High temperature phase equilibria and phase diagrams

P e r g a m o n T i t l e s of R e l a t e d Interest ASHBY & JONES Engineering Materials & Η EAR Ν M e c h a n i c s of Materials, n d Edition HULL & BACON Introduction to Dislocations, r d Edition KELLY Concise Encyclopedia of C o m p o s i t e Materials KHAN & MASATAKA A d v a n c e s in Plasticity 9 LANSDOWN Materials t o Resist W e a r NIKU-LARI A d v a n c e s in Surface Treatments SCULLY Fundamentals of Corrosion, r d Edition TAYA & A R S E N A U L T Metal Matrix Composites P e r g a m o n R e l a t e d Journals A c t a M e c h a n i c a Solida Sinica International J o u r n a l of Solids a n d Structures J o u r n a l of Physics a n d Chemistry of Solids Materials a n d Society Materials Research Bulletin Progress in Materials Science Progress in Solid State Chemistry {Free Specimen Copy Gladly Sent on Request) HIGH TEMPERATURE PHASE EQUILIBRIA and PHASE DIAGRAMS KUO CHU-KUN The Institute of Ceramics of Academia Si nica, Shanghai, China LIN ZU-XIANG The Institute of Ceramics of Academia Sνnica, Shanghai, China YAN DONG-SHENG Vice President of Academia Sinica, Beijing 100045, China PERGAMON PRESS M e m b e r of M a x w e l l M a c m i l l a n P e r g a m o n Publishing C o r p o r a t i o n OXFORD · NEW YORK BEIJING · FRANKFURT SAO PAULO TOKYO · TORONTO SYDNEY U.K Pergamon Press pic, Headington Hill Hall, Oxford X OBW, England U.S.A Pergamon Press, Inc., Maxwell House, Fairview Park, Elmsford, New York 10523, U.S.A PEOPLE'S REPUBLIC OF C H I N A Pergamon Press, Room , Qianmen Hotel, Beijing, People's Republic of China FEDERAL REPUBLIC OF G E R M A N Y Pergamon Press GmbH, Hammerweg 6, D - Kronberg, Federal Republic of Germany BRAZIL Pergamon Editora Ltda, Rua Ega de Queiros, 346, CEP 1 , Paraνso, Sao Paulo, Brazil AUSTRALIA Pergamon Press (Australia) Pty Ltd., PO Box 544, Potts Point, N S W 1 , Australia JAPAN Pergamon Press, 5th Floor, Matsuoka Central Building, 1-7-1 Nishishinjuku, Shinjuku-ku, Tokyo 160, Japan CANADA Pergamon Press Canada Ltd., Suite No , 253 College Street, Toronto, Ontario, Canada M T R5 Copyright © 9 Pergamon Press pic All Rights Reserved No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means: electronic, electrostatic, magnetic tape, mechanical, photocopying, recording or otherwise, without permission in writing from the publisher First edition 9 High Temperature Phase Equilibria and Phase Diagrams is published by arrangement with This edition of Shanghai Scientific and Technical Press, Shanghai, China Library o f C o n g r e s s C a t a l o g i n g - i n - P u b l i c a t i o n Data Kuo Chu-Kun High temperature phase equilibria and phase diagrams/Kuo Chu-Kun, Lin Zu-Xiang, and Yan Dong-Sheng.—Isted p cm Phase rule and equilibrium High temperature chemistry I Lin Tsu-Hsiang II Yen T S (Tung-Sheng), - III Title QD503.K86 9 541.3'687—dc20 90-7211 B r i t i s h L i b r a r y C a t a l o g u i n g in P u b l i c a t i o n D a t a Kuo Chu-Kun High temperature phase equilibria and phase diagrams Phase diagrams I Title II LinZu-Xiang III Yan Dong-Sheng 541.363 ISBN - - - PrintoH in ^rMt Rritain hv BPCC Wheatons Ltd., Exeter Preface H I G H temperature phase equihbria studies, materials, science and engineering have had a close relationship through a number of decades For the purpose of improving the properties of existing materials, development of new materials or designing and innovating new fabrication processes, the phase relationships of different components at high temperature are usually consulted Moreover, equihbrium or nonequihbrium states can usually be observed between different phases due to reaction kinetics or some other factor and these will, to a large extent, govern or strongly influence the microstructure and properties of