Ebook - Advanced Science and Technology of Sintering

ADVANCED SCIENCE AND
TECHNOLOGY OF SINTERING
Edited by
Biljana D. Stojanovic
Center for Multidisciplinary Studies
University of Belgrade
Belgrade, Yugoslavia
Valery V. Skorokhod
Institute for Problems of Materials Science
of the Ukrainian Academy of Sciences
Kiev, Ukraine
and
Maria Vesna Nikolic

Joint Laboratory for Advanced Materials
of the Serbian Academy of Sciences and Arts
Springer Science+Business Media, LLC

Library of Congress Cataloging-in-Publication Data
Advanced science and technology of sintering/edited by Biljana D. Stojanovic, Valery

V. Skorokhod and Maria Vesna Nikolic.
p. cm.
Includes bibliographical references and index.
1. Sintering. I. Stojanovic, Biljana D. II. Skorokhod, V. V. (Valerii Vladimirovich) III.

Nikolic, Maria Vesna
TN697.17 A38 1999

671.3 '73-dc21
99-047696
ISBN 978-1-4613-4661-6 ISBN 978-1-4419-8666-5 (eBook)

DOI 10.1007/978-1-4419-8666-5
Proceedings of the Ninth Wor1d Round Table Conference on Sintering, held September 1-4, 1998, in Be1grade,
Yugos1avia
1999 Springer Science+Business Media New York

Originally published by Kluwer Academic/Plenum Publishers, New York 1999
Softcover reprint ofthe hardcover lst edition 1999
10987654321
A C.I.P. record for this book is avai1able from the Library of Congress
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PREFACE
This volume entitled Advanced Science and Technology of Sintering,

contains the edited Proceedings of the Ninth World Round Table Conference on
Sintering (IX WRTCS), held in Belgrade, Yugoslavia, September 1-4 1998. The
gathering was one in a series of World Round Table Conferences on Sintering
organised every four years by the Serbian Academy of Sciences and Arts (SASA)
and the International Institute for the Science of Sintering (IISS).
The World Round Table Conferences on Sintering have been traditionally
held in Yugoslavia. The first meeting was organised in Herceg Novi in 1969 and
since then they have regularly gathered the scientific elite in the science of sintering.
It is not by chance that, at these conferences, G. C. Kuczynski, G. V. Samsonov, R.
Coble, Ya. E. Geguzin and other great names in this branch of science presented
their latest results making great qualitative leaps in the its development.
Belgrade hosted this conference for the first time. It was chosen as a reminder
that 30 years ago it was the place where the International Team for Sintering was
formed, further growing into the International Institute for the Science of Sintering.
The IX WRTCS lasted four days. It included 156 participants from 17
countries who presented the results of their theoretical and experimental research in
130 papers in the form of plenary lectures, oral presentations and poster sections.
The presentation of each contributed paper proved to be a good opportunity for free
and informal discussion. This enabled a broad analysis of the current state of the
science of sintering and gave perspectives for the further development of the theory
and technology of sintering. Fundamental scientific problems were addressed as well
as the technological state-of-the-art in sintering and sintering materials, including
sintered materials of advanced technology used in a variety of research and
industrial applications. In the opinion of the editor, this conference was
characterized by the high level and broad scope of reports on the advanced science
and technology of sintering.
This volume includes 92 papers selected by the editors and organised into
seven sections which comprise this book, as follows: (1) Fundamentals (2)
Nanostructured Powders (3) Mechanical Activation (4) Sintering of Oxide Systems
(5) Electronic Ceramics (6) Non-Oxide Materials (7) Sintering of Metal Powders.
We would like to acknowledge the useful advice and considerable assistance
of the General Secretary of the International Institute for the Science of Sintering
and President of the Organization Committee, Academician Momcilo M. Ristic and
also the International Program and Organization Committee, Session Chairmen, as
well as the creative efforts of the distinguished contributing authors representing
v
many of the world centres for sintering research. We extend our personal thanks for
their cooperative attitudes, timely responses, and many helpful suggestions .
We wish to express our gratitude to the patron of the International Institute
for the Science of Sintering, the Serbian Academy of Sciences and Arts, as well as
the Centre for Multidisciplinary Studies at the University of Belgrade, and the
Institute of Technical Sciences of SASA in Belgrade for their support in the
organization of the conference. We also note with gratitude the financial support for
the conference organization provided by the principal sponsor, the Ministry for
Science and Technology of the Republic of Serbia, Potisje Kanjiza, Kanjiza, the
Cement factory , Kosjeric, the Institute of Nuclear Sciences "Vinca", the Institute of
Chemistry, Technology and Metallurgy, Belgrade, the Institute for Technology of
Nuclear and Other Mineral Raw Materials, Belgrade, the Technical Faculty , Cacak,
the Electronic Faculty, Nis, the Faculty for Technology and Metallurgy , Belgrade,
the Scientific Research Centre, Uzice, IRITEL, Belgrade, ICN Yugoslavia,
Petrohemija, Pancevo and RTB Bor, Bor.
We wish to acknowledge a small group of individuals who worked with great
dedication behind the scenes: Natasa Nikolic, Bojan Marinkovic, Mirjana Kosanovic
and Ljiljana Milosevic for their assistance in preparing materials before, during and
after the conference; Aleksandar Kosanovic and Dragan Tasic for providing
technical service; Voja Glavonjic and his staff from the Printing Office of the Serbian
Academy of Sciences and Arts for preparing all materials for the conference; Dr
Stamenka Radic for translation services, Nikola Cajkanovic, Ljiljana Nedeljkovic,
Ivana Sevicki and Vukica Dapa for simultaneous translation during the conference,
and Emina Ljutic for efficient typing of the conference materials.
It is also our pleasure to thank Goran Brankovic and Aleksandar Tucic for
their help in the preparation of the proceedings, as well as Tatjana Sreckovic, Vesna
Minic, Lidija Mancic and Zorica Marinkovic for performing various tasks and
preparing materials for the conference.
Lastly, we would like to acknowledge with affection the patience, tolerance,
and moral support we have been given by our colleagues and families through those
extended periods of time when we had to pay attention to organizing the conference
and editing these proceedings.
Valery V. Skorokhod
Maria Vesna Nikolic
vi
CONTENTS
Part I
FUNDAMENTALS
Influence of External Fields on Sintering 3

Y. Kornyushin
Liquid-Phase Sintering of the Systems with Interacting Components . . . . . . . . . . . . . 19

A. P. Savitskii
Simulation of Two-Dimensional Microstructural Development During Liquid Phase

Sintering 29
Z. S. Nikolic
Sintering Kinetic Analysis by Dilatometric Data Obtained at Different Heating

Rates 41
I. H. Moon and D. M. Won
Computer Study of Microstructure Formation by Rearrangement During Liquid

Phase Sintering 55
J. M. Chaix, S. M. Lee, and C. L. Marin
Computer Simulation of Neck Growth During Sintering Process . . . . . . . . . . . . . . . . 61

Z. S. Nikolic, I. Mitrovic, and V. V. Mitic
Phenomenology of Sintering Kinetics Using UOz as a Model 67

M. V. Nikolic and S. M. Radie
Contraction of the Complex Models by the Stoichiometric Network Analysis 75

Z. Cupic and Lj. Kolar-Anic
Electron Structure of YNizXz (X = Si, P) Compounds 81
I. D. Shcherba, V. M. Antonov, l. M. Telychyn, B. M. Jatcyk, L. 0 . Dobrianska,
and I. I. Margolych
vii
Computer Generation of Two- and Three-Dimensional Packings as a Background
for Numerical Modeling of Sintering Processes 89
V. V. Kartuzov, E. V. Kartuzov, and I. V. Kartuzov
Part II
NANOSTRUCTURED POWDERS
Scientific and Technological Problems in Nanostructured Materials Science . . . . . . . 97

R. A. Andrievski
Aerosol Synthesis of Nanostructured Materials 103

O. B. Milosevic
Preparation of Fine, Spherical, Composite Powder by Spray Pyrolysis II3

R. Marie, T. Fukui, and S. Ohara
Synthesis of Submicronic Oxide Powders by Aerosol Spray Pyrolysis: Modeling

of the Evaporation Stage 119
J. Vodnik and O. Milosevic
Nanostructure Composition of Diamond-WC-Co . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

I. Uvarova, T. Babutina, K. Konchalovskay, I. Timofeeva, and A. Petuchov
Pecularities of Fine-Dispersion SiC and Si 3N4 Powders Obtained from

Titanium-Magnesium Production Waste 131
M. V. Vlasova and V. A. Lavrenko
Sintering of Nanocrystalline Zirconia-Based Ceramics 137

V. V. Srdic , M . Winterer, and H. Hahn
Analysis of Thermal Treatment of ZnO Derived by the Freeze-Drying Method 143

N. Nikolic, Z. Zakula, O. Milosevic, and T. Sreckovic
The Effect of Shock-Wave Treatment on the Structural Characteristics of Synthetic

Diamond Powders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
M. A. Vasylkovska, Ya. V. Zaulichny, V. I. Kovtun, and M. V. Vlasova
Structural Properties of Ultradispersed Bi-Pb-Sr-Ca-Cu-O Particles Synthesized

from Aerosol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
L. Mancic, Z. Zakula, and O. Milosevic
Interaction of the Powder Particles with the Plasma of the Impulse Discharges
and the Use of This Process for Creation of Protective Coverages. . . . . . . . . . 159
V. V. Mikhailov and A. E. Gitlevich
Part III
MECHANICAL ACTIVATION
Mechanical Activation of BaC03-AIP3-Si02 167

S. Boskovic, D. Kosanovic, D. Bahloul-Hourlier, P. Thomas, and S. Kis
viii
Mechanochemical Synthesis of Nanophased Carbide TiC 175
I. Uvarova, M. Savyak, I. Timofeeva, and L. Isayeva
Mathematical Modeling of Combu stion-Type Interaction During Mechanical

Alloying 181
B. B. Khina and Yu. S. Sholpan
Evolution of the Micro structure of Disperse ZnO During Mechanical Activation

and Its Influence on Sinterability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
T. V. Sreckovic, M. G. Kakazey, V. A. Melnikova, T. V. Tornila,
and M. M. Ristic
Physical Properties of Mechanically Activated Grains 193

M. Petrov and S. Milosevic
Change of the Physical-Chemical Characteristics of the Materials by Mechanical

Activation 199
Lj. Andric, D. Zivanovic, and S. Milosevic
Mechanically Activated BaC03-AIP3-Si02 Mixture as an Additive for Liquid

Phase Sintering of Si3N4 . . . .. . . . .. . . . ... . . . . . . .. .. 205
Dj. Kosanovic, S. Boskovic, and S. Zec
Mechanical Activation of Mica 211

D. Zivanovic, Lj. Andric , Z. Sekulic, and S. Milosevic
The Influence of Mechanical Treatment on Activation of the ZnO-Sn0 2 System 219

A. Tucic, N. Nikolic, and B. Marinkovic
Part IV
SINTERING OF OXIDE SYSTEMS
Vacuum Sintering of Zirconia Based Ceramic s 225

S. Kulkov, T. Sablina, and N. Savchenko
A Study of Reactivity and Sinterability of Uranium Dioxide Powder through

Surface Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
G. P. Tiwari and A. G. C. Nair
Sintering and Creation of Porous Structure of Bioactive Ceramics 237

E. Fidancevska, J. Bossert, and M. Milosev ski
Analysis of the Sintering Process of ZnO and CdO by the Application of Sintering
Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
V. M. Minic, Z. S. Nikolic , and M. M. Ristic
Ceramic Properties of the Sintered Materials in the Sn-Sb-Cu-O System 251

M. Zaharescu, S. Mihaiu , and S. Zuca
Grain Growth in System CdO-BiP3 259

G. Brankovic, D. Krsmanovic, and B. Jordovic
ix
The Influence of the Composition and Time of Isothermal Sintering
on the Microstructure of the CdO-Bi 203 System 265
D. R. Krsmanovic, B. A. Jordovic, and G. 0 . Brankovic
Characterization of Thick Films of Fe.O, Obtained by Chemical Deposition 27 I

V. Z. Pejovic, B. D. Stojanovic, and N. B. Lekovic
Evolution of the Surface and Internal Structure of Silica Aerogels During

the Isothermal Sintering Process 277
I. Hinic, G. M. Stanisic, and Z. V. Popovic
Sintering Conditions and Hydraulic Activity of 4CaO . 3AlP3 . S03 283

M . I. Muntean, F. G. Paul, and C. Novae
Thermal Shock Behavior of Sintered Alumina Based Refractories . . . . . . . . . . . . . .. 289

T. D. Volkov-Husovic, R. M. Jancic, Z. V. Popovic, M. Muravljov, D. Jevtic,
and T. Kovacevic
Sintering of Sulphoaluminate Clinker . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 295

B. Zivanovic, Lj. Petrasinovic, S. Prokic, and T. Milovanovic
Prognosis of the Mineralogical Composition of Sintered Portland Cement

Clinker 301
Lj. Petrasinovic-Stojkanovic, M. Djuric, B. Zivanovic, M. Komljenovic,
and S. Omic
EDS Analysis of Sintered Material Degradation in an Aggressive Environment . . . . 307

S. Miletic, M. Hie, P. Jovanic
Evolution of the Phase Composition During Sintering of the MgO-Al 203-Si02

System. . . . .. . . .. 317
M. Atanasovska, M. V. Nikolic, and S. M. Radic
Experiences in the Chemical Gypsum-Phosphogypsum Preparation from the Triad

"Synthesis-Structure-Properties" Viewpoint. . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
M. B. Rajkovic, D. Simovic, and G. T. Vladisavljevic
Model of Drawing Think Glass Sheet from a Rectangular Preform and Its
Applications 329
A. D. Milutinovic-Nikolic, N. M. Talijan, and R. R. Aleksic
Crystallisation Kinetics of Layered Silicates in Glass 337

M. Tosic, R. Dimitrijevic, T. Sreckovic, J. Nikolic, and M. Duricic
The Effect of Atmosphere on HDS Catalyst Sintering 341

R. Marinkovic-Neducin, J. Kiurski , E. Kis, and R. MiCic
The Stability of Porous Alumina Catalyst Support against Sintering 347

T. B. Novakovic, Z. M. Vukovic, and N. N. Jovanovic
x
Part V
ELECTRONIC CERAMICS
Synthesis and Sintering of PZT Ceramics 355

A. Varela, M. A. Zaghete, A. Z. Simoe s, M. Cilense, and E. Longo
Advances in Sintered Electronic Materials 367

B. D. Stojanovic
Sintering of ZnO Doped Sn02 377

K. Perazolli, R. S. Biscaro, T. R. Giraldi, E. Longo, and J. A. Varela
Far Infrared Properties of BaTi03 Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385

P. M. Nikolic, B. D. Stojanovic, S. Durie, K. Radulovic, D. Vasiljevic-Radovic,
V. Blagojevic, D. I. Siapkas, and T. T. Zorba
Characterization of Domain Structure in BaTi0 3 Based Ceramics by Scanning

Electron Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
Lj. M. Zivkovic, B. D. Stojanovic, and Z. S. Nikolic
Fractals in Ceramic Structure 397

V. V. Mitic , Lj. M. Kocic, and I. Z. Mitrovic
The Influence of Heating Rate on Sintering Process of BaTi0 3 Ceramics 403

V. P. Pavlovic, V. B. Pavlovic, B. D. Stojanovic, T. Srekovic, B. Marinkovic,
and M. M. Ristic
Microstructural Characterization BaTi03-Composite Ceramics 407

V. Paunovic, D. Stefanovic, Lj. Vulicevic, and V. Dimic
Semiconducting Properties of Doped Barium-Lead-Titanate Ceramics . . . . . . . . . . . . 413

B. D. Stojanovic, T. V. Sreckovic, V. B. Pavlovic, B. A. Marinkovic,
and Z. Preradovic
Synthesis and Dielectric Properties of BaTi0 3-Novolac Composite 419

Lj. Vulicevic, D. Stefanovic, L. Lukic, S. Preradovic, and D. Mancic
Resistivity Versus Geometry Relation in Bulk-Sintered and Thick Film

MnCoFe-Oxide Thermistors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
0 . S. Aleksic, P. M. Nikolic, M. N. Sirnic, V. Z. Pejovic,
and D. G. Vasiljevic-Radovic
BaTi03 Structure Prognosis 431

V. V. Mitic and I. Z. Mitrovic
Synthesis and Sintering of Manganese Doped Sn0 2 in Several Atmospheres 437

S. M. Tebcherani, J. A. Varela, L. Perazolli, A. S. Camargo, and E. Longo
Sintering of MnZn Ferrite in the Presence of BiP3 Phase 445

M. Feder, V. M. Vilceanu , N. Teoharie, E. Segal , 0 . Caltun, and G. Cosmeleata
xi
The Influence of Sintering on the Properties of Lithium Ferrite . . . . . . . . . . . . . . . . . 453
E. Andronescu, B. Trifanescu, V. Vilceanu, M. Feder, and D. Crisan
Part VI
NON-OXIDE MATERIALS
Developments in the Powder Metallurgy of Non-Oxide Cermets 461

H. Pastor
Sintering Behaviour and Microstructure Development in Electroconductive

Si3N~-TiN Composites 475
Lj. M. Zivkovic, S. M. Boskovic, and M. S. Miljkovic
Structural and Mechanical Characteristics of ZA27-7 wt. % SiC Composites 483

S. Covic, M. Tasic, I. Bobic, and D. Bozic
Explosive Consolidation of Aluminum Nitride Powder . . . . . . . . . . . . . . . . . . . . . . . . 489

V. N. Radic
Characterization of Metal and Semiconducting Powders Using a Coherer . . . . . . . . . 497

P. M. Nikolic, S. Durie, and M. M. Ristic
Part VII
SINTERING OF METAL POWDERS
The Influence of Thermo-Plastic Deformation on the Structure and Mechanical

Properties of Powder Metallurgy Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 507
Yu. V. Milman
The Influence of Sintering Conditions on the Microstructure and Magnetic

Properties of Sintered SmCos Magnets 519
N. M. Talijan, V. P. Menushenkov, A. D. Milutinovic-Nikolic, A. S. Lileev,
and Z. D. Jovanovic
The Influence of Different Binders and Metals on the Properties of Sintered

Metal-Graphite Materials 527
C. Lacnjevac , J. Uzelac, N. Denic, and R. Vasic
Thermophysical Properties of Hot-Deformed Powder Materials. . . . . . . . . . . . . . . . . 531
V. Yu. Dorofeyev and Y. G. Dorofeyev
Copper Matrix Strengthening in Cu-AIP3 System by Mechanical Alloying and

Milling of Pure Copper and Prealloyed Copper Powders 537
V. Rajkovic, S. Zec, and M. Mitkov
Hardening Mechanisms in Some Prealloyed PM Treated Copper Powders 545

D. Bozic, V. Rajkovic, and M. Mitkov
Recrystallization of Cold-Pressed Aluminium Powder 551

S. Tadic and S. Zec
xii
Generation of Dislocations During Cold Sintering of Iron Powder 557
Z. M. Jankovic and B. A. Marinkovic
Investigation of Mathematical Rerlations between Technological Parameters and

Properties of Cold-Sintered Iron 565
M. R. Duricic and Z. Acimovic-Pavlovic
Thermal Recovery of Cold Sintered Mechanically Activated Powder System

Cu70%Fe30 % 569
R. Lj. Simeunovic, B. D. Stojanovic, and A. M. Maricic
The Interface Characterization of Laminar Nickel-Alumina Composites 575

D. Jankovic, D . Kicevic, and M. Mitkov
The Influence of AIP3 Addition on Electrical Properties of Sintered Copper . . . . . . 581

M. T. Ristic , M. V. Nikolic, Z. Jankovic, and A. MariCic
The Effect of the Deformation Degree on the Kinetics of Structural Relaxation

of the Fes9.sSis.2B3Coo.s Amorphous Alloy 587
A. M. Maricic, R. Lj . Sineunovic, and M. M. Ristic
Investigating Possibilities of Sintering Process Monitoring by Acoustic Emission

as an On-Line Method 593
M. Tasic, Z. Andie, and D. Bojovic
The Effect of Annealing on the Transport Properties of the Metastable CUSSCo lS

