Tailoring of Mechanical Properties of Si N Ceramics 3 4 NATO ASI Series Advanced Science Institutes Series A Series presenting the results of activities sponsored by the NATO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Lif e Sciences Plenum Publishing Corporation B Physics London and New York C Mathematica l Kluwer Academic Publishers and Physical Sciences Dordrecht, Boston and London D Behavioural and Social Sciences E Applie d Sciences F Compute r and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris and Tokyo I Globa l Environmental Change NATO-PCO-DAAT BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than 30000 contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways: - via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, I-00044 Frascati, Italy. - via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French and German (© WTV GmbH and DATAWARE Technologies Inc. 1989). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium. Series E: Applied Sciences - Vol. 276 Tailoring of Mechanical Properties of Si N Ceramics 3 4 edited by Michael J, Hoffmann and Günter Petzow Max-Planck-Institut für Metallforschung, Institut für Werkstoffwissenschaft, Pulvermetallurgisches Laboratorium, Stuttgart, Germany Springer Science+Business Media, B.V. Proceedings of the NATO Advanced Research Workshop on Tailoring of High Temperature Properties of SiN Ceramics 3 4 Schloss Ringberg / Munich, Germany October 6-9,1993 A C.I.P. Catalogue record for this book is available from the Library of Congress. ISBN 978-94-010-4430-1 ISBN 978-94-011-0992-5 (eBook) DOI 10.1007/978-94-011-0992-5 Printed on acid-free paper All Rights Reserved © 1994 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 1994 Softcover reprint of the hardcover 1st edition 1994 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photo copying, recording or by any information storage and retrieval system, without written permission from the copyright owner. CONTENTS Preface ListofParticipants I. Processingand Densification Colloidal ProcessingofStructurallyReliableSiaN4* 3 F.F. Lange, E.P. Luther SiliconNitrideMaterialsfor EngineApplications * 19 J.G. Heinrich, H. Kriiner HighTemperatureResistant Silicon-NitrideCeramicsbyOptimized 43 Two-StepGas PressureSintering R. Oberacker, G. Grathwohl II. Microstructure- Development, Characterizationand Influence on Mechanical Properties Analysis ofMicrostructuralDevelopment and Mechanical Propertiesof 59 SbN4Ceramics * M.J. Hoffmann 3D-CharacterizationofSinteredMicrostructureswith Prismatic 73 Grains - A Preconditionfor MicrostructuralModellingofSiaN4 Ceramics ** F. Miicklich, J. Ohser, S. Hartmann, M.J. Hoffmann, G. Petzow MicrostructuralContributions to the FractureResistanceofSilicon 87 NitrideCeramics * P.F. Becher, S.L. Hwang, H.T. Lin, T.N. Tiegs Improvement ofStrength and ToughnessofSiliconNitrideCeramics * 101 Y. Tajima, K. Urashima vi III. PhaseDiagrams andSiAlON Composites CalculationofPhaseDiagramsofMulticomponent Systems 113 M. Hillert {3SiAlONTransformation 125 Q';::::: D.P. Thompson High PerformanceSiliconNitrideCompositeCeramicsThroughGrain 137 Boundary and MicrostructuralTailoring T.S. Yen SiAlONCompositeCeramics* 149 Th. Ekstrom IV. Grain BoundaryPhases N.1. PropertiesofOynitrideGlasses Structure, Formation, and Stability ofOxynitrideGlasses 167 R.E. Loehman Rheological BehaviorofYSiAlONGlasses - ItsIncidenceonthe 175 High-TemperatureDeformationofSi3N4CeramicsSinteredwith Al203and Y203Additives T. Rouxel, H. Lemercier, J.-L. Besson Devitrification BehaviorofOxynitrideGlasses 187 St. Hampshire N.2. DevitrificationinSiliconNitrideCeramics Crystallization oftheNanophasein SiliconNitrides 201 R. Raj CrystallizationofGrain Boundary Phasesin SiliconNitrideand 217 SiAlON Ceramics * M.H. Lewis vii High-Temperature PropertiesofYb-Containing Si3N4 233 M.J. Hoffmann Processing, PhaseFormationand CreepBehaviorofSi3N4with YzOa 245 and Al20a H. Schubert, E. Gehrke N.3. AnalysisandCharacterizationofIntergranular GrainBoundaryFilms HighResolutionElectronMicroscopy Studieson SiliconNitride 259 Ceramics • H.-J. Kleebe, M.K. Cinibulk, I. Tanaka, J. Bruley, J.S. Vetrano, M. Rahle Compositionsand ThicknessesofGrain Boundary Films inCa-Doped 275 SiliconNitride Ceramics 1. Tanaka, J. Bruley, H. Gu, M.J. Hoffmann, H.