the final material produced The study of high temperature phase diagrams of nonmetallic systems dates back to the turn of the century Silica, and mineral systems containing silica, where the first to be studied since they relate, by and large, to the composition of traditional ceramics, refractories, glasses, and cement The phase diagrams of these systems were immediately found useful by ceramists of that period and since then a new field of phase equihbria studies and phase diagrams of oxide systems has opened up as an important and pioneering part of ceramic science Over the past halfcentury or more, the progress of high temperature phase research can be summarized into two main streams: firstly, the diversity of components in the systems studied and secondly, the advancement of phase diagram studies themselves The components involved in early studies were essentially silica, alumina, alkali and alkali earth oxides However, with the evolution of technical ceramics in the forties and fifties, such as pure oxide ceramics, electronic ceramics, and special glasses, etc., new components have been introduced into the phase diagram systems being studied; for example, oxides of titanium, niobium, zirconium and tantalum are a few of the materials currently being used in research and development The last couple of decades have also seen an expansion in the components being researched in high temperature phase studies; the more traditional oxides being joined by nitrides, oxynitrides, carbides, chalcogenides, etc These ¡X ÷ Preface new ceramics are interrelated with various kinds of structural and functional ceramics, and this area of work has attracted widespread attention from metallurgists, geologists, mineralogists, solid state chemists and solid state physicists, as well as material scientists and engineers Progress in phase diagram study includes the improvement of experimental methods, innovation of new techniques and adaption of those from other fields As the field of high temperature study has expanded this has resulted in a concurrent expansion in related fields such as high temperature generation, temperature measurement and control, controlled gas pressure, high pressure techniques, phase analyses, structural and microstructural analyses and so on In addition, since the seventies, with the general application of computers, the accumulation of thermochemical data of various compounds, and the advances in the theory of high temperature thermodynamics and phase equilibria relationships, the thermodynamical calculation of phase diagrams and multi-phase equilibria data have become a reality These calculations are usually checked by a few experimental results, thus rendering both approaches self compatible and complementary In the mid-eighties, Shanghai Scientific and Technical Publishers and the authors of this book Professors Kuo Chu-kun and Lin Zu-xiang, set out a plan for "Phase Diagrams of High Temperature Systems" This would certainly be an invaluable text from any point of view Through their unfaiUng effOrts, this arduous task has been successfully completed and the contents include the fundamentals of phase diagrams, experimen­ tal and computational methods, examples of applications, as well as the experience and results accumulated by the authors throughout their years of work on high temperature phase diagram studies I am sure that its publication will be welcomed and have the full support of readers from various disciplines Any amendments or corrections of any part of this text will also be greatly appreciated by the authors I personally look upon this as an important contribution that is worthy of recommendation Y A N D O N G ( T S Y A N ) Member, Chinese Academy of Sciences CHAPTER Introduction FROM the viewpoint