkZr.N films, in the as deposited state, plotted within the TiN-AlN-ZrN quasi-ternary phase diagram. The solid line indicates the transition between preferred cubic and wurtzite phases

Ab initio obtained mixing enthalpies (from the binary constituents c-TiN, c-ZrN, and w-AIN) for c-Tio.4gAlo.52N, c-Ti0.4Al0.55Zr0.05N, c-Tio.39Alo.51Zro.1N, and c-Tio.34Alo.37Zro.29N are 104, 116, 119, and

120 meV/at, respectively, and hence increase with increasing ZrN content. When using a cubic solid solution between TiN and ZrN, i.e. c-Tii_yZryN (with y = Z/(1-J)) as a constituent next to w-AIN, we obtain mixing enthalpies of 104, 98, 87, and 72 meV/at for z = 0, 0.05, 0.10, and 0.29, respectively. The latter reference and the comparison of the mixing enthalpies with the DSC experiments, which exhibit an overall exothermic contribution of 192, 232, 227, and 140 W-K/g for the coatings c-Tio.48Alo.52N, c-Ti0.4Al0.55Zr0.05N, c-Tio.39Alo.51Zro.1N, and c-Tio.34Alo.37Zro.29N, suggests that there is no separation into the constituents c-TiN, c-ZrN, and w-AIN but into c-Tij.̂ ZrvN and w-AIN. This is verified by XRD analysis of samples annealed to various temperatures using the DSC equipment with the same setup, atmosphere, heating and cooling rates.

Figure 6 shows the structural evolution during annealing of our Tio.48Alo.52N (a) Tio.4Alo.55Zro.05N (b] and Tio.39Alo.51Zro.1N (c) films by means of XRD patterns after annealing to 700, 850, 1100, 1200, and 1500 °C. The Zr-free Tio.48Alo.52N film exhibits a small shift of the XRD reflexes during annealing to 700 °C as compared with the as deposited state, see Fig. 6a, suggesting only minute structural changes like recovery and relaxation which contribute to the exothermic DSC feature in this temperature range. The XRD patterns of the Zr-containing films Ti0.4Al0.55Zr0.05N and Tio.39Alo.51Zro.1N annealed to 700 °C reveal also a shift in the peak position to higher diffraction angles but also an increase in peak broadening, see Figs. 6b and c. The latter is an indication for a reduction in grain size and/or an increase in microstresses which can result from the onset of a decomposition process. This can better be seen after annealing at 850 °C, where the XRD reflexes exhibit on both sides (lower and higher diffraction angles) an increase in intensity and width, suggesting the formation of Al-depleted and Al-enriched domains. After annealing at 1100 °C, a pronounced shoulder-formation on both sides of the 'matrix' XRD peak can be seen clearly. These shoulders indicate the formation of TiN- and AIN-rich cubic domains for Tio.48Alo.52N, and TiN-, ZrN- and AIN-rich cubic domains for the Zr-containing films. While the Zr-free film, Tio.48Alo.52N, exhibits the formation of w-AIN already after annealing at 1100 °C, no

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