-J. Kleebe, R.M. Cannon, D.R. Clarke, M. Rahle TheIntergranularFilmin SiliconNitrideCeramics: ADiffuseInterface 291 Approach D.R. Clarke V. HighTemperature Properties CreepDamageMechanisms inSbN4 305 S.M. Wiederhorn, W.E. Luecke, B.J. Hockey, G.G. Long CreepMechanismsin SiliconNitride Ceramics 327 D.S. Wilkinson TensileCreepRuptureand Subcritical CrackGrowthofSiliconNitride 339 T.Ohji Internal Stresses in SiliconNitrideandTheirInfluenceonMechanical 353 Behavior W. Pompe, H. Kessler CyclicFatigue-CrackGrowth in SiaN4-Ceramics 365 R.H. Dauskardt viii Subcritical CrackGrowthofSi3N4underThermalLoadingbyLight 379 Irradiation G.A. Schneider Subcritical CrackGrowthResistanceinSiliconNitrideCeramics 389 1. Tanaka VI. Mechanical PerformanceandApplications FractureBehaviorofSiliconNitrideat ElevatedTemperatures • 403 M. Matsui, M. Masuda Mechanical Performanceofa CommercialSiliconNitride Pre-Exposed 415 toa SulphidizingAtmosphereat HighTemperature C. Saraiva Martins, M. Steen, J. Bressers, 1. GuerraRosa CeramicsforEngines • 429 K.D. Morgenthaler, H. Buh] Fabricationand HighTemperaturePropertiesofSiliconNitride 443 Ceramics withTransitionMetalSilicidesDispersion Y. Tajima, K. Mizuno, K. Matsubara, M. Watanabe AuthorIndex 451 Subject Index 453 •Presentedas PlenaryLectureat SiliconNitride93, Stuttgart. ..Not orally presentedat the Workshop. PREFACE Significantprogresshasbeenmadeinrecentyears indevelopingsiliconnitrideceramics. The advances that have been achieved are mainly based on an increasing understanding of processing and microstructure-properties relationships. New analytical methods and high resolution transmission electron microscopy (HRTEM) coupled with extensive phase equilibria studies have provided new insights into the grain boundary region and offer the possibility to tailor the microstructure for specific applications. Because ofthe anticipated break-through in industrial applications there are still considerablt; research activities at industriallaboratoriesaswellasotherresearchcentres. Thisvolume presentsthecontributionstothe internationalworkshop "TailoringofHigh Temperature Properties ofSi3N4-Ceramics" with 60 participants from 12 countries held on 6th - 9th October 1993 at SchloB Ringberg in Germany, the conference site ofthe Max Planck-Society. Additionally, it contains all invited papers ofthe International Conference "Silicon Nitride 93" held before the workshop on 4th - 6th October 1993 in Stuttgart/Germany. The book covers all recent research activities on silicon nitride ceramics andgivesanoverviewwithrespecttorecentdevelopments. The presented papers are divided into six main chapters: the topics of the first two chapters are mainly covered bycontributions presented at "SiliconNitride 93" and include a detailedanalysisofthe microstructure-propertiesrelationshipsatroom temperature. Thethird chapter demonstrates the importance of phase diagrams for silicon nitride ceramics and discusses the potential of SiAION ceramics. The largest space is taken up by the chapter "GrainBoundaryPhases"whichexposespropertiesofoxynitrideglasses,thecrystallizationof amorphous phases in silicon nitride ceramics, and the analysis and characterization of intergranular grain boundary films. Recent investigations ofthe high temperature properties suchas creep behaviour, fatigue, and subcritical crackgrowth are introduced inchapterfive. Thelastchapterdealswiththemechanicalperformanceandpotentialapplications. A workshop can not suceed without the contribution ofa number ofpeople. Therefore, the organizers would like to acknowledge the session chairmen D.R. Clarke, T.Y. Tien, F.F. Lange, R. Raj, W. Pompe, P.F. Becher, and RJ. Brookfor keeping the sessions movingand for promoting livelydiscussions. We especially express ourgraditude to the chairman ofthe final discussion R.M. Cannon who also helped us to prepare the workshop programme. Finallywe would liketo thankJutta Weber-Bock for herefficient handlingofthe secretarial workinvolvedinpreparingtheprogrammeandeditingtheproceedings. The organizers also gratefullyacknowledge the financial support provided by: Deutsche Forschungsgemeinschaft, Bonn Germany; Max-Planck-Gesellschaft, Munich Germany; NATOScientificAffairsDivision,BrusselsBelgium. Stuttgart MJ. Hoffmann June 1994 G. Petzow ix ListofParticipants including List ofInvitedSpeakers, SiliconNitride93 Prof.Dr. FritzAldinger, Max- Planck-Institut fUr Metallforschung, Institut fUr Werkstoffwissenschaft, PML, Heisenbergstr. 5, D - 70569Stuttgart, GERMANY Dr.-Ing. UlrichBast, SiemensAG, ZFEBTMR23, Otto-Hahn-Ring 6, D - 81739Munchen, GERMANY Dr. PaulBecher*, OakRidgeNationalLaboratory, Metals & CeramicsDivision, Box2008, OakRidge, TN37831-6068, USA Dr. WolfgangBraue, German AerospaceResearchEstabl. (DLR), MaterialsResearch .Institute, Porz-Wahnheide, LinderH6he, D - 51147K6ln, GERMANY Prof.Dr.RJ. Brook, UniversityofOxford, Department ofMaterials, ParksRoad, Oxford OX1 3PH, ENGLAND Dr. RowlandM. Cannon, UniversityofCalifornia, LBL, HearstMiningBldg., Berkeley, CA94720, USA Prof. I-WeiChen, University ofMichigan, Dept ofMaterialsScience & Eng., Dow2086, 2300Hyward St, Ann Arbor, MI 48109-2136, USA Prof.Dr.D.R Clarke, University ofCalifornia, Dept. ofMaterialsEng. III, SantaBarbara, CA93106, USA Dr. ReinholdIiDauskardt, StanfordUniversity, Dept. ofMaterials Science& Engineering, Stanford, CA94305-2205, USA Dr. C.Dewitte, Development Engineer, NGK CeramicsEuropeS.A., Rue des Azalees 1, B - 7331 Baudour, BELGIUM Dr. ThommyEkstrom*, University ofStockholm, Arrhenius Laboratory, Inorganic Chemistry, S - 10691 Stockholm, SWEDEN xj