Better Ceramics Through Chemistry...

Better Ceramics Through Chemistry V

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Cambridge University Press978-1-107-40965-1 - Materials Research Society Symposium Proceedings: Volume 271:Better Ceramics Through Chemistry VEditors: Mark J. Hampden-Smith, Walter G. Klemperer and C. Jeffrey BrinkerFrontmatterMore information

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MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS VOLUME 271

Better Ceramics Through Chemistry V

Symposium held April 27-May 1, 1992, San Francisco, California, U.S.A.

EDITORS:

Mark J. Hampden-SmithUniversity of New Mexico

Albuquerque, New Mexico, U.S.A.

Walter G. KlempererUniversity of Illinois

Urbana, Illinois, U.S.A.

C. Jeffrey BrinkerSandia National Laboratories

Albuquerque, New Mexico, U.S.A.

MATERIALS RESEARCH SOCIETYPittsburgh, Pennsylvania






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Contents

PREFACE xv

MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS xvi

PART I: MOLECULAR ROUTES TO CERAMIC MATERIALS

*NEW CHEMISTRY FOR THE SOL-GEL PROCESS: ACETONE AS A NEWCONDENSATION REAGENT 3

Subhash C Goel, Michael Y. Chiang, Patrick C. Gibbons, andWilliam E. Buhro

*HETEROMETALLIC AGGREGATES AS INTERMEDIATES ON THEMOLECULAR ROUTES TO MULTICOMPONENT OXIDES 15

Liliane G. Hubert-Pfalzgraf

FURTHER STUDIES ON ALUMINUM OXOALKOXIDE CLUSTERS 27R.A. Sinclair, M.L. Brostrom, W.B. Gleason, and R.A. Newmark

STUDIES ON THE FORMATION OF TIN(IV) OXYGEN COMPOUNDSBY SOL-GEL-PROCESS 33

H. Reuter, M. Kremser, D. Schroder, and M. Jansen

HYDROLYSIS-CONDENSATION OF ALKYLTIN-TRIALKOXIDES 45Francois Ribot, F. Banse, and C. Sanchez

HYDROLYSIS AND CONDENSATION OF MODIFIED TIN(IV) ALKOXIDECOMPOUNDS TO FORM CONTROLLED POROSITY MATERIALS 51

Christophe Roger, M.J. Hampden-Smith, and C.J. Brinker

POLYNUCLEAR TITANIUM OXOALKOXIDES: MOLECULAR BUILDINGBLOCKS FOR NEW MATERIALS? 57

Y.W. Chen, W.G. Klemperer, and C.W. Park

RAMAN AND SURFACE ENHANCED RAMAN SPECTROSCOPY OFTITANIUM CARBOXYLATES 65

Beatrice A. Van Vlierberge-Torgerson, Dilum Dunuwila, andKris A. Berglund

HYDROLYSIS OF ZIRCONIUM PROPOXIDE BY AN ESTERIFICATIONREACTION 71

I. Laaziz, A. Larbot, C. Guizard, A. Julbe, and L. Cot

MOLECULAR DESIGN OF CARBOXYLIC PRECURSORS FOR ZIRCONIA 77Allen W. Apblett, Jin Lei, and Galina D. Georgeva

PROPERTIES OF ZrO2 GELS PREPARED BY CONTROLLED CHEMICALMODIFICATION METOOD OF ALKOXIDE 83

Hisao Suzuki, Hajime Saito, and Hiroaki Hayashi

SINGLE-COMPONENT ROUTES TO PEROVSKITE PHASE MIXED METALOXIDES 89

Clive D. Chandler, M.J. Hampden-Smith, and C.J. Brinker

SYNTHESIS OF BARIUM TITANATE BY A BASIC pH PECHINI PROCESS 95Suresh Kumar and Gary L. Messing

•Invited Paper






PREPARATION OF STRONTIUM TITANATE POWDERS BYDECOMPOSITION OF POLYMERIC PRECURSORS 101

S.L. Peschke, M. Ciftcioglu, D.H. Doughty, and J.A. Voigt

SYNTHESIS, STRUCTURE, AND CHARACTERIZATION OFLa^Ba TiO? (0 <, x < 1) 107

Joseph E. Sunstrom IV and Susan M. Kauzlarich

COMBUSTION SYNTHESIS OF Sr-SUBSTITUTE LaCo04Fe06O3POWDERS 113

J.J. Kingsley, L.A. Chick, G.W. Coffey, D.E. McCready, andL.R. Pederson

SYNTHESIS OF FERROELECTRIC PEROVSKITES THROUGH AQUEOUSSOLUTIONS TECHNIQUES 121

G. Guzman-Martel, M.A. Aegerter, and P. Barboux

NEW GROUP 2 COMPOUNDS USEFUL FOR PREPARATION OF THINFILMS OF ELECTRONIC CERAMICS 127

William S. Rees, Jr., Kerstin A. Dippel, Michael W. Cards,Celia R. Caballero, Debra A. Moreno, and Werner Hesse