of conventional terminology we would not expect a universally acceptable definition of the term "high temperature" Plasma physicists may call some hundred million degrees Kelvin in an ionized gaseous atmosphere a high temperature However, on the other hand, high temperature is often considered to be temperatures as low as minus one hundred degrees centigrade in the thinking of scientists and engineers who work with low temperature systems or the physics and chemistry of superconductivity In material science the term "high temperature" may be used to cover the temperature interval from 0 ° C (for polymer chemists) to 0 ° C (for some ceramists and metallurgists) At present only a few solid materials can stand at temperatures above 0 ° C This temperature may be considered as an acceptable upper limit for phase diagram studies in most experimental laboratories In this book we roughly define high temperature phase diagrams or systems as those in which the liquidus temperatures are above 0 ° C In accordance with this definition, most, if not all, systems of interest in the non-metallic materials will be included So far the investigation of high temperature equiHbria and phase diagrams concerns only the systems containing condensed phases, with or without the participation of a gaseous phase The heterogeneous equilibria research of high temperature systems may stem from the beginning of this century when members of the staff* at the Geophysical Laboratory of The Carnegie Institution of Washington developed and established the quenching technique which is extremely useful for the examination of rock-forming systems and which has been used to examine many siHcate phase diagrams These early studies have led to a fundamental under­ standing of the reactions and solidification process occurring in silicate and aluminosilicate melts, and the results have been directly employed to interpret the formation of minerals and rocks The research work in this field attracted the attention of ceramists since the chemical composition and fusion behaviour of the systems are so similar to those of cement, porcelain, glass and refractory materials In the early thirties, with the support of the American Ceramic Society, Hall and Insley compiled and High temperature phase equilibria and phase diagrams published the first collection of phase diagrams which consisted of mainly the silicate and oxide systems Slightly later, German chemists studied fusion diagrams and phase relationships between high temperature oxides Although the fusion diagrams deviated, more or less, from the equilibrium condition due to insufficient reaction time and vaporization, this work still provided information and built an important foundation for application and further investigation of the equilibrium phase relations During the past thirty years the development of high technology advanced ceramics and glasses stimulated the research programme of phase diagrams At the same time the interest in high temperature system studies extended to a series of new components, such as TÍO2, Z r , B2O3, N b and, in addition, a new group of phase diagrams of non-oxide components came into being Since then equilibria and phase diagram studies have become not only the basis of mineralogy and petrology but also a fundamental discipline of material science In China the study of high temperature phase diagrams began in the fifties At that time a project on high temperature oxide and ffuoride systems was being carried out at the Ceramic Department of the Institute of Metallurgy and Ceramics, the predecessor of the Shanghai Institute of Ceramics Several years later the phase diagram studies were redirected towards rare earth sesquioxide-containing systems, with a view to searching for new materials