Alloy. . . . .. . . . . . . . . . . . . . .. . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . 599
N. Mitrovic, A. Rankovic, A. Kalezic, and S. Dukic
The Influence of Volume Fraction and Size of SiC Particles on the Mechanical
Properties of Metal Matrix Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 605
Z. Gnjidic and D. Bozic
Investigation of the Microstructure and Distribution of Solute During Solidification

of AI-Cu Alloy 61 r
v. J. Radojevic, A. V. VaiCic, S. N. Nikoli c, and A. D. Milutinovic-Nilokic
Properties of Cold Rolled Sintered Copper Alloys after Annealing 617
S. Nestorovic and D. Markovic
The Effect of Copper Contents on the Structure of the Aluminium-Copper Alloy 623
B. Zlaticanin, S. Durie, B. Jordovic, and B. D. Stojanovic
Acousto-Electronic Superconducting Switch 629

P. V. Nistiriuc, N. P. Bejan, M. I. Sajin, P. H. Deshanu, V. N. Bejan, V. Nistiriuc,
and A. I. Shoulga
Sharp Shift Devices 633

P. V. Nistiriuc, M. P. Bejan, M. I. Sajin, P. H. Deshanu, I. V. Nistiriuc ,
and Yu. Sholpan
xiii
Thickness Dependences of Kinetic Properties of Quantum Wires of Pure and
Doped Bismuth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 637
P. P. Bodiul, AN. Burchakov, D. V. Gitsu, and A. A. Nikolaeva
Contributors 643
Index . . . . . . . .. . . .. 655
xiv
Part I. FUNDAMENTALS
INFLUENCE OF EXTERNAL FIELDS ON SINTERING
Yuri Kornyushin
Racah Institute of Physics

The Hebrew University
Jerusalem 91904, Israel
ABSTRACT
Two types of driving forces caused by the presence of external fields are described: one
type arises due to the evolution of the heat in the volume of a sample (electric contact, hf,
inductive heating or penetrating radiation, e.g., neutrons could be the sources of the heat) ;
another type of the driving forces arises due to the energy of the field (electric, magnetic) ,
present in the bulk of a polar material. Influence of these driving forces on sintering,
structure and propert ies is discussed . The role of mobile and immobile dislocations , grain
boundaries , and pores is considered . Cycling and pulsing regimes of sintering are
investigated .
Porous polar material s are studied on the basis of the Clausius-Mos sotti approximation .
Equilibrium shape of a pore in a polar material is calculated . It's contribution to the
anisotropy of a sample is discussed . Peculiarities of the kinetics of pores in polar materials
in external field are regarded.
INTRODUCTION
Directions and rates of diffusional processes of mass transfer are important constituents
of the process of sintering. They are determined by thermodynamic driving forces and kinetic
characteristics of a system. Kinetic characteristic s include magnitudes of kinetic coefficients,
e.g., diffusion coefficient, and conditions of realization of different mass transfer
mechanisms. A vacancy mechanism of mass transfer is a regular one in crystalline materials.
Mean free path of the excess vacancy, which is determined by defect structure of a material
and by the distance from a free surface, governs in an essential way rates of diffusional
processes.
The process of sintering is usually considered to consist of three parts' . Initial stage of
sintering is usually regarded to be determined by the processes of connection of separate
particles, and a regrouping ; plastic deformation and boundary diffusion playa leading role
during this stage, while the contribution of the bulk diffusion is negligible. Boundary
Adv anced Science and Technology oj Sinter ing, edited by Stoj anov ic ct al.
Kluwer Academic /Plenum Publishers, New York, 1999 3
diffusion approximation is justified in the temperature interval where the boundary mass
transfer is dominant over the one in the bulk of a crystal. The intermediate stage is the most
complicated one and the final stage is characterized by the presence of the isolated pores in a
sample. Kinetics of a pore system in this stage is controlled by mass transfer along grain
boundaries and dislocation lines (if available) at lower temperatures and by bulk mass
transfer mechanisms at higher temperatures.
Remaining after the final stage isolated pores influence physical-mechanical properties
of a product undesirably in the majority of cases. Arising after a coagulation, large pores are
usually especially harmful and their removal is especially difficult. Electrophysical
technologies, such as electric contact, hf, inductive heating, allow to overcome such
difficulties in a series of cases'.
In polar materials in strong external fields, when the moments are oriented along
external field, pores cause distortion of the lines of the field, leading to the increase in the
energy of the field in the bulk of a sample. This leads to the elongation of the pores in the
direction of the field, causing a decrease in the energy of the field. The equilibrium shape of
a pore is a result of a competition between decreasing energy of the field and increasing
surface energy. But as the size of the pore increases, the decrease in the energy of the field
becomes so significant as to cause the decrease in the Gibbs free energy with the pore
growth. This happens when the pore size becomes larger then a certain critical one, the
typical value of which is about one micron. So the larger pores tend to grow, leading to the
cavitation phenomenon. These phenomena were described by the author'? and could be
observed in, e.g., alloys on the Co base as the Curie temperature of Co is 1400 K 6, and in
this temperature range the diffusion processes are active. The kinetics and some properties
of samples of polar materials in strong external fields are going to be discussed further on.
BULK HEATING
It was predicted theoretically that the evolution of the heat in the bulk of a sample (e.g.,
Joule heat) leads to specific driving forces of the diffusional processes? The sources of these
driving forces are the divergent temperature gradients, arising as a result of the bulk heating
of a sample (as the heat, evolving in the bulk of a sample has to be extracted out of a sample,
the temperature, T , appears to be higher in the bulk of a sample comparative to the
temperature of the surface of a sample)2.7.8.
Driving Forces
The temperature gradient causes the thermal diffusion flux of vacancies,
J =-k T (D/(T) )gradT , (I)
where is k T the thermal diffusion ratio, D =D (T) is the diffusion coefficient, and (T) is the
temperature of a sample averaged over it's volume.
Eq. (1) is a linear approximation which is applicable when the temperature gradient is
smooth enough and small enough, which is the case.
Eq. (I) determines the additional number of vacancies leaving unit volume of a material
per unit time due to the regarded driving forces:
(2)
4
where q is the heat production per unit volume of a material per unit time (in the case of
ohmic heating this is the Joule heat, q = crE2 , where o is the specific electric conductivity, E
is the intensity of the effective electric field), c is the heat capacity (per unit volume), T, =
(aT/at) is the heating (cooling) rate , and K is the thermal conductivity coefficient.
To obtain Eq. (2) , the equation of the heat flow 2 ,
K!:1T =(cT, - q) , (3 )
was used.
The thermal diffusion ratio, k , is determined by the formula",
kT =N; (u - u m)/kT , (4)
where N; is the mean equilibrium number of the vacancies per unit volume of the material at
the temperature T , u is the vacancy formation enthalpy for the given process of diffusional
transport (e.g., in the case of the transport of vacancies from the cores of dislocations to the
plane surface of a sample, u is the enthalpy of the vacancy formation on dislocation), u m is
the enthalpy of the vacancy migration, and k is the Boltzmann's constant.
The contribution of the specific driving forces, arising from the bulk heating is the most
important at the isothermal regime, when T, = 0 , and at large enough values of the power,
q, being introduced into the bulk of a material. Such conditions are readily fulfilled during
sintering of thin or miniature samples, when heat emission from the surface contributes
essentially to the heat balance. This contribution may be decisive during ohmic sintering of
metallic samples thinner than I mm. In this case electric field intensities, E , of the order of I
V/cm and larger may be applied". Under these conditions the heating of large pores differs
very significantly from one during furnace sintering. This follows from the fact that the
contribution of the specific driving forces accordingly to Eq. (2) does not depend on the
nature of defects, and, in particular, on the pore size. However, the Laplace forces increase
with decreasing pore size.
In some cases it is worthwhile to intensify artificially the surface heat emission. In this
case the value of q can be increased and time required to complete diffusional process is
reduced concomitantly. As a result, the energy required to complete the process is smaller
than that during a conventional furnace sintering. One ought to take into account the
advantages of more compact and energy-saving equipment in the case of ohmic or hf
sintering as compared to a traditional furnace one .
Initial Stages of the Bulk Heating Sintering
The very first stages of electric sintering are essentially non-stationary ones. Evolution
of the Joule heat during the very first moments of electric sintering leads to sharp
temperature differences . Such an essentially non-stationary regime of the heat and mass
transfer can be described by essentially non-linear theory only. Similar situation arises when
sintering is caused by electric discharge':', Here we shall consider early, but not the very first,
stages of electric sintering!' . The temperature gradients are considered to be small, and
linear approximation is applicable. The boundary diffusion is regarded to be the main
mechanism of the mass transfer. In this case the number of the atoms , leaving one contact
per unit time on one particle, N aJ , is described by the integral of (Ja,n) along the closed path,
surrounding the contact (here J, is the atomic flux, and n is the unit vector, perpendicular to
the path). The line integral around the closed path can be transformed to the surface integral
of div.l, (the integral is extended over the surface of a contact). The processes of the mass
5
transfer during electric sintering are much faster than those, arising due to the surface
tension forces during conventional sintering. This means that the influence of the surface
tension forces is often negligible during electric sintering. In this case the surface flux of the
atoms, J, , can be expressed as
Ja=-Db (kTb/(TgradT , (5)
where Db is the boundary diffusion coefficient, and k Tb is a boundary thermodiffusion ratio.

Let us the consider Joule heating under the isothermal conditions. When a component
of the temperature gradient, perpendicular to the boundary is not taken into account, the
number of atoms, leaving the contact area on a single grain per unit time is given by the
following expression:
(6)
where o, E , K are local electric conductivity, electric field, thermal conductivity on the
contact, and s is area of the contact.
If perpendicular to the boundary component of the temperature gradient is taken into
account, the right-hand part of Eq. (6) acquires an unessential factor of the order of unity.
As the current passes two contacts in each particle, we have for the rate of the process :
(7)
where V is the volume of a sample per number of the constituing particles, and Va is the
atomic volume.
Let us consider now a model of identical particles of an initial radius Ro . To simplify
the calculations let us assume that after the pressing and during the considered early period
of sintering each particle is a cubically symmetric figure, formed by a sphere of a radius R(t) ,
of which 6 segments are cutted off by planes. We consider that at the early stages of
sintering s(t) is essentially smaller than R2 , although in real powder systems set) and R2 are
often of the same order of magnitude. This model does not take into account anisotropy ,
arising due to the electric current.
In the first approximation on [s(t)/R 2 ] small parameter we get that
V = 8Ro3 - (22/rc)Ros . (8)
Eq. (7) and (8) yield
(9)
where Vo is the initial volume of a sample per one particle.

Eq. (9) yields
Vet) = Vo - (22/rc)Ros(O)expAt . ( 10)
As follows from Eq. (10), the shrinkage kinetics equation has a form,
2][(expAt)
[yeO) - V(t)]/V(O) = [33s(O)l2rc 2Ro - I] . (II)
6
It is worthwhile to note that Eq. (11) is applicable as far as it's right-hand part is
essentially smaller than the maximum possible value of the shrinkage, which is supposed to
be essentially smaller than unity.
Eq. (II) was obtained under the assumption that the A parameter is not changed during
the regarded process. This assumption is valid when the heat evolution, q , that is the
effective electric field, E , also, are not changed during the process . During initial stages of
electric sintering and when s(t) R0 2 , the contribution of contacts into electric resistance of
a sample is the main one, and therefore effective electric field in the contacts remains
practically unchanged during regarded process . Changes in effective electric field, E , during
regarded initial stages of electric sintering could be taken into account by retaining the
second and higher powers of the small parameter, [s(t )/R02 ] , when performing calculations .
Final Stages of the Bulk Heating Sintering
Let us consider processes determined by diffusion of vacancies through the bulk of a

material. Let our sample contains several ensembles of sources (sinks) of vacancies, which
are identical in each given ensemble. Each of the i-th ensemble is characterized by it's own
equilibrium value of vacancy concentration, N, , an enthalpy of the vacncy formation on any
source (sink) of the ensemble, U; , and a relaxation time of the number of vacancies to their
equilibrium value, 't; . In this case in a stationary regime the continuity equation for vacancies
can be written as follows :
divJ + ~;[(N - N;)/'t;] =0 , (12)
where N is a vacancy concentration, and the vacancy flux, J , is as follows :
J =-DgradN + kTa(D/(TgradT, (13)
where kv the is thermodiffusion ratio for the atoms.

When (u; - Uj ) kT, and a linear approximation of the thansport theory is applicable,
the equation for the surplus vacancies concentration , n; =N - N, , is as follows:
(14)
where the thermodiffusion ratio for the vacancies,
(15)
In a simple atomic theory" Eq. (4) takes place, which may be written here as follows :
(16)
The quantity (D't; )112 has a meaning of a mean free path of the excess vacancy, (I) , in
the bulk of a material related to the i-th type sinks.
The rate of the diffusional changes of the i-th type sources (sinks) is proportional to n; .
For example, in the case of pores, the rate of the changes in the pore volume of the pores of
the i-th type, (v, )/ , is described by the following relationship:
(17)
7
where No is the number of the atoms in the unit volume of a materi al, n pi is the number of the
pores of the i-th type in the unit volume .
The quantity n j is proportional to the right-hand part of Eq. (14) , the value and the sign
of which is determined by E and other parameters. In the bulk of a material Laplacean in the
left-hand part of the Eq . (14) can be neglected and thus ni can be determined without solving
the differential equation of the second order.
For the pore of the i-th type , when the pressure inside the pore and external pressure
are neglected,
Uj = Uo - (2y/n No), (18)
where Uo is the enthalpy of the vacancy formation on the plane surface, y is the specific
surface energy, and r. is the pore radius .
The enthalpy of the vacancy formation is lower on small pores . According to this at E =
o Eqs . (14) and (18) describe the process of coagulation of smaIl pores into large ones . In a
general case from Eq . (14) follows that the pores of the ensembles, whose right-hand part of
Eq . (14) is positive, shrink, and these are the ensembles of smaller pores. The condition of
the healing of the pores is as follows :
(19)
where Lk ' denotes a summation over the ensembles of the pores only. Only the pores with
the radius smaller than r* are being healed .
At kT > 0 r* increases monotonically with increasing E , going asymptotically to
infinity when E ~ E*,
(20)
At E ~ E *, according to Eq. (19), no pore can grow.

Eq . (19) can be represented in another form,
where Lk" denotes a summation over all the ensembles of sinks and sources but the
pores.
At k T > 0 Eq . (21) determines the field value, E, , which is sufficient for the pores of
the i-th ensemble to shrink .
The Role of the Mobile and Immobile Dislocations. This role was considered' :',
Eq. (14) shows that the rates of the diffusional processes are determined essentially by
the differences of the enthalp ies of formation of vacancies on different types of sources
(sinks) and by mean free paths of the surplus vacancies in respect to different ensembles of
the sources (sinks), (D 'tj )"2 . The greater the amount of the sources (sinks), which are
present in a crystal, the smaller the mean free path of a surplus vacancy and the higher the
rate of the diffusional processes".
Dislocations are typical sources (sinks) of vacancies in a crystal. However, when the
density of the dislocations increases, many segments of dislocations, blocked by intersections
with another dislocation lines, are formed . Such segments cannot serve as sources (sinks) for
a considerable while, as their function as sources (sinks) results in the bending of the
segments between the points of the intersections, and therefore to the increase in the
8
enthalpy of the vacancy formation on the regarded segment of the dislocation (impurity
atoms play, obviously, an important role in the immobilizing of the intersection points) . That
is why only thermally mobile dislocations should be taken into account as possible sources
(sinks) of vacancies. Now let us calculate density of the thermally mobile dislocations .
Let us consider randomly distributed linear dislocations, parallel to the Descartes's
coordinates. Let the densities of the dislocations of each of the three directions be the same
and equal to 1/3 of the total density, nd . Let us approximate a line of a dislocation by a
square cylinder with a base side, b , (b is of the order of magnitude of the Burgers's vector),
and a grain (in the case of a single crystal - the sample) - by a cube with the rib, L . Let us
regard some dislocation and some intersection point. Obviously, next intersection point can
be found at the distance between x and x + dx with the probability,
(22)
Taking into account that 2ndL 2 3 , one can calculate the number of the segments of
the length between x and x + dx: (2/3)ndbL[exp(-2/3)ndbx](2/3)ndbdx .
Let us suppose that the segments shorter then some characteristic length, I , (x ~ I) can
not serve as sources (sinks) in the regarded diffusional process . The total length of such
segments on one dislocation can be calculated. For this the number of the segments of the
length between x and x + dx should be multiplied by x and integrated from 0 to I . The result
is : L{ I - [I + (2/3)ndbI]exp[-(2/3)ndhIJ) .
The ratio of this length to the length of the dislocation, L , is a relative density of the
thermally immobile dislocations . Therefore for the density of the thermally mobile
dislocations, ndt , we have:
(23)
Obviously, ndt "" nd at 2nd bl 3 ; then, with the increase in nd bl , ndt achieves a
maximum at nd =n m , and after that ndt decays exponentially with further increase in n-b! .
The value of the maximum, ntm = 1.261bl , is achieved at nd =n m=2.431bI .
The density of the thermally mobile dislocations, arising in the process of annealing of
the deformed bee iron, containing small amount of impurities, was reported to be
measured 15. At nd = 3x10" cm-2 , the mobile dislocation density, ndt, was 10" cm- 2 With
these data Eq. (23) yields bl = 1.145xlO- ll ern" . At b = 3x10-8 em this corresponds to 1=
3.8xlO -4 cm. The maximum density of the thermally mobile dislocations, ntm , was i .ixio''
cm- 2 at n m = 2.22x10 11 cm-2 It is worthwhile to note that in the regarded case the
maximum was a rather pronounced one. At 10-11 nd = I, 2.22, 3, and 6, 10-10 ndt were 8.2,
11,IO,and3.4 .
So, when the intersection points of the dislocation lines are pinned by, e.g., impurity
atoms, the optimal dislocation density exists at which the density of the thermally mobile
dislocations is of a maximum value and the rates of the diffusional processes are of the
maximum values also. The diffusional stage of the process of sintering is one of such
processes.
Calculation of the Relaxation Parameters. To calculate the relaxation parameters,

let us consider a case when there is only one type of the sources (sinks) of vacancies in a
crystal and there is a macroscopically homogeneous surplus of the vacancy concentration in
a sample. It is supposed that vacancy concentration in the vicinity of the sources (sinks) has
an equilibrium value. The coordinate dependence of the vacancy concentration around the
given source (sink), in the domain of it's influence, is determined by the stationary
9
distribution, that is, by the Laplace equation. The relaxation parameter, l/Dr. , will be
calculated for some typical sorts of sources (sinks) of vacancies:
Grain boundaries. Let us approximate a grain by a sphere of a diameter, d , and a
microscopic dependence of the vacancy concentration, N, on the distance from the centre of
a grain, r, by following equation:
N = N; + (air) - (2ald) , (24)
where a is some constant.

Then the vacancy flux near the grain boundary is 4aDld2 , and the number of the
vacancies, coming to a grain boundary per unit time, and calculated per unit volume, is
24aDId 3 , which; on the other hand, may be written as (N) - N, )/r. = aid: . From this
follows that l/Dr. =241d 2 for the grain boundaries, which means that the mean free path of
the excess vacancy inside a grain with respect to the grain boundaries is about 0.2d .
Pores. Let us consider an ensemble of identical homogeneously distributed spherical
pores of a radius, r , and a pore concentration, np The porosity is supposed to be small,
which allows us to approximate a volume of influence of each pore (a volume from which a
given pore attracts the surplus vacancies) by a sphere of a radius O.62np- 1I3 , and to
approximate a microscopic dependence of the vacancy concentration on the distance from
the centre of the pore, r , as
N = N e + (alro) - (air) . (25)
The vacancy flux near the surface of a pore is aDlro2 , and the number of vacancies,
coming to the surface of the pores per unit time, and calculated per unit volume, is 41taDnp ,
which, on the other hand, may be written as (N) - N, )/r. = alror. . From this follows that
II Dr. = 41tnp ro for the pores.
Let us consider a case when there are spherical pores of different radii, rk , in the
sample, but no other defects . Then we have
(26)
where (rp) is the average radius of the pores and (n p) is the total number of the pores in the
unit volume of a sample.
Dislocations. Speaking about dislocations, one should take into account that the
vacancies are generated and annihilated by the dislocation jogs. When the averaged distance
between the jogs, lj :<': ndt- 1I2 , the jogs could be regarded as a limiting case of pores , where
the size of the Burgers vector, b , corresponds to the radius of a pore, ro , and so following
equation can be applied:
(27)
Here an interaction between a vacancy and a stress field of dislocations is not taken into
account. This interaction can be neglected when it's energy is much smaller than kT , which
is the case at ambient temperature and higher ones. At ndt = 1010 cm-2 , lj = 10-5 ern , b =
3xlO-8 cm , Eq. (27) yields I1Dr. = 4.19x108 cm-2 .
When lj ndl- l 12 , almost all the volume of a sample can be approximated by cylinders,
surrounding parallel, uniformly situated dislocations. The radius of the cylinder is about
O.564ndt-1I2 . The concentration of vacancies in a separate cylinder can be approximated as
IO
N =N; - aln(pllj) , (28)
where p is the distance from the axis of a dislocation.