STABILIZATION OF METAL ALKOXIDES (M = Ba, Cu) BYALKANOLAMINES 135

L.G. Hubert-Pfalzgraf, M.C. Massiani, J.C. Daran, andJ. Vaissermann

SOLID STATE STRUCTURES, DECOMPOSITION PATHWAYS, ANDVAPOR PHASE BY-PRODUCTS OF Y(acac)3 TYPE OMVPEPRECURSORS FOR THIN FILMS OF YTTRIUM-CONTAINING CERAMICMATERIALS 141

William S. Rees, Jr., Henry A. Luten, Michael W. Cards,Eric J. Doskocil, and Virgil L. Goedken

AGGREGATION AND HYDROLYSIS REACTIONS OF BISMUTHALKOXIDES 149

Kenton H. Whitmire, Carolyn M. Jones, Michael D. Burkart,J. Chris Hutchison, and Andrew L. McKnight

SOL-GEL SYNTHESIS OF YBasOuO? . USING YTTRIUM, BARIUM,AND COPPER POLYETHER ALKOXIDE PRECURSORS 155

Catherine J. Page, Carol S. Houk, and Gary A. Burgoine

PREPARATION OF BSCCO PRECURSORS BY WATER EXTRACTIONVARIANT OF SOL-GEL PROCESS 161

A. Deptuta, W. Lada, T. Olczak, and A. Di Bartolomeo

FROM CERAMICS TO SUPERCONDUCTORS: RAPID MATERIALSSYNTHESIS BY SOLID-STATE METATHESIS REACTIONS 169

Randolph E. Treece, Edward G. Gillan, Richard M. Jacubinas,John B. Wiley, and Richard B. Kaner

CHARACTERIZATIONS OF SOL-GEL CORDIERITE PRECURSORS 175Yun Fa Chen, Said El Hadigui, and Serge Vilminot

SOL-GEL PROCESS FROM HETEROBIMETALLIC ALKOXIDES TOINCORPORATE LANTHANIDES IN AN ALUMINA MATRIX 181

Chaitanya K. Narula

SYNTHESIS OF NEW COMPOUNDS BY ION-EXCHANGE REACTIONS 187M.E. Villafuerte-Castrej<5n, and A. Aragdn-Pifia






COMPARATIVE STUDY OF THE SOL-GEL AND METALLO-ORGANICDECOMPOSITION (MOD) PROCESSES FOR THE PREPARATION OFINORGANIC MATERIALS 193

Gustavo R. Paz-Pujalt, W. Nie, and C. Lurin

PART II: PARTICULATE AND POLYMERIC SOLS

*COMPLEXATION OF Zr(IV) PRECURSORS IN AQUEOUS SOLUTIONS 201J. Livage, M. Chatry, M. Henry, and F. Taulelle

FRACTAL GROWTH DURING GELATION 213Edward J.A. Pope

SOLVENT QUALITY EFFECTS IN SOL-GEL PROCESSING 219Joseph K. Bailey

A RAMAN SPECTROSCOPIC STUDY OF THE INITIAL STAGES OFHYDROLYSIS OF TETRAETHOXYSILANE 225

J.D. Barrie and K.A. Aitchison

SILICON-29 NMR STUDY ON THE INITIAL STAGE OF THE CO-HYDROLYSIS OF TETRAETHOXYSILANE AND METHYLTRIETHOXY-SILANE 231

Yoshiyuki Sugahara, Yoichi Tanaka, Shuji Sato, Kazuyuki Kuroda,and Chuzo Kato

STRUCTURAL CHARACTERIZATION OF GELS PREPARED FROM CO-HYDROLYSIS OF TETRAETHOXYSILANE AND DIMETHYLDIETHOXY-SILANE 237

Florence Babonneau, Laurence Bois, and Jacques Livage

ELECTRONEGATIVITY-BASED COMPUTATION OF 29Si CHEMICALSHIFTS 243

M. Henry, C. Gerardin, and F. Taulelle

RAMAN AND INFRARED STUDY OF METAL ALKOXIDES DURING SOL-GEL PROCESS 249

O. Poncelet, J-C. Robert, and J. Guilment

REACTION KINETICS FOR THE HYDROLYSIS OF TITANIUMISOPROPOXIDE CARBOXYLATE COMPLEXES 257

Charles D. Gagliardi, Dilum Dunuwila, Beatrice A. VanVlierberge-Torgerson, and Kris A. Berglund

USAXS AND X-RAY MICROSCOPY INVESTIGATIONS ON SILICA ANDPRECURSORS OF ZEOLITES 263

Theo P.M. Beelen, Wim H. Dokter, Harold F. van Garderen,Rutger A. van Santen, Mike T. Browne, and Graeme R. Morrison

RHEOLOGY OF ZIRCONIA-ALUMINA GELCASTING SLURRIES 269A. Bleier, O.O. Omatete, and C.G. Westmoreland

PRODUCTION OF SPHERICAL POWDERS OF INORGANIC COMPOUNDSBY WATER EXTRACTION VARIANT OF SOL-GEL PROCESS 277

A. Deptula, J. Rebandel, W. Drozda, W. Lada, and T. Olczak

NOVEL PRECIPITATION ROUTE TO SILICA GRAIN 285Barbara Simms and Tom Gallo

*Invited Paper

VII






THEORETICAL AND EXPERIMENTAL INVESTIGATIONS OF THEGROWTH OF SILICA AND TITANIA PARTICLES IN LOW MOLECULARWEIGHT ALCOHOLS 291