More recently, Chinese researchers have aimed their investigation at the systems relevant to heat engine ceramics and to crystal growth technology, as well as the exploitation of new materials This work is currently being carried out in the Shanghai Institute of Ceramics and the Institute of Physics Table 1.1 lists some seventy high temperature phase diagrams published in Chinese journals The recent progress in high temperature phase diagram research can be summarized as follows (1) Applications of phase diagrams to material science The applications of and interest in phase equilibria and phase transformations in various areas of material science has grown signifi­ cantly On the one hand, the experimental results of phase equilibria and phase diagrams convey information about development of new materials, improvement of existing materials and estimation of potential use of products On the other hand, the appearance of new materials also introduces new components for examination T w o essential points of change in experimental phase diagram investigation are: (i) In addition to rock-forming oxides, many new components are introduced into the high temperature systems Listed in Table L are the statistics of frequency of appearance of twenty-one oxides in the phase Lin Zu Xiang, Yu Hui Jun Lin Zu Xiang, Yu Hui Jun Kuo Chu Kun, Yen Tung Sheng Han Wen Long, Kuo Chu Kun Gd203-Zr02 Y203-Zr02 La203-BeO Gd203-BeO Sm 3-BeO, H0 20 3-BeO, Y2 3-BeO RE (RE = La, Nd, Gd, Ho, Y}-Ti0 SrNb -NaNb0 -LiNb0 Kuo Chu Kun, Yen Tung Sheng Kuo Chu Kun, Yen Tung Sheng Lin Zu Xiang, Yu Hiu Jun CaF CaF2-La203 2-La 20 CaF2-Al203 CaF2-A1203 La La203-Zr02 20 3-Zr0 Han Wen Long, Huang Yu Zhen, Kuo Chu Kun, Yen Tung Sheng Kuo Chu Kun, Huang Yu Zhen, Huang Yuan Mou, Yen Tung Sheng Huang Zhen Kun, Lin Zu Xiang, Yen Tung Sheng Tang Oi Sheng, Liang Jin Kui, Shi Tin Jun, Zhang Yu Lin, Tian Jin Hua, Li Wen Xiu Tan Bin Vi, Tan Hao Ran Kuo Chu Kun, Yen Tung Sheng Authors Publication Wuli Xuebao (Acta Physica Sinica) 28,62 (1979) Guisuanyan Xuebao (Journal Chinese Silicate Society) 7, (1979) Kexue Tongbao (Science Bulletin) 26, 411 (1981) Kexue Tongbao (Science Bulletin) 26,414 (1981) Xisuanyan (Silicate) 2,150 (1958) 1959 yan Guisuanyan Yanjiu Guongzhou Baogaohui Lunwenji (Proceedings National Meeting on Silicate Research, 1959), p 283, Kexue Chubanshe (Science Press) 1962 Guisuanyan Xuebao (Journal Chinese Silicate Society) 1, (1962) Huaxue Xuebao (Acta Chimica Sinica) 30,381 (1964) Guisuanyan Xuebao (Journal Chinese Silicate Society) 3, 159 (1964) Guisuanyan Xuebao (Journal Chinese Silicate Society) 3,229 (1964) Guisuanyan Xuebao (Journal Chinese Silicate Society) 4,22 (1965) Guisuanyan Xuebao (Journal Chinese Silicate Society) 4, 82 (1965) Guisuanyan Xuebao (Journal Chinese Silicate Society) 4, 211 (1965) 1.1 Phase diagrams published in Chinese journals MgO-AI 20 3- Ti0 CaF2-CaA12Si20s System TABLE Introduction Zr0 2-AI 20 3-Si0 Guisuanyan Xuebao (Journal Chinese Silicate Society) 11, 380 (1983) Guisuanyan Xuebao (Journal Chinese Silicate Society) 10,412 (1982) Gao Zhen Xin Sun Wei Rong, Huang Zhen Kun, Chen Jian Xin Guisuanyan Xuebao (Journal Chinese Silicate Society) 11, 189 (1983) Fu Zhen Min, Li Wen Xiu and phase Guisuanyan Xuebao (Journal Chinese Silicate Society) 10, 141 (1982) equilibria Wang Pei Ling, Liu Jan Chen, Chao Guo Bing, Wu Jing Oi, Li Oe Yu U^WO^-UίiO^^U^GeO^^ Che Guan Sheng Wuli Xuebao {Acta Physica Sinica) 1061 (1983) GuanTang Chan,DiTang Oi Sheng CheChan, Wuli Xuebao (Acta32,Physica Sinica) 32, 1061 (1983) Li V04-Li4Si04-Li4Ge04 BaB204-Na20, BaB204Huang Qing Zhen, Liang Jin Kui Wuli Xuebao {Acta Physica Sinica) 30, 559 (1981) BaB -Na 0, BaB Huang Qing Zhen, Liang Jin Kui Wuli Xuebao (Acta Physica Sinica) 30, 559 (1981) 2 Na2C03, BaB204-Na2B204 