It is accepted in Eq . (28) that N = N; when p '" lj . The flux of the vacancies in the
vicinity of the cylinder, where p '" lj , is -aDllj . The number of vacancies, crossing the
surface of the cylinder, p '" Ij , in the unit time, and calculated per unit volume , is 21taDndt.
On the other hand this number is equal to the number of vacancies, annihilating on
dislocations per unit time, (N) - Ne)!'t =-(al2'!)ln(8 .541/ndt) . From this follows that
liD'! = -41tndt Iln(8.541/ndt) . At 8.541/ndl = 10-3 and ndt = 1010 cm- 2 we have liD'! =
1.82xlO 10 cm- 2
It is worthwhile to note that a relaxation parameter, liD'! , in regarded case is a little
sensitive one to the value of Ij (the dependence is the logarithmic one).
The Role of the quality of the surface. In those cases when the process depends upon
mass transfer to or from surfaces (for example , pore surfaces) , its rate is determined in many
aspects by both the structure and quality of the surface'", Usually a vacancy concentration in
a thin layer near the surface is assumed to be equal to the equilibrium value with respect to
the vacancy formation in the given spot of the surface . This is valid only in a case when the
time interval during which a vacancy is formed on the surface is considerably smaller then
that during which a vacancy exists in the above layer. This condition is fulfilled usually in
perfect crystals, where diffusional currents are small. Diffusional currents in real crystals may
be so intense that equilibrium is not achieved. The rate of approach of a vacancy
concentration to the equilibrium one near the surface depends on the density of sources
(sinks) of vacancies on the surface (surface defects) . When the density of these defects is
sufficiently high, the above rate is considerable, and the mass transfer process proceeds
14
quickly. Otherwise, the rate of the motion of the surface is slow . As calculations ShOW , the
rate of the change of the isolated pore of the radius r has a factor v/ [D(/) + (D + v(l) )r],
where v is a parameter, which characterizes the ability of the ensemble of the surface sources
to supply deficient vacancies and (I) is the mean free path of the surplus vacancy in the bulk
of a material.
Theoretical Conclusions, Concerning Final Stages of Sintering. On the basis of

results, described above, equation, describing kinetics of the pores of the i-th ensemble were
derived. In a general nonstationary case it has a form :
(dz /dr ) =-(D/No rj)[(6/1td 2

) + (bndlllj) + (n p) (r p) r' {[k T (0"2 - cTt)/41tK(T)] +
(Ne/k(T [(6/1td2)(Ug b- uo) + (bndtllj)(ud - uo)] + (2yNe/k(T)No r; )x
[(6/1td2 ) + (bndtllj) + (n p) (rp) - rj)]} , (29)
where Tj is the radius of a pore, belonging to the i-th ensemble, Ugb and Ud are the enthalpies
of the vacancy formation on grain boundaries and dislocations, respectively.
Equation, describing kinetics of the averaged pore radius is
(d(rp) /dt) = -(D/No)[(6/1td2 ) + (bndtllj) + (n p) (r p) r ' {[k T (0"2 - cTt)/41tK(T) l(lIrp) +
(Ne/k(T[(6/1td 2)(Ug b- uo) + (bndlllj)(Ud - uo) - (2yNe/k(T)No)(np)]x
(lIr p) + (2yNe/k(T)No)[(6/1td2 ) + (bndillj) + (n p)(rp)](lIrp2) } (30)
11
On the basis of the described theoretical results, we may conclude that the rate of the
given diffusional process is determined by the following factors :
Heating method. Bulk heating effectively accelerates mass transport processes if the
production of the heat in the bulk of a material, q , is high enough . This occurs when small
or thin products, with a thickness of the order of I mm or thinner, are sintered .
The structure of the crystalline defects of the sintered powders. The higher the
concentration of defects, the more intense the mass transport processes are, as a rule . But
the dependence of the process rate on the dislocation density is not monotonic. It has a
maximum at some dislocation density, typical value of which is about io" em - 2
The ability of both the bulk and surface vacancy sources to emit or absorb vacancies.
As a healing of large pores (larger than 1 jl in diameter) is enhanced due to the bulk heating ,
the process of coagulation of small pores into large ones is impeded (in contrast to a
conventional furnace sintering) . Hence, the conclusion may be drawn that the samples
sintered by bulk heating will contain a larger number of small pores and smaller number of
large pores than found in the regular furnace sintered samples. Such a more uniform pore
structure, consisting mostly of small pores , tends to improve mechanical and other physical
properties of products.
A comparative experimental investigat ion of sintering of iron powder by means of
electric contact, inductive, and conventional furnace sintering was performed". The results
had shown that the electric contact sintering allows to achieve the same level of mechanical
properties during essentially smaller period of a treatment comparatively to the conventional
furnace sintering.
Cycling and Pulsing Regimes
During cycling around temperature interval of the first order phase transformation an
intensification of the diffusional mass transfer processes may be observed in some cases.
Such an influence takes place only when the phase transformation is the one of a martensitic
type 17, as in this case every phase transformation is accompanied by some plastic
deformation during which the surplus vacancies are formed . Form ation of surplus vacancies
causes changes in sources (sinks) of vacancies, which is a mass transfer by itself, and this
enhances the process of sintering . Vacancies are formed on locations where the enthalpy of
the vacancy formation is smaller . Then the surplus vacancies annihilate on locations where
the enthalpy of the vacancy formation is larger . This process contributes to a further
development of the process of diffusional sintering . Other processes of the mass transfer,
typical for the nonisothermal electric sintering, take place concomitantly and were
investigated"
Equation, which determines time and coordinate dependence of temperature is the heat
flow equation, Eq. (3). At cycling or pulsing regimes, the heat production, q = crE 2 , varies
periodically. Let us separate all the sources (sinks) of vacancies , existing in a sample, into
two grades. Let the first grade be the one, which realizes sintering , and the second one doe s
not contribute to the sintering process directly [e.g., dislocations; they do not contribute
immediately to the process of sintering (consolidation of a material) during their activity as
sources (sinks)]. As was shown 14, all the source s (sinks), which are described by parameters
'ti and N, ,can be replaced by one effective type of sources (sinks) with
(31)
Dependence of the vacancy concentration on time and coordin ates during the process
of sintering is determined by the continuity equation :
12
divJ + [(N - Net)/'ttl + [(N - Nd/'t2] + (dN/at) =(dNv/dt) , (32)
where Net and r, refers to the first grade sources (sinks), Ne2 and t, refers to the second
grade ones, and (d N, /dt) is the production of vacancies per unit time in the unit volume of
the sample, caused by direct and reverse martensitic phase transitions . The vacancy flux, J ,
is determined by Eq. (13).
Substituting Eq. (13) into Eq. (32), and taking into consideration Eq. (3), we obtain
equation, which determines time and coordinate dependence of the vacancy concentration:
(33)
The changes occurring during time intervals considerably larger than the cycling period
are of a primary interest. So let us time-average Eq. (33) over the cycle period . Let us
consider only the bulk of a material, where macroscopic inhomogeneity of the vacancy
distribution is inessential. This inhomogeneity is essential only in a surface layer of the
thickness of about [D'tt't2/('tt + 't2)]112 . When time-averaged temperature and vacancy
concentration remain unchanged (quasi-stationary regime), we obtain following relationship,
valid in the bulk of a sample :
(34)
The left-hand part of Eq. (34) refers to the first grade processes, that is to the rate of
the sintering process. The right-hand part of Eq. (34) represents action of different sources
and driving forces of diffusional processes. The first term represents conventional sources
and driving forces of a furnace sintering. The second term describes a contribution of the
divergent thermal diffusion fluxes, caused by the inhomogeneity of the temperature gradient
in the bulk-heated sample. The third term describes a contribution of the surplus vacancies,
formed by the plastic deformation at direct and reverse martensitic transformations during
cycling . The larger the third term the greater the enhancement of the sintering process. From
this follows that the cycling and pulsing regimes are more effective at higher frequencies
(shorter periods) .
It is worthwhile to regard separately two following cases:
(i) First of all let us consider a case when Net < N < Ne2 . In this case the sources of a
second grade emit vacancies, which annihilate on the sinks of a first grade . In the early
stages of sintering this leads in some cases to the decrease in the curvature of the grains and
thus the process of sintering progresses. As in the regarded case N < Ne2 , the contributions
of the first and the third terms in the right-hand part of the Eq. (34) are positive. This means
that the rate of the sintering on the early stages of the process increases monotonically with
the increase in the frequency of cycling.
The final stages of sintering consist in the healing of pores . So to enhance the process
of sintering we have to create conditions when the source of a first grade (e.g ., pores) emit
vacancies. But in the regarded case first grade sinks absorb vacancies. Thus the sintering
process (in it's final stages) is impeded, and the higher the frequency of the cycling, the
slower the rate of the final stages of sintering is.
(ii) Now let us regard a case when Ne2 < N < Ne l In this case the first grade sources
emit vacancies, which annihilate on the second grade sinks. That is why in the regarded case
the increase in the surplus vacancy concentration impedes the bulk vacancy diffusion
mechanism of the activity of the first grade sources , thus diminishing a negative contribution
13
of this mechanism to the early stages of sintering. So, in the early stages, cycling and pulsing
enhances sintering, and the higher the frequency, the more essential the enhancement is. As
in the regarded case the emission of the vacancies by the first grade sources is slowed down
when surplus vacancy concentration is increased, the rate of the final stages of sintering (the
healing of the pores) is slowed down also, and the higher the frequency of the cycling the
lower the rate of the final stages of sintering is.
Discussion of the Bulk Heating Driving Forces
Experimental data on ohmic sintering":" show that during prolonged sintering,

especially at higher temperatures, the peculiarities, caused by the driving forces arising due
to the bulk heating become more and more pronounced. This corresponds to the increasing
contribution of the stationary stage processes to the final structure and properties of sintered
samples, and according to the theory the contribution of the regarded driving forces are the
largest at the isothermal regimes. After the bulk heating sintering, according to the theory,
samples have a specific defect structure: greater amount of pores of smaller sizes, which
influences significantly mechanical properties of sintered materials.
It is interesting to note that the same mechanism prevents radiational swelling of
materials with positive k T 19.
POLAR MATERIALS
A diffusional flow in solids" may cause changes in shape and volume of pores and leads
to a diffusional motion of pores in different extemal fields". In particular, a pore in a
magnetic material may change it's shape and move by means of diffusion". A good example
of material, where active diffusional processes occur below the Curie point is Co, as it's
Curie point, is 1400 K 6 . Diffusional processes, typical for the final stage of sintering, and
some physical properties of sintered materials will be discussed in this chapter.
Clausius-Mossotti Approximation
The Clausius-Mossoti approximation is a model to describe effective conductivity or

susceptibility of mixtures22. 25 Extension of the original Clausius-Mossotti approximation' <"
takes into account the shape of a sample. It is supposed that regarded sample consists of
grains and a matrix, and grains (particles of the components) are assumed to be ellipsoids,
oriented along the external homogeneous magnetic field. Material of a matrix could be a
magnetic one. Magnetic field and induction are supposed to be homogeneous ones in matrix
and in grains, but are of different values in the matrix and in the different types of grains as is
assumed in the original Clausius-Mossotti approximatiorr". All the fields and inductions are
supposed to be directed along the external homogeneous field as is assumed in the original
version of the Clausius-Mossotti approximationr '
Equilibrium Shape of a Pore
Let us consider a porous ferromagnetic ellipsoidal sample of a volume, V , in external

homogeneous magnetic field, H. Let us assume that there are pores of different types, i , in
the sample. Each type is characterized by a demagnetization factor, ndmi , and it's volume
fraction,f; . As it is assumed in the Clausius-Mossotti approximation, a magnetic field in the
matrix, Hm , is supposed to be a homogeneous one, and magnetic fields in each pore , H, , are
14
supposed to be homogeneous ones also, and all the fields are supposed to be directed along
the external field (external magnetic field is assumed to be strong enough to align all the
magnetic moments along itself).
In some cases pores may cause deformation of a matrix around them and accompanying
elastic and magnetoelastic energies . To evaluate a contribution of the magneto elastic energy
in the balance let us use the following relation for the density of magnetoelastic energy",
Wme = BiklmMiMkUlrn (Bik1rn is magnetoelastic tensor, M, is the i-th component of the specific
magnetic moment and Ulm is the strain tensor) . In accepted model M, is constant. Using a
theorem on the bulk mean value of Ulrn 27, one may obtain that the formation of a pore brings
with it magnetoelastic energy of the order of magnitude about BM2YVp/Krp(B has a value of
the same order of magnitude as that of the magnetoelastic tensor components, vp and rp are
the volume and the radius of a pore, and K is the bulk modulus) . As the change in the
2
magnetic energy is of the order of M vp and usually By/Kr p I , the magnetoelastic energy
is negligible.
Formation of a pore increases the area of the surface of a sample. The main
contribution to this increase is the area of the surface of a pore. This is because the change in
the area of the external surface of a sample is only a fraction of the area of the surface of a
pore, which (the fraction) is (2/3)(v p/V )1I3 , and therefore tthis contribution is negligible .
According to the linear theory of elasticity, the stress tensor consists of a term which is
proportional to the external applied pressure, P , and another term which is proportional to
the specific surface energy, y . Hence, a change in the elastic energy due to the formation of
2
a pore consists of term s proportional to p 2 , y, and yP : ...(P vp/K) + ... (yPvp/Krp) +
2
... (yv p/Krp ) . As a rule, P K , y Kr; , and y K(Mrp)2 . In this case a contribution of
the regarded change in the balance of energies is negligible .
When only linear terms on P and yare taken into account, a change in the Gibbs free
energy per unit volume of a sample (specific Gibbs free energy) due to the formation of a
pore in the Clausius-Mossotti approximation is as follows 23. 25 :
(35)
where Ns is the demagnetization factor of a sample as a whole, (ndm) = Lk!kndmk , ndmk , Sk ,

and Vk are demagnetization factor, surface area, and volume of the k-th type pore,
respectively.
Equilibrium shape of the k-th type pores corresponds to the minimum of on the
eccentricity of the k-th type pores , Ek, and is determined by the following equation :
(36)
For a case of identical pores of a small volume fraction Eq. (35) yields:
(37)
where the following dimensionless quantities were introduced :
(38)
where vp is the volume of one pore.

The dependence of the surface area of a spheroidal pore , sp , on the volume of a pore ,
15
Vp , and the eccentricity, E , and the dependence of the demagnetization factor, n dm , on E
were taken into account, deriving Eq . (37) . There exists an equilibrium value of the
eccentricity, e, , which corresponds to the minimum of <1> (X,E) on E . Eqs . (36) and (37) show
that the equilibrium shape of a pore does not depend neither on the shape of a sample, nor
on the external pressure. Expressions for Ee have been reported earlier':' for small nearly
spherical pores and for large very extended pores. Using Eq . (38) those expressions can be
rewritten as follows:
Ee = 0.99xl 12 for x I ,and
e, = I - 0.1 (3.08/x)617(lnx/3.08r6n [ I - (Inx/3.08)]617[ 1- (Inx/3.08) -(Inlnx/3.08)]-6n
for x ~ 8.37. (39)
A relative error in e, in Eq. (39) is less than 4%. The equilibrium eccentricity and the
axes ratio, AR , of a pore of an intermediate size, x , were computed numerically:
Table 1. Equilibrium eccentricity and AR as functions of x .
x 0.061 0.122 0.244 0.488 0.977 1.950 3.900 7.800

e, 0.257 0.345 0.463 0.610 0.766 0.884 0.953 0.983
AR 1.035 1.065 1.128 1.262 1.556 2.139 3.301 5.294
This table and Eq. (39 ) show that the larger the pore is, the larger is it' s elongation.
Eq. (36) shows that when the porosity of a sample is essential, the shape of each pore is
determined by the factor (I - f )M 2 instead of just M 2 as it was for a single pore.
Pore Contribution to Anisotropy
Anisotropic equilibrium pores may cause an additional anisotropy of various physical

properties, such as mechanical properties and induced ferromagnetic anisotropy".
Let us consider a case when an equilibrium pore in a ferromagnet is formed at a
sufficiently high temperature by means of diffusion. If the shape of the pore remains
unaltered during a rapid cooling (quenching), the anisotropic shape of the pore contributes
to the energy of magnetic anisotropy, and this contribution is as follows :
(40)
where Ndml. is the demagnetization factor of a sample as a whole in the direction

perpendicular to the longitudinal axis of a pore .
According to Eq. (40) even a spherical pore contributes to the anisotropy of a sample if
the sample itself is anisotropic. At Ne =N dml. , M 2 = 2x 10 erg/ern ' , n dm = 0.1 , V p = 0.01 V,
6
Eq . (40) yields et>alV = 4.4 x10 erg/ern ' . Hence, in some cases, such as thin films and
4
sintered materials this contribution appears to be of a great importance.
16
Peculiarities of Diffusional Kinetics of Pores
Volume change rate of a small nearly spherical pore is obviously determined chiefly by
the specific surface energy and external pressure. In this case ferromagnet demonstrates no
specificity. Here let us consider the case when the surface diffusion is active enough for a
pore to preserve permanently it's equilibrium shape, and if the regarded pore is large
enough, to be essentially elongated.
As numerical calculations show, the Gibbs free energy of the equilibrium pore, 4> e =
4> (X,Ee ) , at some positive N *, increases from zero with the increase of x and then has a
maximum at some x =Xc (a critical size). The position of this maximum depends on the value
of N * only. With further increase in x , the Gibbs free energy decreases, reaching zero at
some x = Xo , and then decreases below zero with still further increase in x . For N * = 1/3 ,
the computation yields Xc = 5.16 and Xo = 7.6 . As N * decreases , x, and Xo increase to
infinity.
When bulk diffusion is possible, a pore of a size smaller then the critical one, is being
healed. While the pores of a size larger then the critical one , grow . The rate of a diffusional
change in the pore volume of a long pore has been calculated". In the absence of sources and
sinks of vacancies in the bulk of a material
(41)
where Vc is the critical value of the pore volume, and
0= (5xln5xr6n S 0.013 . (42)
When the density of sources (sinks) of vacancies is sufficiently high, then
(43)
where the mean free path of the excess vacancy, (I ) , is supposed to be much smaller than
the smallest radius of the curvature of the pore .
Eqs . (41) and (43) are valid for 21tM 2Ndm > P only.
Discussion of the Polar Materials
The model presented above is approximate. It does not take onto account (i) a possible
deviation of the equilibrium shape of a pore from the shape of a spheroid and (ii) a
directional deviation of the magnetic moment near the pore . Apparently these simplifications
overestimate the Gibbs free energy of a system. Therefore the curve which represents the
equilibrium Gibbs free energy as a function of x for a real system runs below the theoretical
curve . As a consequence, Xc and Xo are also overestimated. So all the described effects
(elongation of a pore and peculiarities of diffusional kinetics of a pore) may be easily
observed in real systems . It should be mentioned that a diffusional relaxation, which causes
the equilibrium elong ation of a pore , and a change in the volume of a pore , leads also to a
change in the shape of a sample .
It should be emphasized that to obtain Eqs . (41) and (43) no assumption on the
conditions of the shape of a sample is needed . Contribution of a change in the shape of a
sample to v, and (dvp/dt) has been estimated to be about (4v p/5V) and it was shown that it is
negligible. Hence, Vc and 0 in Eqs . (41) and (43) are locally time-independent parameters. A
17
slow change in these parameters may lead to changes in the signs of the rates of the change
of the volume of pores. A large pore may grow at first, then it may stop it' s growth .
All the calculations of the effects of anisotropy and diffusional kinetics of pore s were
performed for a single pore, and they are valid as far as the poros ity of a sample remains to
be a small.
REFERENCES
I . Ya. E. Geg uzin. Physics of Sinte ring, Nauka, Moscow (1967).