Michael T. Harris, Osman A. Basaran, and Charles H. Byers

THE FAST SOL-GEL SYNTHETIC ROUTE TO SUPPORTED GLASSFILMS: SYNTHETIC FEATURES, SCOPE, APPLICATIONS ANDMECHANISTIC STUDIES 297

Y. Haruvy and S.E. Webber

STABILITY OF AQUEOUS SUSPENSIONS OF HIGH SURFACE AREAZIRCONIA POWDERS IN THE PRESENCE OF POLYACRYLIC ACIDPOLYELECTROLYTE 303

Michel M.R. Boutz, R.J.M. Olde Scholtenhuis, A.J.A. Winnubst,and A.J. Burggraaf

PRODUCTION OF SOLS FROM AGGREGATED TITANIA PRECIPITATES 309John R. Bartlett and James L. Woolfrey

PART III: CERAMIC THIN FILMS,COATINGS, MEMBRANES, AND FIBERS

*STRESS AND PHASE TRANSFORMATION PHENOMENA IN OXIDEFILMS: REAL-TIME SPECTROSCOPIC MEASUREMENTS 319

Gregory J. Exarhos and Nancy J. Hess

•CHEMICAL PROCESSING OF FERROELECTRIC NIOBATES EPITAXIALFILMS 331

Shin-Ichi Hirano, Toshinobu Yogo, Koichi Kikuta, Hisanobu Urahata,Yasuhide Isobe, Toshiyuki Morishita, Koji Ogiso, and Yasuhiro Ito

•CHEMICAL PROCESSING AND PROPERTIES OF NANOCRYSTALLINEBaTiO3 339

Z. Xu, H.K. Chae, M.H. Frey, and D.A. Payne

OPTIMIZATION OF SOL-GEL DERIVED PZT THIN FILMS BY THEINCORPORATION OF EXCESS PBO 345

G. Teowee, J.M. Boulton, and D.R. Uhlmann

ELECTRICAL AND OPTICAL PROPERTIES OF SOL-GEL PROCESSEDPb(Zr,Ti)O3 FILMS 351

S.D. Ramamurthi, S.L. Swartz, K.R. Marken, J.R. Busch, andV.E. Wood

ELECTRICAL PROPERTIES OF CRYSTALLINE AND AMORPHOUSPbCZr^j^Oj THIN FILMS PREPARED BY THE SOL-GEL TECHNIQUE 359

Yuhuan Xu, Chih-Hsing Cheng, Ren Xu, and John D. Mackenzie

PREPARATION OF BaTiO3 AND PbTiO3 THIN FILMS ON BaPbO3SUBSTRATES BY THE SOL-GEL METHOD AND THEIR PROPERTIES 365

M. Kuwabara, T. Kuroda, S. Takahashi, and T. Azuma

LOW TEMPERATURE FORMATION OF FERROELECTRIC THIN FILMS 371Chi Kong Kwok and Seshu B. Desu

MICROSTRUCTURAL VARIATIONS IN SOL-GEL PROCESSED LITHIUMNIOBATE THIN FILMS 377

Vikram Joshi, Grace K. Goo, and Martha L. Mecartney

•Invited Paper






THE GROWTH OF SINGLE CRYSTAL-LIKE AND POLYCRYSTALKNbO3 FILMS VIA SOL-GEL PROCESS 383

Chih-Hsing Cheng, Yuhuan Xu, John D. Mackenzie, Jie Zhang,and LeRoy Eyring

PREPARATION AND CHARACTERIZATION OF SOL-GEL THIN FILMSOF KTiOPO4 389

Mark A. Harmer and Mark G. Roelofs

SYNTHESIS OF CUPRATE BASED HIGH-TC SUPERCONDUCTORS BYPOLYMERIZED COMPLEX METHOD 395

Masato Kakihana, Masahiro Yoshimura, Hiromasa Mazaki,Hiroshi Yasuoka, and Lars Borj Esson

APPLICATION OF ETHANOLAMINE METHOD FOR THE PREPARATIONOF INDIUM OXIDE-BASED SOLS AND FILMS 401

Yasutaka Takahashi, Hideo Hayashi, and Yutaka Ohya

GROWTH OF ORIENTED TIN OXIDE THIN FILMS FROM ANORGANOTIN COMPOUND BY SPRAY PYROLYSIS 407

Isao Yagi and Shoji Kaneko

SOL-GEL MULTILAYERS APPLIED BY A MENISCUS COATINGPROCESS 413

Jerald A. Britten and Ian M. Thomas

PHASE TRANSFORMATIONS IN SOL-GEL YAG FILMS 421R.S. Hay

STRUCTURAL AND ELECTRICAL PROPERTIES OF Mn-Co-Ni-OTHIN FILMS PREPARED BY DIP-COATING TECHNIQUE 429

Shoji Kaneko, Naoto Mazuka, and Tamotsu Yamada

MOLECULAR RECOGNITION ON ACOUSTIC WAVE DEVICES:MODIFIED ZEOLITE-SILICA THIN FILMS WITH TAILOREDADSORPTION PROPERTIES 435

Yongan Yan, Thomas Bein, Kelly D. Brown, Ray Forrister, andJeffrey Brinker

STRUCTURE OF THIN SOL-GEL COATINGS NEAR THE SURFACE OFSUBSTRATES 443

Hiroshi Hirashima and Takao Kusaka

LASER DENSIFICATION OF SOL-GEL DERIVED TiO2 - THIN FILMS 449N. Arfsten, B. Lintner, M. Heming, O. Anderson, and C.R. Otter-Mann