Na 2C0 , BaB204-Na2B204 BaB204-LÍ20, BaB204Huang Qing Qing Zhen, Zhen, Wang Wang Guo Guo Fu, Fu, Wuli Xuebao Physica 33,Sinica) 76 (1984), Huang BaB Wuli {Acta Xuebao (ActaSinica) Physica 33, 76 (1984) 20 420 4-Li 20, BaB LÍ2B2O4 Liang Jin Kui Liang Jin Kui Li B2 BaB204-SrO, BaB204-SrB204 Wang Guo Guo Fu, Fu, Huang Huang Qing Qing Zhen, Zhen, Huaxue Xuebao Xuebao (Acta {Acta Chimica Chimica Sinica) Sinica) 42, 42, 503 503 (1984) (1984) BaB Wang Huaxue 20 4-SrO, BaB 20 4-SrB 20 Liang Jin Jin Kui Kui Liang Guisuanyan Xuebao (Journal Chinese Silicate Society) 9, 253 (1981 ) Wuli Xuebao (Acta Physica Sinica) 29, 1497 (1980) Wuli Xuebao (Acta Physica Sinica) 33, 1427 (1984) Guisuanyan Xuebao (Journal Chinese Silicate Society) 9, 143 (1981) phase Li 4Ge0 4-Zn 2Ge0 Tang Oi Sheng, Che Guan Chan, Chen Li Quan Li Shi Chun, Lin Zu Xiang Zao Zhong Yuan, Tang Oi Sheng, Che Guan Chan, Bi Jian Qing, Chen Li Quan Fu Zhen Min, Li Wen Xiu, Xu Pan Xiang, Zan Jin Yu, Qi Xiao Zhen Publication temperature Li 4Ge0 4-Zn 2Ge0 S Authors 1.1 Phase diagrams published in Chinese journals-(continued) High LiNb0 -Zn Nb 20 System TABLE diagrams Chao Tang Tang LilOj-RblOa LiI03-Zn(I03)2 Liang HoCl3-NaCl, ErClj-NaCl H0CI3-KCI, ErClg-KCl KCl-SrCl2 LiS04-MgS04, LÍNO3Mg(N03)2 Su LiCl-KCl-PbS04 Shang BeS04-Al2(S04)3-Na2S04 BeS04-Na2S04 LaOBr-BiOBr Mg(I03)2-LiI03-HI03 Liang LilOj-NalOj KIO3-CSIO3 RblOj-HIOj, CSIO3-HIO3 Liang LÍIO3-KIO3 LÍ2SO4-LÍ2B2O4, LÍ4SO4- Y2O3-AI2O3-SÍ2N2O Qian Jio Xin, Tan Bo Yun, Ma Jin Hua, Su Main Zheng Zhang Qui Yun, Ru Jing Zhi, Sun Shu Ren Shang Bao Xu, Chao Yuan Chun N P Luzhlaya, Xu Xiao Bai P I Fedolov, Zhang Qi Yun P I Fedolov, Zhang Qi Yun Liang Jin Kui, Liu Hong Bing, Zhang Sun Min, Xu De Zhong Tang Di Sheng, Li Wen Xiu, Yu Cui Zhen, He Bao Xiang Tang Di Sheng, Fu Zhen Min, Li Wen Xiu Fu Zhen Min, Li Wen Xiu, Chen Li Quan Fu Zhen Min, Li Wen Xiu, Zhang Yu Ling, Tian Jin Hua Liang Jin Kui, Che Guan Chan, Zhang Yu Ling Liang Jin Kui, Yu Yu De Su Main Zheng, Wang Van Ji Chao Guo Zhong, Huang Zhen Kun, Fu Xi Ren, Yen Tung Sheng Che Guan Chan, Chen Li Quan Wuli (Physics) 11, 222 (1982) Gaodeng Xuexiao Huaxue Xuebao (Chern Journal Chinese University) 3, 433 (1982) Huaxue Xuebao (Acta Chirnica Sinica) 9,23 (1957) Gaodeng Xuexiao Huaxue Xuebao (Chern Journal Chinese University) 4, 159 (1983) Gaodeng Xuexiao Huaxue Xuebao (Chern Journal Chinese University) 4, 163 (1983) Huaxue tongbao (Chemistry) 11, 665 (1985) Huaxue Xuebao (Acta Chimica Sinica) 24,356 (1958) Beijing Daxue Xuebao (Journal Beijing University) No.4, 401 (1963) Kexue Tongbao (Science Bulletin) 17, 70 (1966) Guisuanyan Xuebao (Journal Chinese Silicate Society) 9,90 (1981 ) Wuli Xuebao (Acta Physica Sinica) 31, 621 (1982) Wuli Xuebao (Acta Physica Sinica) 30, 1383 (1981) Wuli Xuebao (Acta Physica Sinica) 30, 234 (1981) Wuli (Physics) 3,395 (1980) Wuli Xuebao (Acta Physica Sinica) 28, 518 (1979) Wuli Xuebao (Acta Physica Sinica) 30, 1219 (1981) Zhongguo Kexue (Scientia Sinica) Ser A, No.4, 379 (1985) Introduction 224 High temperature phase equilibria and phase diagrams A Β A C FIG 7.9 G 33 F Non-equilibrium crystallization in glass depending on whether TÍO2 or Zr02 was added as the devitrification catalyst This was followed by crystallization of a metastable j?-quartz solid solution, and finally the stable phase assemblage of )?