2. Y.V. Kornyu shin. Tran sport Phenom ena in Real Crystals in External Fields, Naukova Dumk a, Kiev
(198 1).
3. Y.V. Kornyushin, On single pore and brittle crac k in a one-do main ferromag net, Fizika Me tallov i
Metall oveden iye 45 : 192 (1978).
4. Yu.V. Kornyushin, On the theory of sintering of ferromag nets, Science of Sint ering 10: I85 (1978 ).
5. Yu.V. Korn yushin , Void in ferromagnet, numer ical calc ulatio ns, JMMM 13:322 (1979) .
6. C. Kittel. Introduction to Solid State Physics , John Wiley & Sons, New York (1966).
7. S.V. Ve nglinskaya and Yu.V. Kornyu shin, On the possibility of healing of extended defects due to
transport ation of vacancies stimulated by electric current, Metallofi zika 61:7 1 ( 1975).
8. Y.V. Korn yushi n, In fluence of external mag netic and electric fields on sintering, structure and
prope rties, J. Ma ter. Sci. (Letters) 15:799 (1980) .
9. L.O . And rushchik , Y.V. Korn yushin and S.P. Oshkaderov, Physical nature of the proce sses taking place
dur ing electric contact sinter ing of metal powders, Science of Sinterin g 2 1:3 ( 1989).
10. A.I. Raic henko. Math ematical Theory of Diffusion in App lications , Naukova Dumka, Kiev (1981) .
I I. Yu.V. Kornyushin , On the kinetics of early stages of electric contact sinteri ng, Phys. Meta ls 5:6 18
( 1983) .
12. Y. Adda and J. Philibert, La Diffusion dans les Solids , V. 2, Press. Univ. France, Paris (1966).
13. Y.V. Korny ushin, O n the theory of diffusional processes in crystals, containing dislocations, Phys.
Metals 5:377 (1983) .
14. Y.V. Kornyushin, On the theory of diff usional shrinkage of a pore in real crysta l, J. Mat er. Sci. 17:3423
( 1982).
15. Y.V. Korny ushin and L.N . Larikov , Separation of thermally mobile and immobile dislocations duri ng
anneal ing of strengthened crysta ls, Metal lofi zika 73:66 ( 1978).
16. W . Hermel, Yu.V. Korn yushin, S.P. Oshkaderov , S. Siege l and V. Shvitai, Investigation of diffusional
healin g of pores under Joule heating conditio ns, Metallofi zika 2:74 ( 1980).
17. L.N . Larik ov and V.M. Falchenko, Mechanism of influence of phase tran sformation on diffusion, in:
Diffusion in Metals and A lloys , M.A. Krishtal, ed ., TpI , Tula (1968).
18. L.O . And rushchik, O.N. Balakshina, YU.V. Kornyushin, S.P. Oshkaderov and V.A. Sh vitai, On the
driving forces and kinetics of diffusional processes during sintering of metal powders, Phys. Metals
9:222 ( 1990).
19. Yu.V. Kornyushin, Effec tive parameters in diffus ional problems under bulk heating, Phys. Meta ls 9:940
(1990).
20 . C. Herring, Diffusional viscosity of a polycrystalline solid, JA P 21:437 (1950).
2 1. Ya. E. Geg uzin and M.A. Krivoglaz, Motion of Macroscopi c Inclusions in Solids , Metallur gizdat,
Moscow (1971) .
22 . R. Landa uer, Electrical conductivity in inhomoge neous media, in: Electric Trans port and Optical
Prop erties of Inhomogeneous Media, J.C. Garland and D.B. Tanner , ed., All', New York (1978) .
23. Yu. Korn yushin, Two extensions of the Cla usius-Mossotti approximation, Scien ce of Sint ering, 29 :63
( 1997).
24 . Yu . Korny ushin, Th e Clausius-Mossotti approxi mation in the theory of sintered mater ials, Science of
Sintering 30:37 ( 1998).
25 . Yu . Kornyushin, More general solution of the Clausius-Mossotti model, Metal Phy sics and Ad van ced
Technologies 20:26 (199 8).
26. A.I. Ak hieze r, V.G . Bar' yakh tar and S.V. Peletm inski i, Spin Waves, North Holland, Am sterdam (1968) .
27. J.D. Eshelby, Th e continuu m theory of lattice defec ts, in: Solid State Physics , Vol. 3, F. Seitz and D.
T urnbull, ed., Academic Press, New York (1956) .
28 . V.M. Dav idovs kii, Yu.V. Korn yushin, Mag netic anisotropy due to nonspherical pores and inclusions in
ferrom agnet, Fizika Metallov I Metallovedeniye 33:440 (1972) .
18
LIQUID-PHASE SINTERING OF THE SYSTEMS
WITH INTERACTING COMPONENTS
Arnold Savitskii
Institute of Strength Physics and Materials Science,

Prospect Academichesky, 2/1, Tomsk 634021, Russia
Introduction
The existing conceptions on the problem of liquid phase sintering fail to give answers to
many questions like the follow ing:
- why do compacts during liquid-phase sintering grow at first and then shrink, but not vice
versa ;
- why is the amount of compact growth the greater, the coarser the solid-phase particles ;
- why no shrinkage is observed , even if temporary, when the content of a liquid additive
does not exceed the solubility limit in the solid phase;
- why does the amount of swelling increase only within the concentration range of the solid-
phase existence with increas ing the additive content in the mixture;
- why is the heat release observed at the first, or growth, stage, but not during shrinkage;
- why is the growth rate in the systems with intermetallic compounds much higher than in
those with solid solutions only.
So there was an objective urgency to develop a new theory of liquid phase sintering which
would be able to find answers to all these questions and to give a quantitative descr iption of vol-
ume changes of compacts during sintering . It is important, that the theory could describe sintering
of any system, including those with interacting component s, compacts of which experience essen-
tial growth, for example, during reactive sintering.
This publication is undertaken with the aim of reviewing our new ideas on this problem in a
short way and to bring them to notice of experts, who are not indoctrinated with such a totally
fresh view on the problem so far. The main principles of the developing theory of liquid-phase
sintering of the systems with interacting components were formulated from the common, thermo-
dynamical, point of view.1 These principle s include quite new concepts concerning, first of all, the
nature of the moving forces for sintering mixtures of interacting components as well as the
mechanism of diffusion interaction between the solid and liquid phases.
Some readers complain that the book 1 of the same title as this survey is rather sophisticated .
Probably, such readers did not manage to read the book from the beginning to the end since they
are interested in sintering theory, but not in sintering of concrete systems, for example, AI-Cu al-
loys. However, the book is written in a such manner that all details of liquid phase sintering can
become clear only as a result of analysing the major part of the real experimental data obtained for
a few binary systems having different types of phase diagrams .
Advan ced Science and Technology ofSintering , edited by Stojanovic et aJ.

Kluwer Academ ic/Plenum Publishers, New York, 1999 19
Moving Forces for Sintering of Compacts from Interacting Components
and Determination of the Sintering Phenomenon
A starting point of the theory of liquid-phase sintering may be considered to be the recogni-
tion of the fact that the main, leading process during sintering powder mixtures of interacting
components is the alloy formation. This result has been obtained on the basis of the direct ther-
modynamic estimations which testified that the energy released by a system during the alloy for-
mation was 2-3 orders of magnitude higher than the energy that could be liberated as a result of
complete elimination of interparticle pores. All the other processes are forced to obey the alloy
formation, at any rate, during the starting and the main part of subsequent periods of sintering cy-
cle. It is after establishing the chemical equilibrium that the behaviour of a system may, as it is
customarily considered, be controlled only by the excessive surface energy.
In other words, the main process which controls and determines the sign and amount of vol-
ume changes of a mixed powder body during sintering is the mass transfer due to alloy formation.
The mass transport associated with the action of surface tension forces should be considered as an
important but secondary process. The mass flow caused by capillary forces is the major process
only for non-interacting systems in which some mutual solubility is necessarily available but it is
limited. However, the limited solubility does not bring about such a considerable chemical mass
transfer as it is the case during sintering of interacting components which possess a great one-
sided or mutual solubility or can form intermetallics.
From the viewpoint of the moving forces, a scientific definition of the sintering phenomenon
can be claimed as the follow: sintering is a thermal treatment which results in changing dimen-
sions and physical-mechanical properties ofcompacts under the action of the diffusion alloy for -
mation and capillaryforces.
The new notion of the moving forces for sintering mixtures of interacting components makes
it also possible to define what "activated" and "deactivated" sintering are. If directions of the
mass transfer due to alloy formation and capillary forces coincides with each other, then the sin-
tering process is activated. If those directions are opposite to each other, the sintering process is
deactivated. I
Diffusion Interaction of Solid and Liquid Phases
Though the problem of diffusion interaction between solid and liquid metals is very impor-
tant not only in liquid-phase sintering, but in many other technological processes, no strict theory
of this phenomenon is available .v' There is a generally accepted assumption that dissolution is re-
alised due to removal of atoms from the surface of solid into liquid and then their diffusion trans-
fer from the solid-liquid interface into the liquid bulk.i?
An alternative is our conception that dissolution of solid in liquid is realised by diffusion of
solvent atoms from liquid into solid until the concentration of the alloy formed in the interface
layer enables it to pass into the liquid by melting,"
Diffusion penetration of atoms from melt should change the chemical composition of the
solid phase, so that the melting temperature of its surface layer will be lowered as compared with
pure metal. The presence of second component atoms in the crystalline lattice decreases its in-
teratomic cohesion forces and therefore the melting point. Thus, they are a supersaturated solid
solution or an intermetallic compound which pass into liquid but not pure metal. It is necessary to
stress that due to diffusion from the melt the supersaturation concentration of the second compo-
nent in the surface layer of solid is maintained continuously in the process of passage of solid in
liquid.
However, such an approach to the problem is not obvious and there are theoretical and ex-
perimental works'"" in which the possibility of the alloy formation on the metal surface in the
process of dissolution is completely rejected. Some authors'J'" neglect the process of solid solu-
tion formation during dissolution as an inessential factor. Elliot,14 Bockstigel.P:" Levin et al. 17
consider that during liquid-phase sintering the Fe-Cu system, at first dissolution of iron in liquid
copper takes place up to saturation, which practically completes instantly, and only then does the
diffusion of copper atoms into iron particles take place.
20
Nevertheless, the results of many studies indirectly support the idea that the continuous
transformation of the surface layer of solid into liquid state is preceded at first and then constantly
accompanied by the diffusion of atoms from liquid into solid. Such a mechanism of solid-liquid
interaction explains, for example, the nature of the liquid metal embrittlement of metals and alloys
and has predicted a new class of systems in which this phenomenon is to be observed. 1819 By
varying solubility of a liquid phase in solid by means of their purposeful alloying, we were able to
control this phenomenon, i.e., change plasticity and strength of material being in contact with the
melt in the desired direction ."
Particularly, the concept of primacy of diffusion from liquid into solid has completely justi -
fied itself in the investigations carried out by us on sintering in the presence of liquid phase.
Plastic Flow in Diffusion Zone
As it was already said, the transition of solid into liquid is preceded and then accompanied
by atomic diffusion from liquid into solid through their interface during liquid phase sintering. So
it is essential to concentrate reader's attention even if briefly on the phenomenon of substance
flow in the diffusion zone of solid, known as the Kirkendall effect.
First of all, it should be noted that diffusion of atoms of one metal in the lattice of another is
realised, as a rule, due to a vacancy mechanism. It is caused by the fact, that the most metallic al-
loys are formed by substitution when atoms of a component being dissolved occupy the lattice
sites of a solvent metal.
There are two main types of stresses arising in a diffusion zone and differing by their nature:
concentration and diffusion ones." The concentration stresses are due to the fact that atoms of two
components are mixed in the diffusion zone. The components differ by their nature, i.e., by the
type of crystal lattice, its parameter, elastic module, etc. The concentration stresses takes place
only due to existence of a concentration gradient of a diffusing element in the solvent lattice, par-
ticularly, as far as there is pure metal in front of the growing diffusion zone. It is owing to the co-
herent bond of the diffusion zone with pure metal whose lattice parameter remains unchanged that
the concentration stresses arise.
The diffusion stresses in a diffusion zone of solid next to the interface are induced by in-
creasing in the crystalline lattice the number of sites occupied by foreign atoms of diffusing com-
ponent, i.e., by increasing the total number of atoms of the solid phase, or its mass and volume. In
the diffusion zone of the solid component into which the diffusion flow is directed, an excess of
atoms are to arise. Edge dislocations serve as sinks for excessive atoms in this case, or in other
words, as sources for vacancies . The emission of excessive vacancies by the edge dislocations
causes climbing of the latter in the direction perpendicular to their slide planes and, hence, the
flow of substance in the diffusion zone (the Kirkendall effect) . As a result of enlargement of the
volume of the crystal lattice due to formation of new points in the lattice, compressive stresses
appear, and the material suffers deformation of three-dimensional expansion .
The strain of a lattice due to the concentration stresses may has any sign which depends on
what is the nature of metal diffusing from liquid into solid. Unlike this, the sign of the diffusion
stresses and deformation of the lattice into which the diffusion flow of atoms is directed, is always
positive, that corresponds to the volume increase. As by their magnitude the diffusion stresses es-
sentially exceed the concentration ones, the total deformation of a diffusion zone is always posi-
tive. It means that solid phase particles grow in the first stage of diffusion from liquid in solid
during liquid-phase sintering .
Model of Two-Component Powder Body Being Sintered in Solid State
Of significant importance in the physics of sintering is the problem of creating a model of a

two-component powder body which would enable one to visualise the nature and mechanism of
its volume changes during solid-state sintering as well as to predict the character and order of vol-
ume changes during liquid-phase sintering. The model of a powder body being sintered in the
presence of liquid phase is to be in a logical way related to the model of the two-component pow-
der body being sintered in solid state and to follow from it as a result of transition of the additive
into melt. Thus, we are forced to consider a model of a two-component compact being sintered in
21
In a real binary powder compact in the initial state particles of one component are mostly
surrounded by particles of the other component over a sufficiently wide range of mixing ratios. All
of them are in a more or less tight contact with each other. Hence, a group of particles of an
arbitrary shape and size, where the central particle is the additive component while adjacent
particles surrounding it are the main component, can be used as an elementary volume, or a model
of a two-component particulate solid. The empty spaces between the particles in the model
represent interparticle pores in a compact (Fig. I, a) . This model can be shown to explain
qualitatively the pattern of volume changes of compacts during solid-state sintering due to diffusion
interaction between the constituent components .'
a b c
Figure 1. Models of compact being sintered in solid state and in the presence ofliquid phase: a - mutual location of base
particles (in the periphery) and an additive in solid slate; b - mutual location of the particles and liquid additive;
c - volume growth of the particles due to the diffusion from the melt; d - volume decrease of the particles due to
transition of their surface layer into liquid.
Model of Compact Being Sintered in Presence of Liquid Phase
For changing over from the solid-state model to a solid-liquid one it is necessary to transform
the particle of an additive component into liquid state (Fig. I, b). The solid-liquid model should
allow one to understand the nature and mechanism of volume changes of compacts during liquid-
phase sintering as well as sequence of the changes.
However, the main objective of creation of the solid-liquid model is to give one an
opportunity to establish a quantitative relation between the amount of volume changes of compacts
during liquid-phase sintering and their initial porosity, quantity of an additive, value of mass
transfer at the interface due to alloy formation and rearrangement of particles .
The principal difference of liquid-phase sintering of interacting components from the solid-
state one is not in the fact that appearance of liquid phase changes the capillary forces in contact
areas between particles . The point is that after forming melt due to its wetting of particles the total
area of the interaction surface of the components is essentially increased. It is this circumstance
that sharply accelerates the alloy formation process," and all the thermal and volume effects.
The solid becomes capable of transforming into liquid state, as it was mentioned above, only
after the concentration in its surface layer has reached supersaturat ion at a given temperature. Thus,
the second feature of liquid-phase sintering of a two-component powder body is that with time the
direction of the preferential mass transfer changes its sign at the solid-liquid interface.
In the first stage of the component interaction the diffusion of atoms from liquid to solid
produces a volume increase of particles of the ingredient forming the base of a compact, which
results in moving their geometric centres apart and, therefore, leads to the increase in linear
dimensions of the whole powder body (Fig. 1, c). A subsequent transition of the solid phase over its
surface into liquid is accompanied by reduction of particles in volume, drawing their centres
together as a result of action of capillary forces and by shrinkage of the compact (Fig. 1, d) . Thus,
after liquid phase formation a compact during sintering is to display growth at first, and then -
shrinkage (Fig. 2, curves 2-4).
However, the sequence of stages for growth and shrinkage of the compact in the course of
liquid-phase sintering should only take place at a low solubility of the liquid forming additive in
22
solid or at a sufficient content of liquid phase , since only under such conditions for the surface
layer of solid phase to be supersaturated up to the definite concentration a limited amount of the
additive is required , and after reaching the supersaturation there remains an adequate amount of
liquid phase for particles to be dissolved in (Fig. I, d) .
580C
3
I-----=~=:::;:==l 0
4 -1
o 10 20 30 40 t. min
Figure 2. Di latom etry of liqu id-ph as sintcring AI-Cu co mpac ts at 580
"C. Copper co ntent: 1 - 3; 2 - 4 ; 3 - 5; 4 - 6 wt %. 5 - tempera ture in a
compact, 6 - in the dil atom etcr tub e.
If the solubili ty of liquid in solid is high or intermetallics are formed at a small content of
liquid phase in a compact , the melt may be exhausted during sintering before the concentration in
the surface layer of solid phase achieves such a value which will allow it to pass into liquid state
(Fig. I, c). The reason for fast disappearance of liquid in transient liquid-phase sintering is that
thanks to fine particl es the total surface area of solid phase through which the diffu sion takes place
is very large, and the sizes of particles are of the same order of magnitude as the depth of the
diffusion zone on the ir surface. In this case the proces s of transition of solid into liquid will not
take place, to say nothing about the dissolution-reprecipitation process , and the powder body will
undergo only growth (Fig. 2, curve I).
A characteristic feature of the compact growth observed during liquid phase sintering is
formation of pores at the sites of former alloying additive particles ." The pores repeat
approximately the shape and size of these particles in the green compact. The model of a two-
component compact being sintered in the presence of liquid phase , which is represented in Fig. I,
predicts the formation of such pores (Fig. I, c), because it presumes the existence of a relatively
rigid skeleton made from particles of the base constituent. The skeleton is "rigid" in the sense that
rearrangement of particle s which could lead to filling the pores remaining at sites of former
additive particles is impossible due to, so called, the arch effect. It is "relatively" rigid in the sense
that some displacements of particles become , nevertheless, possible, which provide macroscopic
volume changes of the compact as a whole . The existence of such a relatively rigid skeleton of a
compact is likely to be due to a fairly close packing of particles in pressed state.
Quantitative Description of Volume Changes of Compact