"CRYSTALLINE THIN AND/OR THICK FILM OF PERVOSKITE-TYPEOXIDES BY HYDROTHERMAL ELECTROCHEMICAL TECHNIQUES 457

Masahiro Yoshimura

ELECTROPHORETIC DEPOSITION OF SOL-GEL-DERIVED CERAMICCOATINGS 465

Yining Zhang, C. Jeffrey Brinker, and Richard M. Crooks

CORROSION RESISTANT ZrO2 SOL-GEL COATING ON STAINLESSSTEEL 471

M. Atik and M.A. Aegerter

PROTECTIVE ZIRCONIA THIN FILMS ON METAL SUBSTRATES 477Andrea Tomasi, Paolo Scardi, and Fabio Marchetti

•Invited Paper






PLASMA SPRAYED ALUMINA-TITANIA COATINGS 485T.J. Steeper, A.J. Rotolico, J.E. Nerz, W.L. Riggs II,D.J. Varacalle, Jr., and G.C. Wilson

A MICROPOROUS SILICA MEMBRANE 493Wilhelm F. Maier and Herbert O. Schramm

THERMAL STABILITY OF SUPPORTED TITANIA MEMBRANES 499Krishnankutty-Nair P. Kumar, V.T. Zaspalis, F.F.M. De Mul,Klaas Keizer, and Anthonie J. Burggraaf

PREPARATION AND CHARACTERIZATION OF MICROPOROUS SOL-GELDERIVED CERAMIC MEMBRANES FOR GAS SEPARATION APPLICATIONS 505

R.S.A. De Lange, J.H.A. Hekkink, K. Keizer, and A.J. Burggraaf

IMOGOLITE AS A MATERIAL FOR FABRICATION OF INORGANICMEMBRANES 511

Jeffrey C. Huling, Joseph K. Bailey, Douglas M. Smith, andC. Jeffrey Brinker

SOL-GEL DERIVED PZT FIBERS 517J.M. Boulton, G. Teowee, and D.R. Uhlmann

PART IV: AGING, DRYING, AND CONSOLIDATION OF GELS

•MECHANICS OF GELS 527George W. Scherer

THE EFFECT OF GEL AGING ON THE PHYSICAL AND OPTICALPROPERTIES OF A GEL-DERIVED GRIN GLASS 535

Mark A. Banash, Tessie M. Che, J. Brian Caldwell, Robert M. Mininni,Paul R. Soskey, Victor N. Warden, and Hui H. Chin

SOL-GEL FILMS WITH TAILORED MICROSTRUCTURES 541Deborah L. Logan, Carol S. Ashley, and C. Jeffrey Brinker

PORE SIZE AND SURFACE TEXTURE MODIFICATION OF SILICAVIA TRIALKYLSILYLATION 547

Duen-Wu Hua and Douglas M. Smith

PORE STRUCTURE EVOLUTION OF SILICA GEL DURING AGING/DRYING: EFFECT OF SURFACE TENSION 553

Ravindra Deshpande, Douglas M. Smith, and C. Jeffrey Brinker

INTERPRETATION OF AEROGEL SHRINKAGE DURING DRYING 559Bharath Rangarajan and Carl T. Lira

PREPARATION OF LOW-DENSITY AEROGELS AT AMBIENT PRESSURE 567Douglas M. Smith, Ravindra Deshpande, and C. Jeffrey Brinker

PREPARATON AND PHYSICAL PROPERTIES OF V2O5 AEROGELS 573Hiroshi Hirashima and Kazumi Sudoh

PART V: CERAMIC COMPOSITES

LEUCITE-POLLUCITE GLASS CERAMICS: A NEW FAMILY OFREFRACTORY MATERIALS WITH ADJUSTABLE THERMAL-EXPANSION 581

R.L. Bedard, R.W. Broach, and E.M. Flanigen

•Invited Paper






SINTERING PROCESS AND MECHANICAL PROPERTIES FOR OXIDE-BASED NANOCOMPOSITES 589

Koichi Niihara, Atsushi Nakahira, and Masahiro Inoue

AMORPHIZATION AT THE METAL-CERAMIC INTERFACE IN Nb—A12O3COMPOSITE THROUGH EXTENSIVE INTERPHASE DIFFUSION 595

Abhijit Ray and Shyam K. Samanta

MODELING AND EXPERIMENTAL INVESTIGATIONS OF PRESSUREINFILTRATION OF SOL-GEL PROCESSED 3-D CERAMIC MATRIXCOMPOSITES 601

Hsien-Kuang Liu and Azar Parvizi-Majidi

PART VI: HYBRID ORGANIC/INORGANIC MATERIALS

*MACRO-DEFECT-FREE CEMENT: A NOVEL ORGANOCERAMICCOMPOSITE 609

J. Francis Young and M. Berg

*METAL COMPLEXES IN OXIDIC MATRICES 621Ulrich Schubert, Boris Breitscheidel, Hermann Buhler, Christian Egger,and Wlodzimierz Urbaniak