-spodumene solid solution, cordierite and cristobalite formed at the expense of the metastable j5-quartz solid solution phase Another example of a metastable intermediate devitrified phase was observed in the N a A I O 2Si02-Na3K02 A I O 4SÍO2 glass with the addition of titania as a nucleation catalyst When devitrification took place at 800°C, carnegieite separated out first It is a high temperature form with an open structure, presumably more similar to the host glass lattice than the low temperature form nepheline During heat treatment at 1100°C or lower temperatures, metastable carnegieite transforms to the stable form nepheline Similar metastable devitrification was also found in unary SÍO2 glass The devitrified glass consists of both the low and high forms of cristobalite Presumably the meta-equilibrium coexistence was a result of tensile stresses developed during cooling Meta-equilibria and meta-equilibria phase diagrams 2 7.4 SOLID-SOLID META-EQUILIBRIA 7.4.1 Metastable polymorphic transformation The polymorphic transformation involving structural reconstruction (refer to section 6.1.5) is often kinetically inhibited when decreasing the temperature or relaxing the pressure because of the low mobility in the solid phase Thus the high temperature or high pressure forms may be permanently kept as metastable phases at low temperatures and normal atmospheric pressure The SÍO2 unary system offers a typical example involving a lot of metastable phase transformations According to structural characteristics, two types of polymorphic transformations in the system can be distinguished The first involves only small displacement of the structural unit, the SÍO4 tetrahedron, thus resulting in a small activation energy, as with the low-high quartz transformation which is fast and reversible On the other hand, the second type of transformation involving structural reconstruction, such as from quartz to tridymite or cristobalite, is very slow and irreversible The high temperature forms of tridymite and cristobalite always remain as metastable phases through the quartz-tridymite and quartz-cristobalite transition points, and change into their metastable low temperature forms during further cooling Figure 7.10 gives a detailed pattern of the stable and metastable transformations in the SÍO2 unary system 7.4.2 M e t a s t a b l e solid solution When forming a sohd solution, the total free energy of the system decreases since a mixing free energy term is added At a given temperature the free energy of a solid solution or high solubility phase is often lower (1Γ)23Κ) Low «4(5K HiRh temperature( ¿? ) ===^temperature( quartz quartz (SiO.W) (l()i)3K) (19Γ>;3Κ) Η)9ϋΚ "I I 1743K High temperature: TridymiteVlLiquid cristobalite jf(74«K) • (173K ~Γ,1Γ)Κ) (Tridymite V ) (Glass) Low |( 183K) temperature cristobalite (TridymitelV^ j|(13(5K) ( T r i d y m i t e 111) j (3i)()K) ; Tridymite 11 ) |(337K) ^Tridymitel ) FIG 7.10 Stable and metastable phases and phase transition in SÍO2 system Bracket indicates metastable phase and metastable transition 226 High temperature phase equilibria and phase diagrams 00 FIG 7.11 (h) Solid solution and phase transition temperature than that of a pure or low solubility phase in a given system Figure 7.11 illustrates how to change the stabihty relationship of phases owing to the sohd solution formation, α and β are the low and high temperature forms respectively, Τ^β is the transition temperature between them As β forms a solid solution, the transition points shifts to Γ^^, Τ^β() FIG 7.16 A l j O j - S i O j equilibrium and meta-equilibrium phase diagram calculated using cationic (atomic) sublattice structural model Dashed line refers to meta-equilibrium conditions REFERENCES Han Wen Long and K u o Chu Kun, Guisuanyan Xuebao, 4, 211 (1965) Han Wen Long, Huang Yu Zhen, K u o Chu Kun and Yen Tung Sheng, Kexue Tongbao, 26, 712 (1981) K u o Chu Kun, Huang Yu Zhen, Huang Yuan M o u and Yen Tung Sheng, Kexue Tongbao, 26, 798 (1981) T S Yan, C K K u o , W L Han, Y H Qiu and Y Z Huang, J Amer Ceram Soc 66, 860 (1983) M Imaoka, Advances in Glass Technology, Compiled by the American Ceramic Society, p 149, Plenum Press (1962) M A Bezborodov, N M Bobkova, S M Brekhovskikh, N