Being Sintered in Presence of Liquid Phase
To find an analytical equation relating the final porosity of a sintered alloy to the green
porosity a principle has been used," according to which the geometrical shape of sintered alloy
particles completely copies the shape of the base component particles in the green compact.
Besides, the following simplifying assumptions were made.25
I. Liquid readily spreads throughout a compact, so that all the base particles are able to
interact with the melt over their whole surfaces.
23
3. Diffusion of atoms from liquid to solid increases the volume of particles, whereas transi-
tion of solid-phase atoms into the melt is accompanied by decreasing particle size. When both dif-
fusion flows are present, the sign and magnitude of the change in particle volume are determined
by the difference between the flows, or by the predominant flow of atoms at the interface.
4. The increase of particles in volume is accompanied by their mutual "moving apart", as a
result of which the whole compact grows. Conversely, when the particles decrease in dimensions,
the action of capillary forces brings them closer to each other, and the compact experiences
shrinkage.
5. The change in the compact volume due to solid-state sintering, rearrangement, the action
of gases trapped in closed pores, and any other reasons is small and can be neglected.
With the help of the model taking into account the green porosity and the sequence of the
diffusion processes at the solid-liquid interface, an analytical equation has been obtained :
= -C,"(1- C) - CC RP
- - - - - - - -=- +
(1- C)(1- C, - CL )
P L
0 ' (1)
l-C-C L
l-C-C L
Here: P - final porosity of the alloy;

Po - green porosity;
C - atomic share of the second component in a compact;
Cs - concentration of the liquid forming component in solid phase after sintering;
CL - concentration of the solid-phase component in liquid after sintering;
R - is a coefficient of rearrangement. It is greater than zero but less than unity. Its value
shows, what share of the green porosity has remained after rearrangement due to liquid formation.
The relative change in compact volume caused by sintering is !J.VNo = (Po - P)/(l - P),
where Vo is the volume of the green compact. Substituting Eq. (I) into this formula we get an
equation whose use can be especially convenient in dilatometric studies of the liquid-phase sin-
tering process.
-llV = 1- (1- Po)(1- C - Cs)

_ - - - - - C_ _-'---'- -'---_ _
(2)
Vo (1- RPo)(1- C)(1- C, - C.)
A disadvantage of the equations (I) and (2) is the lack of kinetic parameters in them: time
and temperature. To introduce such parameters into these equations, it is necessary to find a form
of Cs =fiT, t) and CL = j(T, t) functions . At present it is the major problem to be solved in the the-
ory of liquid phase sintering.
On the basis of mathematical treatment of our experimental results we succeeded in estab-
lishing the existence of a negative rearrangement in the growth stage, the formation of liquid
phase inside particles, their cracking during formation of intermetallic compound and some other
important facts. The main part of these phenomena can be independently observed by means of
microstructure investigations, but there are such phenomena, for example, the negative rear-
rangement, which can be only detected using mathematical treatment of experimental results with
the help of the above equations.
Growth and Shrinkage Due to Alloy Formation as Independent Stages
Though the phenomenon of compact growth during liquid-phase sintering has already been
studied in many works, it was not recognised as an independent stage. Since the nature of diffu-
sion interaction of solid and liquid phases remains common for all the systems, volume changes of
compacts during liquid-phase sintering are qualitatively of the same character. As after establish-
ing the contact between liquid and solid the beginning of their interaction turns out to be diffusion
into the solid phase, the first stage of sintering in all the interacting systems without exception is
the compact growth in volume. The amount and duration of the swelling stage depend on the
24
solubility limit in solid, additive quantity , green porosity , particle size and whether the system is
exothermic or not.
In a similar manner the phenomenon of dissolution of particles in the melt is usually treated
only as an indirect factor ensuring densification during rearrangement as a result of liberation of
the particles from their interlocking. In the presence of liquid phase particles can slide due to
smoothing and lubrication of their surfaces. " The old three-stage theory by Kingery and others in
no way does take into account the compact shrinkage which is directly due to dissolution of parti-
cles in liquid.
Our experimental studies conducted for more than 30 years have finally convinced us that
both the processes of growth and shrinkage caused by mutual dissolution of solid and liquid,
which do not coincide in time, should be considered as independent, separate stages.
Thus, the theory of liquid-phase sintering of mixed powder bodies should include the two
stages of the process which do not take place during sintering of the non-interacting systems : the
volume growth caused by dissolution of liquid in solid, and shrinkage related to dissolution of the
solid phase in liquid .
After saturation of the liquid phase with a solid component, a chemical equilibrium is
reached in the system being sintered, and shrinkage can now go on through the ordinary mecha-
nism of dissolution-reprecipitation like in non-interacting systems or during supersolidus sintering
of alloy powder compacts.
Reasons of High Rate of Compact Growth
A fairly high rate of swelling compacts produced from components which do not form in-
termetallics can presumably be explained, apart of other reasons, by the influence on the diffusion
process of grain and subgrain boundaries arising in the diffusion zone as a result of its deforma-
tion and recrystallization. A selective diffusion of atoms from liquid into solid through lettice de-
fects results in rapid melt formation at grain boundaries and disintegration of particles. When the
average size of particles decreases by one order of magnitude due to disintegration, the area of the
interface through which the diffusion takes place increases by two orders of magnitude . It is pos-
27
sible that there is a diffusion-induced migration of grain boundaries in the diffusion zone.
Heat release during formation of an alloy or intermetallic compound leads not only to the lo-
cal temperature rise Just in the diffusion zone but also to the considerable temperature increase of
the entire compact? Because the heat formation of intermetallics is many times greater than that
for solid solutions, the growth rate of compacts made from mixtures of components forming in-
termetallic compounds is much higher than from those forming ordinary alloys only .
Some Singularities of Rearrangement
Some features of the rearrangement process during sintering for the interacting systems
should be noted. Historically, the first detailed investigations on liquid-phase sintering were car-
ried out on technically relevant systems of cemented carbides and heavy alloys in which the base
particles possess a limited solubility in liquid and practically can not be deformed during com-
pacting . The absolute rigidity or weak deformability of particles in these compacts result in ab-
sence of the very tight and extended contacts and cold-welded bridges between particle s. In such
highly porous compacts with particles which are not bound with each other rearrangement can
easily take place after liquid formation . Thus, it is this rearrangement that gives the main contri-
bution to the shrinkage process in non-interacting systems.
However, later on this shrinkage mechanism was automatically transferred on all the other
systems including the interacting ones, in which liquid is soluble in solid, and the particles are
ductile. In reality, rearrangement in the systems on the base of plastic metals is impossible imme-
diately after liquid formation . IS Deformed particles during their pressing are closely fit to each
other, with the cold-welded contacts arising between them, as a result, their mutual motions are
blocked at the moment when liquid phase is formed .
Thus, the first peculiarity of rearrangement in the interacting systems with ductile metals is
that this process becomes possible after particles get free from interlocking due to dissolution.
Under this circumstance favourable conditions are created for densification due to bringing parti-
25
c1es closer to each other as a result of decreasing their size and mechanical repacking connected
with the presence of interparticle pores in a compact. The shrinkage owing to repacking is taken
into account quantitatively by the rearrangement factor. Although such a division of the rear-
rangement process into "chemical" and "mechanical" parts is purely formal, it enables one to un-
derstand the nature of the rearrangement phenomenon and to allow for it quantitatively .
The experimental results show that destruction of the skeleton and compact shrinkage owing
to rearrangement in the systems with interacting components can take place in the first stage only
under exceptional conditions, namely, in the presence of high porosity and large quantities of liq-
uid. Unlike the non-interacting systems, a typical shrinkage of compacts from interacting compo-
nents sets in at the second sintering stage only after growth has stopped. At this moment as a re-
sult of supersaturation due to diffusion, the surface layer of the solid phase can pass into liquid by
melting," Fine particles can dissolve completely, while large ones can only decrease in sizes. Mu-
tual drawing closer to one another of residuary decreased particles under the action of capillary
forces may be considered as a rearrangement process. Singularity of this rearrangement is that it
takes place within the space liberated for the particles to move freely owing to their complete or
partial dissolution . Thus, although shrinkage at the dissolution stage is realised through rear-
rangement of particles, quantitatively it is determined by the degree of their dissolution .
The second peculiarity of rearrangement linked with shrinkage is that the process takes place
over the whole subsequent sintering cycle after growth: at first, as the particle size diminishes
owing to dissolution of solid in melt," and, then, during the dissolution-reprecipitation proc-
ess.30,31
It is important to distinguish rearrangement during growth of a compact from that accompa-
nying shrinkage. Since the result of the former is an additional growth of compacts, it is desig-
nated as a negative rearrangement. Quantitatively its contribution to the growth value is deter-
mined as the difference in the compact volume increase brought about the Kirkendall flow and its
factual increase. The negative rearrangement is associated with the uneven diffusion from liquid
into solid over particle peripheries . The magnitude of negative rearrangement contribution to the
value of compact growth depends on the average size of the particles. The larger the particles, the
more the compacts swell.
It should be noted that, on the whole, the rearrangement phenomenon needs further investi-
gations, deeper analysis and a quantitative description .
Effects of Porosity on Volume Changes
For all the investigated systems an increase in the green porosity leads to a decrease in the
amount of compact growth and to an increase in the shrinkage degree. Existence of the depend-
ence of relative volume changes on porosity is brought about by arising rearrangement in both
growth and shrinkage stages of sintering. As it follows from Eq. (2), when no rearrangement is
present, i.e., when R = I, the relative volume change of a compact does not depend on its porosity.
Effect of Temperature on Volume Changes
With temperature increase at a given composition of a mixture being sintered there are two
effects to be mentioned. Firstly, due to its influence on the diffusion mobility of atoms the higher
is the sintering temperature, the nearer the additive concentration in the solid phase approaches
the mixture content. Secondly, with the rise of sintering temperature as a result of changing in the
ratio of solubility in the solid and liquid states the mixture gets into the region of the solid-liquid
state according to the phase diagram, and the compact growth is replaced by shrinkage at some
moment of sintering.
Effect of Additive Concentration on Volume Changes
For any interacting system there are two intervals for concentration of an additive within
which features of the dependence of volume change on the additive content are different during
liquid-phase sintering. The critical concentration dividing these intervals is the solidus line on the
phase diagram. Increase of the additive concentration within limits of the existence of solid solu-
26
tions and intermetallic compounds results in an increase of the compact growth. Therefore, for
obtaining high-porous materials the solubility of liquid in solid is to be very high (of the order of
75 at. %) . At the same time, the fraction of liquid should not surpass the so lidus concentration at
the sintering temperature. Under these conditions no shr inkage begins after growth. The Ti-AI
system can serve as an example."
If the concentration of liquid forming ingredient exceeds the solubility limit in sol id at the
sintering temperature, then shrinkage sets in after growth . In th is case the amount of densification
is the greater, the higher the additive content. Therefore, in producing a high-density alloy, the
solubility liquid in the base component is to be possibly low, but the solubility of so lid in liquid
maximum. In any case, the fraction of liqu id in a compact should surpass the solubility limit in
solid at the sintering temperature.V'"
In manufacturing a multicomponent dense alloy, if possible, a liquid forming additive deac-
tivating the sintering process should not be introduced into a mixture in the form of an elemental
powder. If such an alloying addition may not be excluded from the composition in view of its fa-
vourable influence on operating properties of the material, the base component should be alloyed
by this add itive beforehand dur ing fabrication of its powder. In thi s case, the alloy powder as the
base of a compact rather than a elemental powder of pure metal will be sintered, wh ich prevents
the swelling of compacts. On the other hand , additives readily dissolving the base component
should not be present in its particles as alloying ingredients , but should be introduced into the
blend in a form of elemental powders. Otherwise, there will be no heterodiffusion fluxe s promot-
ing shrinkage during sintering."
If it is required that a structural component might change its size very little during sintering,
one ought to balance the values of growth and shrinkage.' This can be done on the basis of the
phase diagram in several ways by varying the type and content of additives as well as the tem-
perature and duration of sintering.
Thus, the understanding of fundamentals and mechanisms of compact changes in volume
during liquid-phase sintering gives poss ibil ity to formulate practically important criteria of
choosing additives, their concentrations and sintering regimes keeping dimensions of structural
parts being sintered constant or providing shrinkage or , vice versa, ensuring the maximum growth
with the aim of obtaining high-porous materials.
References
I. A. P. Savitskii, Liquid Phase Sintering of the Systems with Interacting Components , Academy
of Sciences, Tomsk (1993).
2. 0.1 . Tikhomirova, L.P . Ruzinov, M.V. Pikunov, et al. Study of mutual diffusion in Ga-Cu
system, Fizika metallov i metallovedenie, 29, 4:796 (1970), in Russian.
3. 0.1 . Tikhomirova and O.A. Zakstel'skaya, Peculiarities of phase formation while contacting
liquid gallium and indium alloys with copper, Adgeziya rasplavov i paikamaterialov,: Naukova
dumka, Kiev, 12:46 (1984), in Russian .
4. W.A. Kaysser and G . Petzow, Present state of liquid phase sintering, Powder met. 28, 3:145
( 1985).
5. V .1. Nikitin. Physical-chemical phenomena in effecting liquid metals on the solid, Atomizdat,
Moscow (1967), in Russian.
6. L.K. Savitskaya and A.P. Savitskii, Thermodynamics and mechanism of contact melting, in:
Poverchnostnye Yavleniya v Rasplavakh i Voznikayushchikh iz nikh Tverdykh Fazakh, Kab-
ardino-Balkarskoe knizhnoe izdatel'stvo, Nal'chik (1965), in Russian.
7. B. Chalmers and J.M . Lommel, The isothermal transfer from solid to liquid in metal systems,
Trans. AIME, 215, 6:499 (1959).
8. I.P. Dobrovolskii, B.A. Kartashkin, et al. On nature and mechanism of contact melting, Fizika i
khimiya obrabotki materialov, 2:36 (1972), in Russian.
9. G.A. Sakhno and I.M . Selezneva, Composition and temperature of liquid phase formation dur-
ing contact melting, in: Fizicheskaya Khimiya Poverkhnosti Resplavov, M itsniereba, Tbilisi
(1977), in Russian.
10. G.A. Pribytkovand V .1. Itin , Thermal effects during interaction of solid metal with metallic
melt, Adgeziya rasplavov i paika materialov, Naukova dumka, Kiev , 10:36 (1982), in Russian.
27
II. S.P. Savintsev and AA. Akhkubekov, Application of contact melting to determine the mutual
diffusion coefficient in melts of binary systems, Zavodskaya /aboratoriya,3:30 (1981), in
Russian.
12. V.S. Novosadovand RA Vershok, Calculation of non-stationary kinetics of the contact
melting process, Fizika i khimiya obrabotki materia/ov, 2:61 (1974), in Russian.
13. D.E. Temkin, Kinetics of the contact melting process under stationary regime, Izvestiya AN
SSSR, Metal/y, 3:219 (1967), in Russian.
14. J.E. Elliott, Growth ofsintered metal compacts, Metallurgia, 56, No 1 (1959), 17-27.
15. G. Bockstiegel, Erscheinungsbild und Ursachen von Volumenanderunge beim Sintem von
Presslingen aus Eisen-Kupfer- und Eisen-Kupfer-Graphit-Pulvennischungen, Stahl und
Eisen, 79, 17:1187 (1959).
16. G. Bockstiegel, Dimensional changes during sintering of iron-copper powder mixes and
means to reduce them, Metal/urgie, 3, 4:67 (1962).
17. L. Levin, A Stem and S.F. Dimfeld, Homogenisation during sintering in a system with lim-
ited solubility of components, Z. Metal/kunde, 71, 9:621 (1980).
18. AP. Savitskii and L.K. Savitskaya, Role of contact melting in adsorption decrease of metal
plasticity, in: Poverkhnostnye Yav/eniya v Rasp/avakh i Voznikayushchikh iz nikn Tverdikh
Fazakh, Kabardino-Balkarskoe izdatel'stvo, Nal'chik, (1965), in Russian.
19. A.P. Savitskii and L.K. Savitskaya, New data on embrittlement of metals by liquid melts,
Dok/adyAN SSSR, 174,5:1072 (1967), in Russian.
20. AP. Savitskii, T.V. Loginova and L.K. Savitskaya, Stimulation and suppression of liquid
metal embrittlement by alloying, Fizika i khimiya obrabotki materia/ov, 3:110 (1973), in Rus-
sian.
21. Y.E. Gegusin. Diffusion Zone, Nauka: Moscow, (1979), in Russian.
22. V.V. Skorokhod, S.M. Solonin, et al. Investigation of alloy formation during liquid-phase sin-
tering of powder compositions on tungsten base, Poroshkovaya metal/urgiya, I: 14 (1979), in
Russian.
23. H. Danninger, Pore formation during sintering of Fe-Cu and its effects on mechanical proper-
ties, Powder Met. Inter., 19, I :19 (1987).
24. K. May, Schwindung und Quellung beim Sintem von Metallen, Archiv fur Metal/kunde , 2,
5:154 (1948).
25. AP. Savitskii, L.S. Martsunova, and M. A Emeliyanova, Changes in compact porosity as a
result of diffusion phase interaction during liquid-phase sintering, Poroshkovaya metallurgiya,
1:6 (1981), in Russian.
26. J. Gurland and J.T. Norton, Role of the binder phase in cemented tungsten carbide-cobalt al-
loys, Jour. Meta/s, 4, 10:1051 (1952).
27. M. Hofmann-Amtenbrink, W.A. Kaysser and G. Petzow, Grain boundary migration in re-
crystallized Mo foils in the presence ofNi, Jour. de physique, 46, 4:545 (1985).
28. A.P. Savitskii and N.N. Burtsev, Dilatometric investigations of Ti-AI compacts growth dur-
ing liquid-phase sintering, Poroshkovaya metallurgiya, 3:24 (1983), in Russian.
29. AP. Savitskii, E.S. Kim and L.S. Martsunova, Compact shrinkage during liquid-phase sin-
tering, Poroshkovaya metal/urgiya, 9:9 (1980), in Russian.
30. G. Petzow, W.A Kaysser and M. Amtenbrink, Liquid phase and activated sintering, Sintering
- theory and practice. Material science monographs, 14:27 (1982).
31. W.A. Kaysser and G. Petzow, Present state of liquid phase sintering, Powder met. 28, 3:145
(1985).
32. A.P. Savitskii, G.N. Romanov, and L.S. Martsunova, Deformation of AI-Cu powder bodies
during liquid-phase sintering, Poroshkovaya metal/urgiya, 8:39 (1985), in Russian.
33. R.M. German and K.A D'Angelo, Enhanced sintering treatments for ferrous powders, Inter.
Meta/s Reviews, 29, 4:249 (1984).
34. R.M. German, RH. Rubin, Enhanced sintering through second phase addition, Powder met-
allurgy, 28, 1:7 (1985).
35. AP. Savitskii, L.S. Martsunova, V.G. Gopienko, et ai, Prevention of compact growth during
sintering of complex systems, Poroshkovaya metallurgiya, 8:30 (1981), in Russian.
28
SIMULATION OF TWO-DIMENSIONAL MICROSTRUCTURAL
DEVELOPMENT DURING LIQUID PHASE SINTERING
Zoran S. Nikolic
Faculty of Electronic Engineering, Department of Microelectronics

University of Nish , 18000 Nish, P.O. Box 73, Yugoslavia
Electronic address : znikolic@elfak.ni.ac.yu
INTRODUCTION
The microstructural development can be simulated by modeling of diffusional field, as
well as by modeling of dissolution and precipit ation processes for liquid - solid system. It is
well known from many experiments with mixtures of small and large particles that during
liquid phase sintering smaller particles partially dissolve and a solid phase precipitates on
the larger particles . This solution-precipitation process leads to further densific ation by
rearrangement of smaller and larger particles. The microstructure may change either by
larger particles growing during the Ostwald ripening or by shape accommodation .
In this study , two-dimensional modeling and simulation of micro structural evolution
as a result of grain growth due to grain boundary migration was conside red. The simulation
method developed is based on the submodel s defined for solution -precipitation under
gravity and microgravity conditions. The computer-generated microstructures can be
applied for prediction and estimation of gravity- and microgravity-induced solid-liquid
segregation .
MODEL SYSTEM TOPOLOGY

Let us assume a model system of N contours, closed boundaries as two-dimensional
(2-D) particle representation, of solid phase in the liquid phase . This model will be based on
the assumption that there are no pores during liquid phase sintering.
The model system contours can be represented as an array of moving points , using the
boundary points of contours (sites located on the contour boundary or on the phase
interface) . Let there be the sets of point s (Fig. I)
DS ={Rs;rt,rI,...,r:,} (s=1,2,..,N) ,
Advanced Science and Technology ofSintering , edited by Stoj anovic et al.