FORMATION OF HIGHLY DISPERSED METALS ON FUNCTIONALIZEDSILICA SUPPORTS 633

Francois Rousseau, Z. Duan, M.J. Hampden-Smith, and A. Datye

ENERGY TRANSFER BETWEEN Eu2+, Eu3+ AND Rh6G IN SILICA,ZIRCONIA AND ALUMINA GELS 639

W. Nie, B. Dunn, C. Sanchez, and P. Griesmar

DIFFUSION OF CARBON MONOXIDE IN METALORGANIC THIN FILMSDERIVED FROM TITANIUM ALKOXIDE CARBOXYLATES 645

Charles D. Gagliardi, Dilum Dunuwila, C.K. Chang, andKris A. Berglund

RIGIDOCHROMISM AS A PROBE OF GELATION, AGING, AND DRYINGIN SOL-GEL DERIVED ORMOSILS 651

Stephen D. Hanna, Bruce Dunn, and Jeffrey I. Zink

SYNTHESIS AND CHARACTERIZATION OF ORGANIC DYE DOPEDSILICA GLASSES 657

Ilzoo Lee, Josephine Covino, and Michael D. Seltzer

DENSE XEROGEL MATRICES AND FILMS FOR OPTICAL MEMORY 663F. Chaput, J.P. Boilot, F. Devreux, M. Canva, P. Georges, andA. Brun

TAILORING OF TRANSITION METAL ALKOXIDES VIA COMPLEXATIONFOR THE SYNTHESIS OF HYBRID ORGANIC-INORGANIC SOLS ANDGELS 669

C. Sanchez, M. In, P. Toledano, and P. Griesmar

STRUCTURE-RELATED MECHANICAL PROPERTIES OF ORMOSILS BYSOL-GEL PROCESS 681

Yi Hu and John D. Mackenzie

MONITORING OF HETEROPOLYSILOXANE THIN FILM PROPERTIESUSING RHEOLOGICAL AND ACOUSTIC CHARACTERIZATION METHODS 687

C. Guizard, P. Lacan, J.M. Saurel, F. Hajoub, and L. Cot

•Invited Paper






THE EFFECT OF ULTRASONIC RADIATION ON GELATION ANDPROPERTIES OF ORMOSILS 693

Kazuki Morita, Yi Hu, and John D. Mackenzie

PREPARATION OF ARYL-BRIDGED POLYSILSESQUIOXANEAEROGELS 699

Douglas A. Loy, Kenneth J. Shea, and Edward M. Russick

CHARACTERIZATION OF MICROPOROUS SILICA GELS PREPAREDFROM MODIFIED SILICON ALKOXIDES 705

W.G. Fahrenholtz and D.M. Smith

HYPERVALENT SILICONATE MATERIALS. SYNTHESIS ANDCHARACTERIZATION OF NOVEL LADDER AND NETWORK IONOMERS 711

Kenneth J. Shea, Douglas A. Loy, and James H. Small

MULTIFUNCTIONAL (METH) ACRYLATE ALKOXYSILANESA NEW TYPE OF REACTIVE COMPOUNDS 719

H. Wolter, W. Glaubitt, and K. Rose

CHARACTERISATION OF HYDROLYSED ALKOXYSILANES ANDZIRCONIUMALKOXIDES FOR THE DEVELOPMENT OF UV-CURABLESCRATCH RESISTANT COATINGS 725

K. Greiwe, W. Glaubitt, S. Amberg-Schwab, and K. Piana

MULTIFUNCTIONAL ACRYLATE ALKOXYSILANES FOR POLYMERICMATERIALS 731

K. Rose, H. Wolter, and W. Glaubitt

PART VII: NOVEL ROUTES TO NON-OXIDE CERAMICS

•PREPARATION OF NON-OXIDE CERAMICS BY PYROLYSIS OFORGANOMETALLIC PRECURSORS 739

Leonard V. Interrante, Wayde R. Schmidt, Paul S. Marchetti, andGary E. Maciel

CHEMICALLY DESIGNED, UV CURABLE POLYCARBOSILANEPOLYMERS 749

Kevin J. Thome, Stephen E. Johnson, Haixing Zheng,John D. Mackenzie, and M.F. Hawthorne

PROCESSING OF SiC-BASED FIBRES FROM POLYCARBOSILANE 755Vasilios Kalyvas, J.C. Ko, G.C. East, J.E. Mclntyre, B. Rand, andF.L. Riley

POLYMER-DERIVED SILICON CARBIDE FIBERS WITH IMPROVEDTHERMOMECHANICAL STABILITY 761

W. Toreki, C D . Batich, M.D. Sacks, M. Saleem, and G.J. Choi

SYNTHESES, STRUCTURES AND PROPERTIES OF POLYCARBOSILANESFORMED DIRECTLY BY POLYMERIZATION OF ALKENYLSILANES 771

John Masnovi, Xin Y. Bu, Kassahun Beyene, Paula Heimann,Terrence Kacik, A. Harry Andrist, and Frances I. Hurwitz