N Ermolennko, E E M a z o and E A Porai-Koshits, Diagrammy Steklobraznykh Sistem, Redaktsionno-Izdatel'skii Otdel B P ! im L V Stahna, Moskva (1959) Jiang Zhong Hong, Guisuanyan Xuebao, 9, 323 (1981) T P Seward, III, Phase Diagrams, Materials Science and Technology, I (1970), A M Alper (ed.), p 295, Academic Press Li Jai Zhi, Guisuanyan Xuebao, 279 (1979) 10 G H Beall, B R Karstetter and H L Rittler, J Amer Ceram Soc 50, 181 (1967) 11 D A Duke, J F MacDowell and B R Karstetter, J Amer Ceram Soc 50, 67 (1967) 12 F E Wagstaff, Phys Chem Glasses, 10, 50 (1969) 13 T P Seward, III, D R Uhlmann and D Turnbull, J Amer Ceram Soc , 278 (1968) 14 J C Baker and J W Calm, Solidification, p 23, Amer Soc Metals, Metals Park (1971) 15 A K Sinna, B C Geissen and D E Polk, Treatise on Solid State Chemistry, v o l , N B Hannay (ed.), p 1, Plenum Press (1976) 16 J Oroshnik and J Kraitchman, J Electrochem Soc 115, 649 (1968) 17 W A Plishkin and H S Lehman, J Electrochem Soc 112, 1013 (1965) 18 N Goldsmith and W Kern, RCA Rev 28, 153 (1967) 19 K Strater, RCA Rev 29, 618 (1968) 20 B E Deal, P J Fleming and P L Castro, J Electrochem Soc 115, 300 (1968) 236 High temperature phase equilibria and phase diagrams 21 S Yamazaki, K Wada and I Taniguchi, Japan J Appl Phys 9, 1467 (1967) 22 T L Chu, J R Szedon and C H Lee, J Electrochem Soc 115, 318 (1968) 23 S R Nagel, J B MacChesney and K L Walker, IEEE J Quantum Electronics Q E - , (1982) 24 Zhang Ying Hua, G a o Xin Hua and Yan Yi Min, Tezhong Boli, 1, 13 (1984) 25 J P D e Neufville, S C Moss and S R Ovshinsky, J Non-Cryst Solids, 13, 191 (1974) 26 O K Shavalina, B A Baum and P V Gel'd, Izv AN SSSR, Neorg Mater 7,1864 (1971) 27 R K Waits, J Vac Sei Technol 6, 308 (1969) 28 J C Suits, Phys Rev 131, 588 (1963) 29 S Fujime, Japan J Appl Phys 5, 643 (1966) Index Analytical expression 118 Atmospheric control 94 Bond type Mass spectrometry 92 Melting behaviour 43 compound 28 Methods dynamic 78 sol-gel 67 static quenching 72 Microscopy 83 optical 99 Miscellaneous methods 204 Calculation strategy 153 Compositional points 108 Crystallization paths 43 Data collection 154 Optical pyrometer 70 Phase boundaries 118 condensed 21, 37 composition 114 diagrams 2, 12 binary 140 equihbria 12 identification 99 metastable 228 rule 13 transitions 203, 205, 208, 210 dilatational 204 Polymorphism 20 transition 196, 201 Projection parallel 127 perspective 126 Electron microprobe analysis 102 Electron microscopy 102 Equilibria heterogeneous calculation 148 three-phase 18 two-phase 16 meta- , , 2 , 2 phase diagrams 214, 229 Eutectic point 27 Eutectic surface 57 Glass devitrification 223 formation 221 Hysteresis phenomena 93 199 Quantitative analysis Intermediate compound , Isothermal projections 131 Refractory materials 103 141 Solid Liquid immiscibility 33, 144 -liquid equilibrium 180 -liquid equihbrium 181 solutions , , , 2 , 2 state reaction 66 237 238 Index Space diagram 41 Structural model 172 Systems binary 27, 59 metastable 215 multicomponent 16 one-component 16 quantitative 55 reciprocal 52 ternary 61, 138, 183 Temperature calibration 68, 71 measurement 68 Ternary compound 48 Thermodynamic data , Vapour deposition 68 pressure 89 ... t i o n Data Kuo Chu-Kun High temperature phase equilibria and phase diagrams/ Kuo Chu-Kun, Lin Zu-Xiang, and Yan Dong-Sheng.—Isted p cm Phase rule and equilibrium High temperature chemistry I... Society, Hall and Insley compiled and High temperature phase equilibria and phase diagrams published the first collection of phase diagrams which consisted of mainly the silicate and oxide systems... limited solubility.^ 25 26 High temperature phase equilibria and phase diagrams and are equilibrium phases A similar condition is observed for β phase at temperature T2 When the temperature is further