Kluwer Academic/Plenum Publishers, New York , 1999 29
where R S is the position vector of the center of the s - th contour, and rt
is the position
vector of the I - th point on the interface of this contour with its origin at the center of the
contour, and ns is the number of its boundary points. Then the solid phase of the model
N
system is defined by the union u DS
s; 1
Figure 1. Domain definiti on.
A time-dependent microstructure will be mapped onto a 2-D by three discrete

matr ices: the integer matr ix lIeij llnxm' where the value of the element eij indicates the phase
present at the point (i, j), so that
0 for liquid phase

eij = { > 0 for solid phase, i.e. 1,2,...,N
and two real matrices for the concentration IIcijlln xm and the flux IIfijlln xm . Thu s, its
domain and the topological inform ation concerning contour neighbors characterize each
contour.
SOLUTIONPRECIPITATION MODELING
Let there is a system consisting of a dispersion of spherical particles with different
radii in a liquid in which the solid phase has some solubility. Thus, the concentration of the
dissolved solid, C, around a particle of radius r s is given by the Gibbs-Thomson equation
In(S-) =
Co
2YsIQ
kT
.~ ,
r,
(I)
where Co is the equilibrium concentration of liquid in contact with the flat solid , Ysl is the
solid/liquid interfacial energy , Q is the molecular volume of the solid, and kT has its usual
meaning. If !!.C = C - Co is small, then Eq. (I) becomes
2YsIQ
!!.C=C o . _ I
_ .- (2)
kT r,
30
This Eq. is not valid for a very small particle since t!.C becomes infinite as its radius goes
to zero. However, the number of the small particles at any simulation time is sufficiently
small so that Eq. (2) can be assumed to be valid for all particles.
Grain coarsening is a typical multibody free boundary problem in which the domains
alter their morphologies in response to the diffusion field . After solution-precipitation the
particles grow in supersaturated liquid phase, and after the supersaturation becomes small
large particles start to grow at the expense of small particles . This tendency for particles to
grow or to shrink depends on the size of particles relative to a critical particle size r* (the
radius of critical particle for which dr]dt = 0):
DS (r s < r:) will dissolve

D (rs = r)
S
neither grow nor shrink
{ D S (r > r *) will grow
s
If (r) is the arithmetic mean particle size, then for reaction controlled growth' r* = 9(r )/8,
and for diffusion controlled growth r* = (r) . Notice that the critical particle size is time-
dependent , i.e. r' (t) .
PROCESS SIMULAnON
The application of the computer simulation is very often identified with the application
of formal algorithm procedures. In recent years, a range of computer simulation models has
been developed with the aim of simulating the detailed evolution of microstructure during
liquid phase sintering e.g. computer simulation of multiparticle diffusion", grain growth
simulation based on the Monte Carlo method", etc.
Generally speaking, all of these models have a structure like process simulation system
shown on Fig. 2. Database and knowledge-database are the starting point for the realization
of this structure together with hardware and software interfaces such as mathematics-
numerical-statistics software , simulation methods, and computer graphics.
Process Modeling Knowledge

Base
Numerical Modeling
Data
Simulation Modeling Base
Applicatie S,"',~ -t
PROCESS SIMULATION
Graphical S,stem
Figure 2. Process simulation system structure.
31
2-D modeling and simulation of microstructural evolution as a result of grain growth
due to solution-precipitation process will be now considered.
Process Modeling
Mass diffusion outside the particles can be assumed to be the only mass transfer
process. If C = C( x , y, t ) then diffusion through the liquid phase is defined by the partial
differential equation of the parabolic type
aatc = DL . [ 0
ax2
2
C+ aaic).
2
(3)
Numerical Modeling
Let there is an exper imental domain of a rectangular shape that is partitioned into
subregions by a mesh. Let there be two distance coordinates x and y, and time t as
independent variables, and the respective grid spacings Lll, ~y, and ~t . Subscripts i, j , and k
may then be used to denote that space point having coord inates i/sx, j~y, and k/st , so called
the grid-point (iJ,k) . For an approximate solution of the Eq. (3), the classical five points
approximation (the Schmidt method ) can be used 4
Ci,j.k+l = (1- 2 AI - 2 A2 )Ci.j,k + Ax (Ci+l ,j, k + Ci- I,j,k ) + A y (Ci,j+l ,k + Ci,j-I,k )

(i = 2,3,..., n - I; j = 2,3,..., m - I; k =0,1,...)
where Ax = D L!:it/{Lll) 2 , and Ay = DL!:it/{~y f with the saturated concentration of liquid
phase as the initial condition and the time dependent boundary conditions"
C i,l,k = C i ,2,k
C i,m,k = Ci,m-I ,k
C1,j ,k =C 2,j, k
C n,j ,k = Cn- I,j ,k (i = 1,2,. ,n; j = 1,2, ... ,m; k = 1,2,...)
For reasons of computational stability, values of distance and time interval (Lll, t1y, and t1t)
must be taken so that Ax + A y does not exceed 0.5.
The defined numerical model assumes the contours' surfaces that have discretized with
equal- sized square s. The same discretization was used for approximating the curvature at
the contour's surface.
Simulation Modeling
Since the concentration of liquid at boundary points of solid-liquid interface is (Gibbs-
Thom son boundary condition)
S
C(r j) - K(rj) for r j on D ,
where K(r j) is the curvature at r j , thus a higher concentration around a smaller particle
gives rise to a net flux of matter from the smaller to the larger one . Starting from
assumption that solution, diffusion and precipitation processes take place in the liqu id phase
32
and that solid - solid interactions are not allowed , the flux through the finite element
(ax x ~y) of solid phase boundary point (xi' Y j) is
] . =] ! . +] Y . = -D
C"
' ,j
- C' ] '
l+ ,j . 0. ] . +
c , , - c, ] ,
I,j ,- , j . 0. ] .
J
I,j ' ,j ',j L( ax 1+ , j ax ,- ,j
_D
L
(Ci,j - Ci,j+]
~Y
.0..
I ,j+]
+ Ci,j - Ci,j_1
~Y
0
"j- ] '
J
where
if (i,j) E liquid phase
s . ={I0
I.j if (i ,}) E solid phase .
The new domains' position will be calculate as a function of time, i.e. the domains '
definition update by
D ' (t + M) = D ' (t) + W ' (M) (s = 1,2,..., N),
where new subdomain (doma ins' increment) ~D' (~t) is a result of current dissolution
effects and/or precipitation effects . New topology of the model system is a result of the
evolution of the centers of mass as a reference point for model system contours and the
domains ' position, i.e.
D' = {R s (t); r{ (t),r{(t),,r:, (o} (s = 1,2,.,N) .
Results and Discussion

We will test the present simulation method for a study of liquid phase sintering of an
AI20 3 - glass system. An initial model system (Fig. 3a) was obtained by applying random
generating methodology and assuming that for the polycrystalline AI203 the particle size
range was 5 - 10 urn with initial average particle radius (To> = 7.05 urn inside the
experimental region 120 11m x 100 11m .
For the AI203 - magne sium aluminosilicate glass system with an equilibrium
composition of liquid" 14.6 MgO, 44.1 A1 20 3, and 41.3 Si02, in wt%, the following data
were used: Co=29.00mol%7, DL=10-IOm2 s-1 8, Q=4.25 xI0-29m 3(AI203),
r. = 0.5 Jm -2, T = 1873 K . For the simulation we used the analysis and the observation
of Kwon and Messing? that the coarsening will be controlled by the interface reaction .
A selected computed results will be presented to illustrate the application of defined
simulation of the solution-precipitation processes and the contour coarsening process. The
driving force of those processes is not the difference in the contour size, but the
concentration gradient between solid and liquid phases . Smaller contours have the highest
concentration levels and they dissolve in the liquid matrix. The fine contours will disappear
at the start of coarsening, resulting in an increase in mean size. Dissolved atoms diffuse
through the liquid matrix and precipitate on the larger contours . It can be seen (Fig. 3b) the
liquid thickness remains nearly constant because dissolution and precipitation
simultaneously take place over short distances. Further morphological change s may occur
by large contours growing during contour coarsen ing, as it shown in Fig. 3c.
33
0.10
0.08
b
II
~ 0.06
~
>-
ui 0.04
o
z
-c
f-
(J)
0 0 .02
0.00
0.00 0.02 0.04 0.06 0.08 0.10 0.12
DISTANCE , X (CM) = 10.1
(a)
t = 20.0 nun..
0.10
0.08
b
II
~ 0.06
~
>-
u.i
U
z 0.04
-c
f-
(J)
0 0.02
0.00
0.00 0.02 0.04 0.06 0.08 0.10 0.12
DISTANCE , X (CM) =10'1
(b)
GRAIN BOUNDARY MIGRATION MODELING

A particularly interesting approach would be the application of the previous defined
numerical procedures for the prediction and the estimation of liquid-solid boundary
migration because of gravity- and microgravity-induced segregation during liquid phase
sintering.
.Stokes' Law Settling
It is recognized that liquid phase sintering for systems with a large density difference
between the liquid and solid is characterized by macrostructural and microstructural effects
associated with gravity. The experiments evidence remarkable differences (specimen shape,
34
t = 50 .0 ........
0.10 - r - - - - - - - - - - - - - -- ------,
. 0.08
o
II
::2
S:?. 0.06
>-
u.i
o 0 .04
z
;::
CJ)
o 0.02
O .OO +---....--~--__r_"""" '--,....----,.---i

0.00 0.02 0.04 0.06 0.08 0.10 0.12
1
DISTAN CE, X (CM) = 10-
(C)
Figure 3. Simulation results of micros tructural changes. (a) Initial geo metry. (b) After 20 min.
(c) After 50 min.
grain separation, grain size, etc.) between the samples sintered under earth-based and those
sintered in microgravity condit ions. Because of that settling due to gravity, since the time
scales are relativel y long compared to settling times, complicates many experimental tests
of diffusion phenomena, such as coarsening.
If ( x~ , y~ ) and rs and (x~, y~ ) and rq are the center position and the radiu s of the s th
and q th contours respecti vely, then the separation distance between these two ones is
A.sq =~(x~ -xn 2 + (y~ - yn

2
- (rs +rq ),
and the average separation distance is

(A.) = (A. sq ) (s ,q = I,...,N; s * q) .
Since under Earth-based experimental conditions Stoke s' s law settling usually
dominates micro structure formation ", then the average time for gravity-induced settling
contours is
where 1] is the liqu id viscosity, a is the grav itational acceleration, and P s - PL solid-liquid
density differen ce.
The experiments evidence both macrostructural and micro structural effects assoc iated
with gravity force . The method applied for the simulation of the gravitational effect is the
settling procedure in which particles are subjected to a simulated gravity field : the particle
falls under gravity and slides down over the already settled particles'". This procedure can
be modeled by contour motion along the gravitational direction
D S ~ D's if D' s nDJ = 0 (j = 1,2,...,N; s * j ), (4)
35
0.14,.-----------------::::------,
0.12
o 0.10
II
~ 0.08
>-
~ 0.06
z
~
o
(j)
0.04
0.02
0.00 +-----.----r--~--_r_----.----l
0.00 0.02 0.04 0.06 0.08 0.10 0.12
DISTANCE, X (CM) = W'
(a)
t 4.0 17Wn.
0. 1 4 , - - - - - - - - - - - - - - - - ,
0.12
o 0.10
~ 0.08
>-
UJ
o 0.06
z
~
(j)
o 0.04
0.02
0.00 +------.--........--..----...---.-----l
0.00 0.02 0.04 0.06 0.08 0.10 0.12
DISTANCE, X (CM) = 10.1
(b)
Figure 4. Simulation results of liquid-solid boundary migration because of gravity induced segregation.
(a) Initial geometry . (b) After 4 min.
36
where D's is the domain position of sth contour after partially settling. This procedure will
be applied to each particle starting with the particle having the lowest position in the
vertical direction of experimental region .
Brownian Motion
The next numerical model for simulation of liquid phase sintering is developed based
on assumption that Brownian motion dominates under microgravity conditions.
Unbalanced random molecular forces induce Brownian motion . Using the Einstein
expression II for the mean displacement of a grain, the average time between contacts by
Brownian motion of contours is
,Brown -- 3Jr(r)1J(}.,)
kT
2
' (5)
Although the expression (5) assumes only the motion of one contour, we will use it as the
time when contours' motion start. Such a motion can be modeled by contour motion of type
(4) along random direction , where D'S is the domain position of sth contour after one
random step motion ..
During the simulation process both simulators continuously check for possible new
contours ' position and new geometry . All topological information is recording and saving
each time interval for next analysis and computation.
Results and Discussion

In this section a selection of computed results will be present to illustrate the
simulation of gravity and microgravity induced microstructural change s during liquid phase
sintering of W-Ni. The following data will be used : the equilibrium concentration of liquid
Co=35at. %W I2, D L=IQ-9 m 2 s - 1 13, T=17l3K, 1J=5 1Q-3 Pa . s , a=9.8Ims - 2 ,
p s-PL=9gcm-3,Ys/=0.8Jm,214. An initial model system, shown on Fig.4a, was
obtained by applying random generation and assuming that for the solid W the particle
radius range was 3 - 13 urn with initial average particle radius ( r) = 6.8 urn inside the
experimental region 120 um x 140 11m .
During the initial stage solution -diffusion-precipitation processes are just beginning to
occur along the solid/liquid boundary interfaces . The driving force is the concentration
gradient between solid and liquid phases. Smaller contours have higher concentration levels
and they dissolve into the liquid matrix . Pure tungsten dissolved into the liquid and diffused
through the liquid matrix precipitate as W(Ni) solid solution on the larger contours , as
shown on Fig. 4b. It can be seen that during sintering the centers' locations change with
simulation time . The migration of the contours is a result of the settling, where the smaller
dissolving contours give way to new packing of small and large contours. Even small
changes in the locations of the contours relative to one another can have large effects on the
resultant morphological evolution of the model system. The evident consequence of
gravitational segregation is that grain shape accommodation takes place. The large contours
with small contours as neighbors have extensive grain boundary movement, because small
contours, which are very close to bigger ones . dissolve very quickly and disappear. The
growth of larger contours (the precipitated areas of W(Ni)) does not occur uniformly around
the contours. The largest shape distortion is in center-to-center direction as a result of
interparticle diffusion interaction s at relatively small intercontour d.stances.
Figure 5 shows the shape and location of the center of the model system contours
migration under minimized gravity-induced solid-liquid separation. It can be seen from
simulation results that morphological evolution and migration depend on the contour 's
37
0. 1 4 , - - - - : = - - - - - -----,
0.12
0.10
II
:2:
~ 0.08
>-
UJ
o 0.06
z<{
f-
en
o 0.04
0.02
0.00 +-----.---"""T"""--.-------.---~-___l
0.00 0 .02 0.04 0.06 0.08 0.10 0.12
DISTANCE , X (CM ) = 10"
Figure 5. Simulation results of liquid-solid boundary migration under minimized gravity-induced

solid-liquid separation.
location . In the present simulation the small contours tend to be located near the large
contours during Brown ian motion . The large contours with small contours as neighbors
have extensive grain boundary movement because they have the fastest growth . This means
that small contours, which are very close to bigger ones, dissolve very quickly and will
disappear. It can be concluded that sintering in microgravity eliminates settling and the
formation of a connected solid skeleton.
CONCLUSION
This paper outlines a computer-based method for simulation of microstructural
evolution that is a result of grain growth due to simulation-precipitation process during
liquid phase sintering. The initial model based on randomly distributed particles inside the
square experimental region .
The method applied for the simulation of the gravitational effect was the settling
procedure. The computer generated two-dimensional microstructures can be applied for
prediction of gravity induced microstructural evolution during liquid phase sintering .
This paper also outlines a method for simulation of grain boundary migration on
liquid/solid interfaces during liquid phase sintering with the assumption that Brownian
motion dominates under microgravity conditions. The computer generated two-dimensional
microstructures can be applied for prediction of grain motion and grain coarsening under
microgravity conditions. Obtained results shown that sintering in microgravity eliminates
settling and the formation of a connected solid skeleton .
Acknowledgements - The author would like to acknowledge helpful discussions with

Academician Momcilo M. Ristic, Serbian Academy of Sciences and Arts, Yugoslavia. The
38
present work was performed under the project "Prognosis of Materials Properties "
supported financially by the Ministry for Science and Technology of Republic Serbia,
Yugoslavia .
REFERENCES
1. H. Fischmeister and G. Grimv all, in "Sintering and Related Phenomena", edited by G. C. Kuczynski
(Plenum Press , New York , 1973) p.119 .
2. P.W. Voorhees and M .E. Glicksman, Ostwald ripening during liquid phase sintcr ing - efect of volume
fraction on coarsening kinetics , Metall. Trans . A, 15A:1081 (1984)
3. H. Matsubara and R.J. Brook , Computer Simulation of Grain Growth dur ing Liquid Phase Sintering, in:
Sintering Technology, R.M. German , G.L. Messing and R.G . Cornwall , eds., Marcel Dekker , Inc., New
York (1996) 415.
4. J. Crank , The Math ematics of Diffusion, Oxford University Press , Oxford (1956 ).
5. Z.S . Nikolic and R.M. Spriggs, Comput er Simulation of Diffusion Proce ss durin g Liquid Phase Sintering,
Science of Sintering, 26:1 (1994).
6.0h-Hun Kwon and G. L. Messing , Kinetic Analysis of Solution-Precipitation During Liquid -Phase
Sintering of Alumina , J. Am. Ceram. Soc. 73 [2]: 275 (1990) .
7. E. M. Levin , C. R. Robbins and H. F. McMurdie, in "Phase Diagrams for Ceramics" , 2nd edn., (Am.
Cerarn. Soc., Columbus, Ohio, 1981) p. 246 .
8. Y. Oishi , R. Terai and H. Veda , in: Materials Science Research , Vol. 9, Mass Transport Process in
Ceramics , A. H. Heuer , ed ., Plenum Pres s, New York (1985) 297 .
9. T.H. Courtney, Microstructural Evolution Durin Liquid Phase Sintering: Part I. Development of
Microstructure, Metall. Trans. A, 8A:679(1977).
10. Z.S. Nikolic , R.M. Spriggs , V.R.W. Amarak oon and M.M. Ristic , Computer Simulation of Gravit y
Induced Microstructural Change s During Liquid Phase Sintering , 99th Annual Meeting of the American
Ceramic Soc iety, May 4-7, 1997, Cincinnati, Ohio (Theory and Computational Modeling, Symposium
XIX , Paper No SXIXP-023-97).
II. A. Einstein , Investigation on the Theory of the Brownian Movement, Dover, New York (1956)
12. M. Hansen and K. Anderko, Constitution of Binary Alloys , 2nd Edn. McGraw-Hili, New York (1958).
13. Y. Ono and T-Sh igematsu , J. Japan Inst. Met. 41 :62 (1977) .
14. W.J . Huppmann, H. Riegger , K. Roser and G. Petzow, Proc . VI Int. PIM Conf. , Dresden 1977 , Vol. I
(Paper 5)
39
SINTERING KINETIC ANALYSIS BY DILATOMETRIC
DATA OBTAINED AT DIFFERENT HEATING RATES
In-Hyung Moon, Dong-Mook Won
Department of Materials Engineering, Hanyang University,

Seoul 133-791, Korea
INTRODUCTION
The intial stage of sintering, i.e.,the sintering processed during the heating up stage, is
very important for kinetic analysis of any sintering process, especially for the case of an
activated sintering by which the sintered compacts is subjected to the relatively high
sintering shrinkage in this initial stage of sintering. Therefore, the sintering behavior
analysis based only on the isothermal heating is insufficient for the full understanding of the
sintering kinetics .
Since the heating rate (temperature increase per unit time) can be precisely controlled
in a modern dilatometer, the dilatometric measurement data obtained from any sintering
system during heating up stage can be further usefully applied to the kinetic analysis of the
initial stage of sintering by an appropriate control of process variable as well as by
simplifying the analysis condition on the basis of the constant heating rate.
"Sintering study under constant rates of heating (CRT) in dilatometer was firstly
suggested and carried out by W. Young and I. Cuttler. l " They had derived the shrinkage-
temperature relation from the given sintering shrinkage-time equation in order to evaluate
the activation energy for the sintering of ceramic powders. "D.L. Johnson had also used the
non-isothermal dilatometric data obtained by a constant heating and cooling rate for the
determination of the surface diffusion portion in initial stage of sintering 2." Their CRT
studies had a meaning in a sense that the dilatometric data during non-isothermal heating
stage were firstly analyzed for an evaluation of initial sintering behavior . However, "the
analytical equation modified for CRT dilatometric data has the form of shrinkage(or
shrinkage rate) versus temperature relation, being useful only for determin ing the activation
energy by the given diffusion mechanism of the sintering model 3."
If any simple sintering shrinkage-sintering time relation can be derived for the sintering
analysis during the non-isothermal heating stage just as form of the power law relation for
isothermal sintering , this equation can be more useful for an analysis of the initial stage
sintering mechanism . Such a sintering shrinkage-time relation for the non-isothermal
heating stage was able to be derived from the non-isothermal dilatometry with constant
Advanced Science and Technology of Sintenng, edited by Stoj anovic et at.