NMR CHARACTERIZATION OF SILICON CARBIDES ANDCARBONITRIDES. A METHOD FOR QUANTIFYING THE SILICONSITES AND THE FREE CARBON PHASE 777

C. Gerardin, M. Henry, and F. Taulelle

•Invited Paper






HIGH TEMPERATURE STABILITY OF OXYCARBIDE GLASSES 783Hanxi Zhang and Carlo G. Pantano

SILICON OXYCARBIDE GLASSES FROM SOL-GEL PRECURSORS 789F. Babonneau, G.D. Soraru, G. D'Andrea, S. Dire, and L. Bois

THE ROLE OF Si-H FUNCTIONALITY IN OXYCARBIDE GLASSSYNTHESIS 795

Anant K. Singh and Carlo G. Pantano

CHARACTERIZATION OF HIGH SURFACE AREA SILICONOXYNITRIDES 801

Peter W. Lednor, Rene de Ruiter, and Kees A. Emeis

ISOCYANATE-MODIFIED POLYSILAZANES: CONVERSION TOCERAMIC MATERIALS 807

Joanne M. Schwark and Mark J. Sullivan

REACTION SINTERING MECHANISM OF SUBMICROMETER SILICONPOWDER IN NITROGEN 813

Yoshiyuki Yasutomi, Masahisa Sobue, and Jiro Kondo

SYNTHESIS OF ADVANCED CERAMICS IN THE SYSTEMS Si-B-NAND Si-B-N-C EMPLOYING NOVEL PRECURSOR COMPOUNDS 821

H.-P. Baldus, O. Wagner, and M. Jansen

DESIGN AND SYNTHESIS OF CHEMICAL PRECURSORS TO BORONCARBIDE 827

Xiaoguang Yang, Stephen Johnson, M. Frederick Hawthorne,Haixing Zheng, Kevin Thome, and J.D. Mackenzie

ALKYNL SUBSTITUTED CARBORANES AS PRECURSORS TO BORONCARBIDE THIN FILMS, FIBERS AND COMPOSITES 833

Stephen E. Johnson, Xiaoguang Yang, M.F. Hawthorne,Kevin J. Thome, Haixing Zheng, and John D. Mackenzie

BORON CARBIDE NITRIDE DERIVED FROM AMINE-BORANES 839Joachim Bill and Ralf Riedel

POLYMER PRECURSORS FOR ALUMINUM NITRIDE CERAMICS 845James A. Jensen

OPTIMIZATION OF ALUMINUM NITRIDE THERMAL CONDUCTIVITYVIA CONTROLLED POWDER PROCESSING 851

Theresa A. Guiton, James E. Volmering, and Kris K. Killinger

•ELECTROCHEMICAL SYNTHESIS OF ALUMINUM NITRIDE INLIQUID AMMONIA ELECTROLYTE SOLUTIONS 857

Travis Wade, Jongman Park, Gene Garza, Claudia B. Ross,Douglas M. Smith, and Richard M. Crooks

ELECTROCHEMICALLY PREPARED POLYMERIC PRECURSORS FOR THEFORMATION OF NON-OXIDE CERAMICS AND COATINGS 869

Ralph Zahneisen and Christian Riissel

ORGANOMETALLIC PRECURSORS TO VANADIUM AND TITANIUMCARBONITRIDE 875

Francois Laurent, Christophe Daures, Lydie Valade,Robert Choukroun, Jean-Pierre Legros, and Patrick Cassoux

•Invited Paper






NEW ROUTES TO GROUP IVA METAL-NITRIDES 881Chaitanya K. Narula

TITANIUM CARBIDE FROM CARBOXYLIC ACID MODIFIED ALKOXIDES 887Tom Gallo, Carl Greco, Claude Peterson, Frank Cambria, andJohst Burk

PREPARATION OF TITANIUM CARBONITRIDE COATINGS BY THESOL-GEL PROCESS 893

Haixing Zheng, Kris Oka, and John D. Mackenzie

XPS STUDY OF THE NITRIDATION PROCESS OF A POLYTITANO-CARBOSILANE INTO Si-Ti-N-0 CERAMICS 899

G. Granozzi, A. Glisenti, R. Bertoncello, and G.D. Soraru

PART VIII: VAPOR PHASE ROUTES TO OXIDE CERAMICS

*MULTICOMPONENT CERAMIC POWDER GENERATION BY SPRAYPYROLYSIS 907

Shirley W. Lyons, J. Ortega, L.M. Wang, and T.T. Kodas

STRUCTURAL AND THERMAL INVESTIGATIONS ON BARIUM, COPPERAND YTTRIUM MOCVD PRECURSORS 919

Alain Gleizes, Dominique Medus, and Sandrine Sans-Lenain

ELECTRONIC PROPERTIES OF OMVPE GROWN FILMS OFj ^ ON 1M LaAlO3 SUBSTRATES 925illliam S. Rees, Jr., Yusuf S. Hascicek, and Louis R. Testardi