Kluwer Academic /Plenum Publishers. New York, 1999 41
heating rates; the time variable for kinetic analysis was introduced by adopting several
constant heating rates, i.e. by introducing the heating rate as a new variable.
In the present study, firstly, the heating rate was introduced as a new parameter for the
evaluation of the non isothermal dilatometry, and the relations between heating time,
heating temperature and sintering shrinkage were established on the basis of constant
heating rate. The sintering shrinkage, the integrated thermal effect, during the heating was
evaluated by these relations. Secondly, this newly introduced analysis method was applied
mainly for the kinetic analysis of the Ni-doped W powder compact and Cu-powder compact,
which are known to be the typical activated sintering system and the most investigated
sintering system, respectively.
ANALYSIS METHOD
If any reaction kinetics is controlled only by total thermal amount involved, such as the
process of the diffusion controlled sintering or the diffusion controlled grain growth, the
reaction kinetics can be usually analyzed by determining the reaction rate and its
temperature dependence. In such an analysis, the time dependent exponent or temperature
dependent reaction coefficient is generally calculated from data measured by isothermal
reaction process.
If the relation between reaction time and reaction temperature is kept constant during
heating up (dT/dt=const.), the data obtained in this non-isothermal heating stage can be
applied for kinetic analysis so far as the reaction is controlled by thermal process. The total
thermal effect involved is usually expressed in a function of both temperature and time, but
in the case of constant heating rate, it can be expressed either by time- or temperature
dependent function because ofT =ct.
When a powder compact is heated in a dilatometer up to the sintering temperature with
different heating rates, heating curves are characterized by linearity, having the different
slopes depending on the heating rate, as shown in Fig.I . The specimen heated with the
higher heating rate will stay shorter time than the ones heated with the lower heating rate at
each pertinent temperature . If the sintering temperature range is divided into total of n with
an equal interval, there should be also equivalent number of time division,n, with a certain
time interval. These n time-segments should have the same holding time(in other words,
passing time) at each temperature division. But this holding time corresponding to certain
temperature division will be different each other depending on the heating rate; the interval
time will be short for a high heating rate, but long for a low heating rate, as shown stepwise
in Fig. 1. The holding time at certain temperature division is inversely proportional to the
heating rate, because the total heating up time(t) is just the sum of all holding times
segment(dt), and the ratio of reciprocal of heating rates(I /r) is just the ratio of the total
heating up time to sintering temperature. Thus, the ratio of the holding time at certain
temperature division can be expressed as the ratio of the reciprocal of heating rate:
where, the subscript numbers mean the different heating rates.

Fig. I shows three heating paths with different rates of heating. These three specimens
should be subjected to the different thermal effect which can be differentiated by their
different heating rates. Therefore, the temperature dependent function for kinetics can be
transformed to a function of time variable or any time related constant term in order to
simplify the kinetic analysis. The thermal effect of the heating up process can be
characterized enough by the given heating rate so far as the heating rate is kept constant.
42
HR HR HR
- --- ---- --
1 2 3
- --------- ---------------------- --
Time , t
Figure 1. Temperature-time relation by heating at constant rate.
If the dilatometric curves of the shrinkage versus temperature are obtained during
heating up process with different heating rates, these curves will be shown schematically as
given in Fig. 2. Since heating time up to certain temperature is related with the reciprocal of
the heating rate, the shrinkage can be expressed as a function of heating rate at each
temperature ranges concerned . Therefore, the reaction kinetics, the time dependence of
sintering shrinkage, can be determined from the slope of the logarithmic plot of the
shrinkage versus reciprocal of heating rate. Fig. 3 shows a schematic representation of the
logarithmic plot of the relation between the linear shrinkage increment and the sintering
time(represented as the reciprocal of heating rate) at three selected temperatures . From the
data obtained by experimental plot as shown in Fig. 3, the activation energy for any given
sintering process can be calculated by an usual analysis way.
T
HR 3
3
Q) T~
~ OJ
or0> ro
0
.:,,:. T
C I
11l .~
~
c .c
(/)
'C
s: L..
ro
(/) HR
2 Q)
E
L..
11l
OJ
C
HR, C
::J
T ernperaturetC) In(sintering time)

Figure 2. Dilatometric curves obtained by three Figure 3. Logarithm ic plot of the relation between
different heating rates. linear shrinkage and time(a reciprocal of heating
rate) at different temperature.
In a study of sintering kinetics, the sintering shrinkage rate, the time derivative of the
sintering shrinkagc[dy/dt, y = dl/lol is also useful parameter for the analysis of sintering
behavior. Since the heating time is directly proportional to heating temperatu re in case of
CRT (dT/dt=c), the temperature dependence of shrinkage in the form of dy/dT has the same
physical meaning as the sintering shrinkage rate. The shrinkage rate analysis is helpful tool
for the sintering kinetics analysis of the nearly full densified system during heating up stage,
because the shrinkage rate is directly related with the diffusion and densification process of
the sintered compact.
43
When the sintering process is controlled by diffusion mechanism, the integrated
thermal effect involved during the heating up stage can be estimated by an evaluation of the
effective diffusion product Dt, which is given by Dt = f D(t)dt. Since T=ct, the diffusion
coefficient D(t) can be evaluated by putting the pertinent temperature in the equation of D
=Do exp( -QIRT). "Then the area under the curves of D vs. heating time relation is
equivalent to the integrated thermal effect during the heating up process"." By an analysis of
this area we can obtain an useful information for the sintering kinetics as discussed in the
following chapters.
SINTERING ANALYSIS OF THE Ni-DOPED W-POWDER COMPACT
Experimental
The experiment was carried out with the commercial grade W-powders of three
different particle sizes of 0.5, 1.75 and 4.34 tlIIl. These W-powders supplied by Korea
Tungsten Co. have a polyhedral shape and a purity of 99.9% . "OAwt .% Ni was added to W-
powder by Ni-salt solution mixing and reduction method as described elsewhere 5."
The Ni-doped W-powders were compacted into a cylinder shaped compact specimen
with a diameter of 10 mm and a height of 10 mm at the pressure of 21OMPa. The pressed
compact was sealed into thin rubber tube and further isostatically repressed in order to
obtain the green density of 60 1% of the theoretical one. The sintering of the compacts was
carried out by heating up to 1400 C in a commercial dilatometer (Harrop, model TDA-Hl -
AP6-SC) under hydrogen atmosphere. The specimens were heated with the constant heating
rate of 1, 3, 5, 10 and 20 K/min, respectively.
Experimental Results
Fig. 4a - FigAc show the linear sintering shrinkage versus temperature curves obtained
by heating up to the temperature of 1400C in dilatometer with the various heating rates for
the Ni-doped W powder compacts of the different W particle sizes. As shown in these
figures, the sintering shrinkage was very low up to the heating temperature of 800C
regardless of heating rate, but it increased steeply by increasing temperature at the
temperature above 900C. The specimen of the 0.5 tlIIl W-powder was densified up to 98-
99% of theoretical density by heating up to 1400 C, while the sintered density of the
specimen of 1.75 tlIIl and 4.34 tlIIl W-powder were 92-96 % and 73-81%, respectively. The
0.5 tlIIl W powder specimens had undergone all sintering stages, i.e. initial, intermediate
and final stage, during heating up process. As shown in FigAa, the 0.5 tlIIl W specimens
was shrunk no more during heating to the temperature above 1300C with the heating rate
of 1 and 3K/min. The sintering dependence of the powder particle size is well demonstrated
in Fig. 4.
Fig.5 shows the plot of dy/dT vs. T, on the basis of the dilatometric data given in Fig. 4.
As discussed in the previous chapter, dy/dT has the same mean ing of shrinkage rate in the
case of T=ct. As shown in Fig. Sa, the dy/dT, sintering shrinkage rate increased firstly with
increasing temperature and then decreased after certain temperature, showing the maximum
value at intermediate temperature and approaching to zero after certain temperature. The
maximum value of dy/dT in these dy/dT vs. T curves moves also to high temperature upon
increasing the heating rate. It is also found that the areas under the each curve are about the
same, in spite of different heating rates which consequently showed the maxima at the
different temperatures. In contrast to the specimen of 0.5 tlIIl W-powder, the specimens of
44
18
-'#.-
Q)
16
14
1K/min
3K/min
SK/min
C) 12 10K/min
C'O
~ 20K/min
C 10
'C
.c
en
8
~
C'O 6
Q)
c 4
::J 2
0
0 200 400 600 800 1000 1200 1400
Temperature(C)
14
-*'-
Q)
12
10
- - 1K/min
- - SK/min
3K/min
C) ...... .... 10K/min

C'O
~ 8 - - 20K/min
c
'C
.c 6
en
~
C'O 4
Q)
c
::i 2
0
0 200 400 600 800 1000 1200 1400
Ternperaturetc)
14
-- 12
1K/min
*'
3K/min
5K/min
Q) 10
C) 10K/min
C'O
~ 8 20K/min
C
'c
.c
en 6
~
C'O 4
Q)
c
::i 2
0
0 200 400 600 800 1000 1200 1400
Ternperaturet'c)
Figure 4. Dilatometric curves obtained by heating with different heating rates for the specimen of Ni-doped W
powder ; (a) W 0.5 ttrn, (b) W 1.75 ttrn, (c) W 4.34 ttrn.
45
0.10T--------;::======~
_ 1K1min
0.08 .----. 3K1min
1- SKImIn
0.08
I 10Klmln
~ ~ 20Klmln
'U
_ O.l).(
>-
'U
0.02
0.00
0 .02-+-.--.--..--..--,.......,---r-r-.--.--r--r-..--,.......,,.....,
700 800 900 1000 1100 1200 1300 1400 1500
Temperaiuret'c)
0.10T--------;::======:=::;']
_ 1K1min
0.08- .--:.-. 3K/min
_ SK/min
10K/min
0.06-
~ I- 20K/min
'U
_ 0.04-
>-
'0
0.02-
0.00-
~.~ I I I I I I I
700 800 900 100011001200130014001500
Ternperaturet'C)
0. 10T--------;::======::::;,
- 1K1rnin
0.08 .----. 3K/min
_ SKlmin
.......... 10K/min
0.06
~ - 20K/min
'0
_ 0.04
>-
'U
0.02
0.00
0 .02-t--,-....--..--.,-,.......,-....-.....-,-....--..--.,...,,.......,-I
700 800 900 1000 1100 1200 1300 1400 1500
TemperaturetC)
Figure 5. Change of the dy/dT as a function of temperature for the specimen of Ni-doped W powder ; (a) W
0.5 tJIll, (b) W 1.75 tJIll, (c) W 4.34 J.tlI1.
46
4.34 ttrn W-powder had no such maximum point in the range of temperature up to 1400C.
The value of dy/dT increased slowly with increasing temperature. The specimens of 1.75 .urn
W-powder, whose sinterability was expected to be between 0.5 ttrn W and 4.34 ttrn W
specimens due to its particle size, had really shown the intermediate features in the
characteristics of dy/dT vs. T curves. The specimen heated with relatively low rate had the
maximum point. Such a data obtained from the dy/dT vs. T curves will be also useful for
the analysis of the sintering kinetics as will be discussed.
Fig. 6 is the logarithmic plots of sintering shrinkage versus sintering time equivalent
(in y vs. In t) for the various sintering temperatures from the data given in Fig. 4. Since the
value of slope means time exponent in sintering equation, the different slopes mean the
different sintering mechanism . So, one should only consider the data given in straight lines
in parallel for further evaluation. The data given in Fig. 6 can be further utilized for the
evaluation of activation energy for the sintering densification by plotting the logarithm of
the reciprocal time required to get an amount of shrinkage as a function of liT at the
pertinent temperature range. The data obtained below the temperature at the maximum
point of dy/dT vs. T curves are more suitable for the kinetic analysis of the initial stage of
sintering, and the data obtained at the temperature above maximum point are for the
analysis of final stage sintering kinetics.
Figure 6. Logarithmic plots ofln y versus In t for the specimen of Ni-doped W powder ; (a) W 1.75 tnJI, (b) W
4.341lU1.
47
Fig. 7 shows the Arrhenius type plot of the experimental data obtained from Fig. 6 for
the specimen of 1.75,urn Wand that of 4.34,urn W-powder. The activation energy of the
sintering shrinkage in the initial stage of sintering was calculated from the slope of Fig. 7 to
be 291.3 kJ/mole for 1.75,urn W specimen and 309 kJ/mole for 4.34,urn W specimen .
Fig. 8 shows the SEM micrographs of the specimens of 1.75,urn W which were
sintered during heating up to the pertinent temperature with heating rate of 3KJmin. As
shown in Fig. 8a and Fig 8b, the sintered microstructures of the specimens heated up to
1000 and 1100 C were characterized by the morphology of the individual W-particles with
the initial size and the measurably grown neck formation . But the sintered microstructures
of the specimens heated above 1300C, had shown the typical morphology of final stage of
sintering showing some residual pores and the W grain growth (see Fig.8d and 8e). The
microstructural feature of the specimens heated up to 1200C was the mixed state of the
former and the latter. It is worthy of note that the temperature corresponding to the
maximum value of shrinkage rate of these specimens was about 1150C . The sintered
density of these specimens was 65, 70, 86, 90 and 92 % of the theoretical density, by
sintering up to the the temperature of 1000, 1100, 1200, 1300 and 1400C , respectively .
M'4-.---------------------,
~
II
>.
.....-. Actiavtion Energy : 291.3kJ/mol
c 3
Figure 7. The Arrhenius type plot obtained from Fig. 6 for the specimen ofNi-doped W powder ;
(a) W 1.75,urn, (b) W 4.34 /lID.
48
Figure 8. SEM micrographs of Ni-doped 1.75 ~ W-specimens sintered with the heating rate of 3K/min. up
to (a) 1000C, (b) 1100C , (c) 1200C , (d) 1300C, and (e) 1400C.
ANALYSIS OF Cu POWDER COMPACT
The same dilatometric analysis was applied to the Cu powder compact as it was done
to Ni-doped W powder compact. The atomized Cu powder with the average particle size of
50.4 urn was used for this dilatometric analysis. "The Cu green compact was annealed at
500 C for lh in order to avoid swelling phenomenon" caused by the entrapped gas and
oxide in Cu powder during the heating stage." The average green density was
approximately 58 1% of theoretical density(TD).
Fig. 9 shows changes of linear shrinkage during the heating stage with the different
heating rates at 1, 3, 5, 10K/min and isothermal sintering at the temperature of 1050C. The
shape of the curve was similar to Fig. 4a, but the sintered Cu compacts were not fully
densified at the isothermal sintering stage having measured 91 - 92% of theoretical one.
No further densification occurred even through prolonged sintering at 1050C.
Fig. 10 shows the plot of dy/dt vs. T obtained from the data given in Fig. 9 during the
heating stage. Since these figures have the same features as Fig. 4 and Fig. 5, the same
49
14-.--------------yo----------~
1K1min
12 3K1min
5K1min
10Klmin
-2 --t-1r-r-r-r-T'""T"'T"'T"T'"T~_r"lr_r_r_r_'T"'T_r_+~-r"lr_r_r_r_T""T""T'"T"'T""'T...,...,~........~
o 10020030U005006007008009OOl000 50 100 150 200
Temperature( C) Time(min.)
Fig ure 9. Dilatometri c curves obtained by heating with different heating rates for pure Cu.
0. 10Tr=======:;-------~
- 1K1min
0.08 .--. 3K1min
.- - '. 5K1min
10Klmin
0.06
.....
320.04
>-
"0
0.02
0.00
600 700 800 900 1000 1100