REACTION OF BARIUM BIS(0-DIKETONATE) COMPLEXES WITH THESURFACE OF MAGNESIUM OXIDE 933

R.A. Gardiner, P.S. Kirlin, G.A.M. Hussein, and B.C. Gates

OMCVD ELABORATION AND CHARACTERIZATION OF SILICONCARBIDE AND CARBON-SILICON CARBIDE FILMS FROMORGANOSILICON COMPOUNDS 939

R. Morancho, A. Reynes, M'b. Amjoud, and R. Carles

COMPUTATION, VISUALIZATION, AND CHEMISTRY OF ELECTRICFIELD-ENHANCED PRODUCTION OF CERAMIC PRECURSOR POWDERS 945

Michael T. Harris, Warren G. Sisson, and Osman A. Basaran

EFFECT OF DOPANTS IN VAPOR PHASE SYNTHESIS OF TITANIAPOWDERS 951

M. Kamal Akhtar, S.E. Pratsinis, and S.V.R. Mastrangelo

DEPOSITION OF CERAMIC FILMS BY A NOVEL PULSED-GASMOCVD TECHNIQUE 957

Kenneth A. Aitchison, James D. Barrie, and Joseph Ciofalo

AUTHOR INDEX 963

SUBJECT INDEX 967

•Invited Paper






Preface

The application of chemical principles and practices to ceramic processing hasmushroomed during the past decade, and the Materials Research Society's BetterCeramics Through Chemistry symposia have chronicled this growth biennially. Thepapers in the current volume were presented at the symposium Better Ceramics ThroughChemistry V of the Materials Research Society Spring Meeting on April 27-May 1,1992. Financial support was provided by Air Products and Chemicals Inc., Gelest Lie ,the Office of Naval Research, and Radiant Technology Inc.

As in the previous Better Ceramics Through Chemistry symposia, published as MRSSymposium Volumes 32, 73, 121, and 180, the present volume has as its focus sol-gel processing of oxide ceramics. In addition, however, considerable space is devotedto recent advances in related systems such as metal nitrides, carbides, and borides,polymer precursors, and cement composite materials, as well as other synthesistechniques such as chemical vapor deposition, aerosol routes and electrochemicalprocessing. The volume is designed to provide both a retrospective and a preliminaryview of exciting new results of mutual interest to ceramists and chemists.

M.J. Hampden-SmithW.G. KlempererC.J. Brinker

June, 1992






MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS

Volume 239—Thin Films: Stresses and Mechanical Properties III, W.D. Nix,J.C. Bravman, E. Arzt, L.B. Freund, 1992, ISBN: 1-55899-133-6

Volume 240—Advanced III-V Compound Semiconductor Growth, Processing andDevices, S.J. Pearton, D.K. Sadana, J.M. Zavada, 1992,ISBN: 1-55899-134-4

Volume 241—Low Temperature (LT) GaAs and Related Materials, G.L. Witt,R. Calawa, U. Mishra, E. Weber, 1992, ISBN: 1-55899-135-2

Volume 242—Wide Band Gap Semiconductors, T.D. Moustakas, J.I. Pankove,Y. Hamakawa, 1992, ISBN: 1-55899-136-0

Volume 243—Ferroelectric Thin Films II, A.I. Kingon, E.R. Myers, B. Tuttle, 1992,ISBN: 1-55899-137-9

Volume 244—Optical Waveguide Materials, M.M. Broer, G.H. Sigel, Jr.,R.Th. Kersten, H. Kawazoe, 1992, ISBN: 1-55899-138-7

Volume 245—Advanced Cementitious Systems: Mechanisms and Properties,F.P. Glasser, GJ. McCarthy, J.F. Young, T.O. Mason, P.L. Pratt,1992, ISBN: 1-55899-139-5

Volume 246—Shape-Memory Materials and Phenomena—Fundamental Aspects andApplications, C.T. Liu, H. Kunsmann, K. Otsuka, M. Wuttig, 1992,ISBN: 1-55899-140-9

Volume 247—Electrical, Optical, and Magnetic Properties of Organic Solid StateMaterials, L.Y. Chiang, A.F. Garito, D.J. Sandman, 1992,ISBN: 1-55899-141-7

Volume 248—Complex Fluids, E.B. Sirota, D. Weitz, T. Witten, J. Israelachvili,1992, ISBN: 1-55899-142-5

Volume 249—Synthesis and Processing of Ceramics: Scientific Issues, W.E. Rhine,T.M. Shaw, RJ . Gottschall, Y. Chen, 1992, ISBN: 1-55899-143-3

Volume 250—Chemical Vapor Deposition of Refractory Metals and Ceramics II,T.M. Besmann, B.M. Gallois, J.W. Warren, 1992,ISBN: 1-55899-144-1

Volume 251—Pressure Effects on Materials Processing and Design, K. Ishizaki,E. Hodge, M. Concannon, 1992, ISBN: 1-55899-145-X

Volume 252—Tissue-Inducing Biomaterials, L.G. Cima, E.S. Ron, 1992,ISBN: 1-55899-146-8

Volume 253—Applications of Multiple Scattering Theory to Materials Science,W.H. Butler, P.H. Dederichs, A. Gonis, R.L. Weaver, 1992,ISBN: 1-55899-147-6

Volume 254—Specimen Preparation for Transmission Electron Microscopy ofMaterials-Ill, R. Anderson, B. Tracy, J. Bravman, 1992,ISBN: 1-55899-148-4

Volume 255—Hierarchically Structured Materials, LA. Aksay, E. Baer, M. Sarikaya,D.A. Tirrell, 1992, ISBN: 1-55899-149-2

Volume 256—Light Emission from Silicon, S.S. Iyer, R.T. Collins, L.T. Canham,1992, ISBN: 1-55899-150-6

Volume 257—Scientific Basis for Nuclear Waste Management XV, C.G. Sombret,1992, ISBN: 1-55899-151-4






MATERIALS RESEARCH SOCIETY SYMPOSIUM PROCEEDINGS

Volume 258—Amorphous Silicon Technology—1992, MJ . Thompson,Y. Hamakawa, P.G. LeComber, A. Madan, E. Schiff, 1992,ISBN: 1-55899-153-0

Volume 259—Chemical Surface Preparation, Passivation and Cleaning forSemiconductor Growth and Processing, RJ . Nemanich, C.R. Helms,M. Hirose, G.W. Rubloff, 1992, ISBN: 1-55899-154-9

Volume 260—Advanced Metallization and Processing for Semiconductor Devices andCircuits II, A. Katz, Y.I. Nissim, S.P. Murarka, J.M.E. Harper, 1992,ISBN: 1-55899-155-7

Volume 261—Photo-Induced Space Charge Effects in Semiconductors: Electro-optics,Photoconductivity, and the Photorefractive Effect, D.D. Nolte,N.M. Haegel, K.W. Goossen, 1992, ISBN: 1-55899-156-5

Volume 262—Defect Engineering in Semiconductor Growth, Processing and DeviceTechnology, S. Ashok, J. Chevallier, K. Sumino, E. Weber, 1992,ISBN: 1-55899-157-3

Volume 263—Mechanisms of Heteroepitaxial Growth, M.F. Chisholm, B.J. Garrison,R. Hull, L.J. Schowalter, 1992, ISBN: 1-55899-158-1

Volume 264—Electronic Packaging Materials Science VI, P.S. Ho, K.A. Jackson,C-Y. Li, G.F. Lipscomb, 1992, ISBN: 1-55899-159-X

Volume 265—Materials Reliability in Microelectronics II, C.V. Thompson,J.R. Lloyd, 1992, ISBN: 1-55899-160-3

Volume 266—Materials Interactions Relevant to Recycling of Wood-Based Materials,R.M. Rowell, T.L. Laufenberg, J.K. Rowell, 1992,ISBN: 1-55899-161-1

Volume 267—Materials Issues in Art and Archaeology III, J.R. Druzik,P.B. Vandiver, G.S. Wheeler, I. Freestone, 1992, ISBN: 1-55899-162-X

Volume 268—Materials Modification by Energetic Atoms and Ions, K.S. Grabowski,S.A. Barnett, S.M. Rossnagel, K. Wasa, 1992, ISBN: 1-55899-163-8

Volume 269—Microwave Processing of Materials HI, R.L. Beatty, W.H. Sutton,M.F. Iskander, 1992, ISBN: 1-55899-164-6

Volume 270—Novel Forms of Carbon, C.L. Renschler, J. Pouch, D. Cox, 1992,ISBN: 1-55899-165-4

Volume 271—Better Ceramics Through Chemistry V, M.J. Hampden-Smith,W.G. Klemperer, C.J. Brinker, 1992, ISBN: 1-55899-166-2

Volume 272—Chemical Processes in Inorganic Materials: Metal and SemiconductorClusters and Colloids, P.D. Persans, J.S. Bradley, R.R. Chianelli,G. Schmid, 1992, ISBN: 1-55899-167-0

Volume 273—Intermetallic Matrix Composites II, D. Miracle, J. Graves, D. Anton,1992, ISBN: 1-55899-168-9

Volume 274—Submicron Multiphase Materials, R. Baney, L. Gilliom, S.-I. Hirano,H. Schmidt, 1992, ISBN: 1-55899-169-7

Volume 275—Layered Superconductors: Fabrication, Properties and Applications,D.T. Shaw, C.C. Tsuei, T.R. Schneider, Y. Shiohara, 1992,ISBN: 1-55899-170-0

Volume 276—Materials for Smart Devices and Micro-Electro-Mechanical Systems,A.P. Jardine, G.C. Johnson, A. Crowson, M. Allen, 1992,ISBN: 1-55899-171-9

Volume 277—Macromolecular Host-Guest Complexes: Optical, Optoelectronic, andPhotorefractive Properties and Applications, S.A. Jenekhe, 1992,ISBN: 1-55899-172-7

Volume 278—Computational Methods in Materials Science, J.E. Mark,M.E. Glicksman, S.P. Marsh, 1992, ISBN: 1-55899-173-5

Prior Materials Research Society Symposium Proceedingsavailable by contacting Materials Research Society






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