Temperature( C )
Fig ure 10. Change of the dy/dT as a function of
temperature for pure Cu.
50
3
-Q)
0)
C'U
.::.:. 2
c:
'C
s:
'C'"U
~
Q) ---.860t
-
c D--t:J 640t
c: ~820t
~800t
0
-2 -1 0
In(Time)
Figure 11. Logarithmic plots ofln y versus In t for
pure Cu.
analysis method applied to W-specimen was adopted for the evaluation of the activation
energy for the shrinkage process of Cu.
Fig. 11 shows the logarithmic plots of the data obtained from Fig. 9 in the temperature
range near maximum points given in Fig. 10. The activation energy of Cu compact was
calculated to be 218.4 kl/mol from Fig. 11.
DISCUSSION
Meaning of the Area under the Curves of dy/dT vs, T
As described partly in Experimental Results, the sizes of areas under the curves of Fig.
5 are about the same, ranging from 96 to 100 % of the area obtained from 1Klmin heating
rate for the 0.5 tmJ W-specimen. However, the sizes of these areas were decreased slightly
with the increase in the heating rate. The ratio of these areas obtained from various heating
rates was roughly proportional to the ratio of the sintered densities of the pertinent
specimens . The area under the curves of dy/dT vs. T can be obtained by integrating dy/dT
by dT, which results in y, the final shrinkage value at the maximum heating temperature.
The linear sintered shrinkage, in other words, the area under the curves of dy/dT vs. T
curves can represent the sintered density so far as the sintered compact shrinks isotropically
during the sintering.
From the relation of T=ct by the constant heating rate, the curves of dy/dT vs. T can
also be transformed to dy/dt vs. T, and the area under the curves of dy/dt vs. t has the same
meaning with the former. If the sintering kinetics are controlled by diffusional process, the
physical meaning of such areas can be discussed more meaningfully as follows . If we plot
the change of diffusion coefficient as a function of temperature (i.e time) during heating up
to the full sintered density for the 0.5 tmJ W-specimens with the various heating rates, we
obtained the form of curves as shown in Fig.12a where we had used the data of 0 obtained
from the present study. The areas marked with black mean the Dt up to the point where the
shrinkage rate approaches to zero. These areas are also calculated to about the same value,
4.59-4 .67. Therefore the same thermal effect was shown on the sintering of W-specimen.
The proportionality between the diffusional product Dt and the area under the curves dy/dT
vs. T supported that the sintering kinetics was controlled by diffusional process .
51
1.0 20Klmm 1400
lOKI 6Klm. 3K1min l Kzrmn
0.8 1378
-;
.......... (1)
-
C 0.6 1350 3
0 "'0
.......... I
I
...,
(1)
Q)
~ 0.4
.......,
I
I
1313 c
r-+
...,
I
I
0 I
I
I
(1)
--
I
I
..........
0
I
0.2 I
1253
1197
0.0 522
0 200 400 600 800 1000 1200 1400
Time(min.)
1.2
10K/min 5K/min 3K/min lK/mi
1.0
........../).8
t-
.......,
o
_ 0.6
.........
E::,
0 0.4
0.2
j
0.0
o 400 800 0 400. 800 0 400 800 0 400 800
Time(min.)
Figure 12. Diffusion coefficient - time relation during heating with different heating rates .; (a) Ni-doped 0.5
tIlI W-specimens. (b) pure Cu
The same relation was found in the analysis of Cu powder compact. Since the sintered
specimens had different densities after heating up to 1050 C for the Cu powder compacts,
the isothermal sintering was conducted at 1050C in order to obtained the sintered parts of
equal density.
Fig. 12b shows the relationship of the diffusion coefficient vs. time during heating and
isothermal sintering. As shown in Fig. 12a, black areas meant the value of Dt. But in this
case, the thermal effect was estimated for the Cu sintered parts with 91% of TD because the
densification no longer occurred. For that reason, the interpretation of thermal effect should
be cautious compared with the enhanced sintering ofNi-doped W compact. The areas were
calculated to be nearly the same value, 119.3, 123, 120.1 and 125.9, respectively. Therefore,
one may utilize the data given by the temperature dependence of sintering shrinkage
obtained by various heating rates for the evaluation of the sintering kinetics during heating
up stage. Besides the determination of time exponent in sintering time equation and
activation energy for sintering kinetics analysis, the maximum points in the dy/dT vs. T
52
curves and their areas give us plentiful information for the valuable discussion for the
sintering kinetics.
Sintering Kinetics Analysis
The slope of straight lines representing the relation of In y vs. In t is the time exponent
value of the kinetic equation for various mechanisms for initial stage of sintering 7. The
slope of 0.36 was obtained for the 1.75 tim W specimen and 0.26 for 4.34 tim W specimen
from Fig. 6. "The time exponent value of 0.26 is rather close to the value of 1/3 which
means the sintering mechanism of materials transport via grain boundary diffusion from
grain boundary sources between contacting particles to neck, and 0.36 is possibly the
combined mechanism of the grain boundary diffusion and the volume diffusion from the
same source to neck 7." However, such a simple interpretation might not be applicable for
the Ni-doped W activated sintering, because of the complexity of diffusion paths due to the
presence of nickel. The slope of this line for Cu compact was also obtained from Fig.ll . It
is 0.30-0.45, implying that the sintering process is also controlled possibly by both volume
diffusion and grain boundary diffusion. "This range of the slope values and the postulated
mechanism are similar to the data by D.L. Johnson 3 as well as F.B. Swinkels and M.F.
Ashby for the sintering of Cu-powder 8. However, the present author had obtained the slope
of 0.5 in isothermal sintering ofCu- powder with the coarse particle size of 120 -143 t1ffi 9."
The activation energy computed from Fig. 7 was 291.3 and 309 kJ/mol depending on
the W-particle size. "These values are similar to the data of the activation energy for
sintering process of W, 280- 290 kJ/mole, in literature 10.12 ." Such an agreement of
activation energy seems to support the validity of the present analysis method for sintering
kinetics. "However, the values of activation energy for Ni-doped W compact are rather
close to that of W-grain boundary diffusion, 380 kJ/mol, and much lower than that of W-
volume diffusion, 526 kJ/mol 13." The difference in the activation energies for sintering
process of Ni-doped W compact and for W-grain boundary diffusion in literature should be
partly attributed to the role of nickel and partly to the difference in microstructures . The
present Ni-doped W sintered specimen of fine W-particles had much finer grain size than
the conventional bulk specimens used for diffusion testing in literature.
The activation energy computed from Fig. 11 for the sintering process of Cu powder
compact was 218.4 kJ/mol. "This activation energy is somewhat higher value compared
with our previous data obtained from the isothermal sintering of the coarse Cu-powder,
172.6 kJ/mol 9." "It is also much higher value than the activation energy of Cu grain
boundary diffusion , 105-120 kJ/mol, in literature 14." "However, the measured value is
comparable with the activation energy of Cu volume diffusion, 197.4-210 kJ/mol 15-17."
Such an agreement of the activation energy supports that the sintering kinetics is
presumably controlled by both materials transport mechanism, mainly via Cu volume
diffusion and secondly via Cu boundary self diffusion.
CONCLUSION
Simple dilatometric analysis method was introduced for the kinetic analysis of the
initial stage of sintering. The dilatometric data obtained during the non-isothermal heating
process can be successfully applied for the analysis of the kinetic equation based on
isothermal sintering by introduction of the concept of constant heating rate. By transforming
the dilatometric data into the relation of shrinkage rate and temperature, this analysis
method can be applied also to the extended stage of sintering.
53
The present analysis method was applied to the sintering kinetic analysis of Ni-doped
W powder compact as well as Cu-powder compact. The activation energy of the sintering
shrinkage process for the Ni-doped W powder compact of 1.75 fLIII and 4.34 fLIII W powder
was determined to be 291.3 and 309 kJ/mol, respectively. The activation energy for the
sintering of Cu powder compacts was 218.4 kJ/mol. According to this activation energy and
the sintering time exponent of 0.30 to 0.45, the sintering kinetics of Cu powder compact is
more likely to be controlled by both volume- and grain boundary diffusion .
ACKNOWLEDGMENT
The author gratefully acknowledge the financial support of ERC for Interface Science
and Engineering of Materials.
REFERENCES
I. W.S.Young and LB. Cuttler, 1. Amer . Cer . Soc., 53, 659 (1970)
2. D.L. Johnson, "Modem Devel. in Powder Met."(ed. H.H.Hausner), Plenum Press, New York
1971, VolA , p. 189
3. D.L. Johnson, J. Appl. Phys ., 40,182 (1969)
4. P. Shewmon, "Diffusion in Solid", TMS , Warrendale, PA. 1989, p.37
5. LH. Moon , Intern . J. Powder Met.& Powder Tech ., 11,27 (1975)
6. F. Lenel, "New Persp . in Powder Met.", MPIF , Princeton, New Jersey , 1980, Vol. 7, p.187
7. Ja . E. Geguzin, "Physik des Sintern", VEB Deutscher Verlag, 1973, pA4
8. F. B. Swinkels and M.F. Ashby , Acta Met., 29, 259 (1981)
9. LH.Moon and J.K.Lee, Powder Met., 30 , 249 (1987)
10. J.H.Brophy, L.A. Shepard and J.Wulff,"Powder Metallugy"(ed. W. Leszynski) , Interscience
New York, 1961, p.113
II. R.M.German and Z.A. Munier, Met. Tras ., 7,1873 (1976)
12. Y. S. Kwon, Ph.D. Thesis, Hanyang University, 1981
13. K. Vieregge and D. Gupta , "Tungsten and Tungsten Alloys"(ed. L Ahmad et al), TMS , Warrendale,
PA, 1991, p.231
14. L Kauer, W. Gust and L. Kozma, "Handbook of Grain and Interphase Boundary Diffsusion Data",
Ziegler Press, Stuttgart, 1989, Vol. I, p.380
15. M. Beyeler and Y. Adda , J. Phys ., 29,345 (1968)
16. K. Monma, H. Suto and H. Oikawa, J. Jpn .lnst. Met., 28,188 (1964)
17. N.L.Peterson, Solid State Phys ., 22, 429 (1968)
54
COMPUTER STUDY OF MICROSTRUCTURE FORMATION BY
REARRANGEMENT DURING LIQUID PHASE SINTERING
Jean-Marc Chaix,' Sung Min Lee,1,2 and Christophe L. Martin'
1 LTPCM, UMR 5614 CNRS-INPGIUJF, ENSEEG BP 75,

38402 Saint Martin d'Heres Cedex France
2 CISEM , Korean Advanced Institute of Science and Technology,
Kusong-dong 373-1 , Taejon 305-701, Korea
3 GPM2 , INPGIUJF, ESA CNRS 5010, ENSPG BP 46,
38402 Saint Martin d'Heres Cedex France
INTRODUCTION
Rearrangement processes in liquid phase sintering' occur in a very short time when the
liquid appears, and are therofore very difficult to analyse experimentally. Since Kingery's
work ", it has been generally accepted that this stage, drived by capillary forces between solid
particles, tends to form a random close packing of solid particles embedded in liquid and
some residual porosity if the amount of liquid is too low.
However, systems with no solubility such as WC-Cu 3.4 or W-Cu 5 are well known to
lead to cluster formation , large pores and low densification. Direct observation of cluster
formation during rearrangement was performed in W-Cu by Huppmann and Riegger'', who
used Cu-coated W particles to avoid inhomogeneity.
Recently , a 2D computer simulation was developped by one of the authors?", in
cond itions similar to Huppmann and Riegger ' s experiments". The model showed that cluster
formation is an intrinsic behavior : an instability arises? from the well known 910 decrease of
the capillary force with the distance between particles ; this instability amplifies the natural
inhomogeneities of the random packing", while the viscous energy dissipation tends to
stabilize the clusters when they are formed.
This model was however simplified, as dissipation was calculated for particles in a
liquid matrix and the calculations performed in conditions when particle inertia was
negligible with respect to viscosity forces. The present work was undertaken to override
these limitations and analyse the effect of viscosity on microstructure formation and
densification .
Advanced Science and Technology ofSintering, ed ited by Stojanov ic et at.

Kluwcr Academic /Plenum Publishers. New York, 1999 55
MODELING
Basis
The model'" analyses the behavior of a set of randomly distributed particles , initially
coated by the liquid phase . Liquid bridges are assumed to form instantaneously between
particles when the liquid melts. The evolution of the system is calculated from the balance of
forces acting on each particle i and its n neighbouring particles j :
2j(
d ~(- _ -)
2 t ' = s: F e,ij + F V,ij + Fet ,ij
m, - d (1)
] =1
in which Xi denotes the particle vector position, m, the particle mass. The elastic force Fe/,ij
when particles are in contact and the viscous force Fv,ij are described in the next section.
Figure 1. A liquid bridge between two particles; definition of characteristic parameters for viscous
dissipation inside the liquid bridge during particle to particle motion.
The capillary force FC.ij , between two particles i.] is assumed to follow the equation
ij
F- c.ij = C, Exp( - dd o ) (2)
where d ij is the distance between the two particles, and C ; and do are constants. By choosing
suitable values for the constants, the equation can approximate very closely the calculated
capillary force 9 ,1O.
Viscous Force
In a first approximation, the viscous force F; which is opposed to particle to particle
approach can be deduced from calculations derived for particles immersed in a newtonian
liquid 11. If the surface of the sphere is approximated as parabolic, the viscous force applied
to the particle can be simply expressed as
F =
v
67tllIP .lh dhdt (1- ~)2
Z
(3)
where R is the reduced radius of the two particles ( R = R1R2 ) and other geometric
R) +R2
parameters (h, Z, R I, and R2 ) are defmed in Figure 1. In practice, the term (l_hIZ)2 is close
to unity and can be ignored.
A second force is created by particle shearing relative to each other (Figure 2). To our
knowledge, no calculation is available for this force: it can be assumed to follow the case of
56
glass particle sintering", in which the shearing component is nearly one third of the distance
change one. Therefore, the viscous force FV,ij was calculted from
, (along the liquid bridge) (4)
, (perpendicular to the liquid bridge) (5)
where ~ and Vj are vector velocities of the particles i, j , It must be stressed that the
equation is only valid on the assumption that the liquid is Newtonian .
Figure 2. Illustration of the shearing of liquid bridges induced by the relative rotation of three particles
When the liquid film between particles becomes very small, the liquid no longer behaves
as a newtonian liquid", and transmits force as a visco-elastic solid. The characteristic limit
thickness d.; ranges" between 0.05 and 0.1 urn. In the present , a simple model, the Maxwell
model", has been considered, which consists of two parallel mechanical elements, pure
viscous and pure elastic: when the film thickness is below d., the elastic force, Fel,ij operates.
We assume that it is proportional to the strain rate of the visco-elastic liquid layer and be
expressed as
-
F elij = E
k-dij) (6)
, de
where E is the elastic constant of the visco-elastic layer.
RESULTS
Simulation Conditions
The evolution of a sample of 5000 randomly packed particles has been calculated . The
particle array consists of two kinds of particles, one with a radius of 0.8 p.m and the other
with a radius of 0.9 p.m. The ratio of the number of the particles is 7 to 3. Each particle is
assumed to be coated with liquid, similar to the experimental conditions of Huppmann and
Riegger",
57
The particle density is LOg/em' and the initial distance is 0.18 J.1ffi For capillary force ,
C: and do are taken as 6 J.1N and 0.56 J.1rn, which corresponds to a wetting angle 8, a liquid
volume fraction 20 %, and surface tension 1.28 N/m. The critical thickness of the liquid film
de and the elastic constant E are taken as 10 nm and 0.01 N respectively.
Two values for viscosity of the liquid were used in order to analyse the effect of
viscosity on densification and microstructure formation: a low one (l mPa sec), which
corresponds to a liquid metal , and a large one (l ()() mPa sec)
Densification and Time Scale

The evolution of the density of the sample is plotted on Figure 3 for the two values of
viscosity. The densification is more rapid and significantly larger for high viscosity, which is
unexpected. This results from the fact that for high viscosity, the local particle displacements
are small, while for small viscosity, particles can move, contact other particles and bounce
several times. The observation of microstructure evolution will precise this point.
Density (%)
96 r - - - - - - - - - - - - ,
94
92
90
88
86
84
82
1 mPa -sec
80
100 mPasec
78
76 l...-~.........o....._J.................___'___L~___L~__J
0.0 0.5 1.0 1.5 2.0 2.5 3.0

time, usee
Figure 3. Densification kinetics for a 5000 particles sample

for two values of the liquid viscosity .
A noticeable feature of Figure 3 is that densification is almost finished after about

3 usee. This time scale is confrrmed by the analysis of the kinetic energy of particles , which
shows that particles stop moving within this time. This implies that the rearrangement by
particle motion may finish much earlier than usual experimental time scale. It could even be
faster than the heat transfer inside a powder compact during heating to sintering
temperature.
Microstructure
Figure 4 shows the microstructure after 1 usee for the same initial sample. Clusters and
large pores form as previously calculated':" or experimentally observed" . The shape of these
large pores is strongly dependent on viscosity. For small viscosity, rounded shaped pores are
58
formed, due to large relative motion (local rearrangement) between particles inside and
outside the forming clusters. For large viscosities the motion of particles with respect to
their neighbours is strongly inhibited, so that local rearrangement is limited: clusters tend to
form, but involving a simple contraction and almost no rearrangement inside clusters .
Densification occurs regularly and is quicker. Pores are formed with a crack shape, just like
in the case of drying mud by water evaporation . These crack shaped pores are more easily
eliminated from their tips by capillary forces than rounded shaped ones, which leads to a
higher final density.
CONCLUSION
A model describing particle motion during rearrangement has been developed . The
proposed equation of motion includes the effects of capillary force, inertia of particles,
viscous drag and elastic collision.
The model was applied to rearrangement of 2-dimensional particle arrays of particles
coated with liquid forming material. During rearrangement, particles are agglomerated ,
forming particle clusters and pores, in agreement with former calculations and experiments.
This feature originates from the nature of the capillary force which increases with decreasing
inter-particle distance.
The time scale of rearrangement, calculated on this small sample (5000 particles) of
less than lum particles, is very small: about 3 usee. It could be faster than the heat transfer
inside a powder compact during heating to sintering temperature.
The energy dissipation due to the viscosity of the liquid is a determining parameter, for
both density and microstructure. At low liquid viscosity, the final density is calculated to be
lower than at high liquid viscosity. This may be due to the formation of a strong skeleton
and an irregular structure of particle clusters at low liquid viscosity, while crack shaped
pores developped for high viscosities can be partly eliminated. The initial microstructure of
coated particles however favors densification with limited rearrangement, so that new
calculations have to be performed with less regular structures.
59
Acknowledgements
This work was done under a Joint Research Program between the Korea Advanced
Institute of Science and Technology (KAIST) and the Institut National Polytechnique de
Grenoble (INPG), supported by the Korean Ministry of Science and Technology under
contract no. 97-I-0l -03-A-057. The authors wish to thank Dr C. H. Allibert (INPG) and
Prof. S.-J. L. Kang (KAIST).
REFERENCES
1. R. M. German, Liquid Phas e Sintering, Plenum Press, New York (1985).
2. W. D. Kingery, Densification during sintering in the presence of a liquid phase , J. Appl. Phys., 30:301
(1959).
3. R. J. Nelson, D.R. Milner, Liquid flow densification in the WC-Cu system, Powder Metallurgy, 14:39
(197 1).
4. D.R. Meredith, D.R. Milner, Densification mechan isms in the tung sten carbide- cobalt system, Powder
Metallurgy, 1:38 (1976) .
5. F. Sailland, Densification par Frittag e avec Phase Liquide d'Alliages Lourds W-Ni-Cu, Thesis, INP
Grenoble (1991) .
6. W. J. Huppmann and H. Riegger, Modelling of of rearragement processes in liquid phase sintering, Acta
Metall., 23, 965-971 (1975) .
7. J. M. Chaix,Liqu id phase sintering : the rearrangement stage results in cluster s and large pores, C. R.
Acad. Sci . Paris, Sene 11,316:855 (1993 ).
8. 1. M. Chaix,Particle rearrangement during liquid phase sintering: a model to analyse the microstructure
formation, in: Proc. PM'94 World Congress, Editions de Physique, Paris, I:1557 (1994).
9. V. N. Eremenko, Yu. V. Naidich and I. A. Lavrinenko, Liquid Phase Sint ering , Consultants Bureau,
New York (1970) .
10. K. S. Hwang, R. M. German , F. V. Lenel, Capillary forces between spheres during agglomeration and
liquid phase sintering, Metall. Trans . A., 18:11 (1987).
11. H. F. P. Purda y, An Introduction to the Mechan ics of Viscous Flow, Dover Pub. 1949.
12. A. Jagota, P. R. Dawson, Micromechanical modellin g of powder compacts-II. Tru ss formulation of
discrete packings, Acta Me tall. Mater., 36:2563 (1988).
13. A. S. Akhmatov, Molecular Physics of Boundary Friction , Fizmatgiz (1963).
14. D. H. Kaelble , Physical Chemistry ofAdh esion , John Willey & Sons 1971
60
COMPUTER SIMULATION OF NECK GROWTH
DURING SINTERING PROCESS
Zoran S. Nikolic, Ivana Mitrovic, and Vojisla v V. Mitic
Facul ty of Electronic Engineering, Department of Microelectronics

Univers ity ofNish, 18000 Nish, P.O. Box 73, Yugoslavia
Electronic address: znikolic@elfak.ni.ac.yu
iNTRODUCTION
Modeling and simulation of sintering process offer better possibilities in comparin g
theoretical to experimental results . Very often it is impossible to obtain, especially by
investigat ing a time depended process through experiments, relevant parameters by which
the process can be described either quantitatively or qualitatively.
The great complexity of the sintering process and the impossibility of following the
action of its main mechanisms have encouraged interest in an investigation of this process
by both modeling and simulation. At that, the efficiency of simulation is determined, most
frequently, by the very manner and quality of consideration of physics of both elemental
processes and phenomena that condition the quality of their modeling, as well.
In an earlier paper' the neck growth kinetics was determined by a modified model of
the sintering diagram". The dependence of a neck radius on temperature and on sintering
time was obtained by numerical integration of rate equations of the mass transport
mechanisms . The suggested method is particularly suitable for the prognosis of the sintering
process , as enabling definition of the basic parameters of the process in question .
The purpose of this paper was to solve the problem of modeling and simulation of
neck growth kinetics during sintering process . Having defined the total process rate as well
as the conditions of its action, we suggested the simulation method for the neck growth
during sintering proces s. The main characteristic of the method is to take into account an
arbitrary number of mechanisms and analyze their simultaneous and successive action .
Numerical integration of rate equations represents the basis of this method. Process
simulation could be done under conditions of either constant or changeable temperature.
We also defined functional dependence for the determination of contact surface as a 3-D
function of topological parameters for the model of two spheres or for the model of an
aggregate of spheres . In some cases polyhedral approximation instead of spheres is
acceptable too, where the polyhedron can be constructed as a 3-D graph .
Advanced Science and Technology ofSintering, edited by Stojan ovi c et al.

Kluwer Academic /Plenum Publishers, New York , 1999 61
NET SINTERING RATE
Let
(dx ) <I, (x,T; A,B)

dt k
(k = 1,2,..,m)
be the equations that define the rates of elementary transfer mechanisms as a function of
neck radius (x) and sintering temperature (1), where A =(al ,...,a r ) and B =(hI,..,h s ) are
system state vector and process parameters vector, respectively. As the sintering process is
characterized by simultaneous and successive action of these mechanisms, then the net
sintering rate during this process can be calculated as a sum of the forrrr'
dx
- = II (x,T; A,B) + ... + 1m (x,T; A,B).
dt
NECK GROWTH KINETICS

Let {Xi Ix i+1 - Xi = const}n and {TJn be arranged, according to increasing values, as
sets of neck size values and sintering temperature respectively. Let the sintering process is
defined by points (xi' Ti) by that the increment in temperature from T, ~ Ti+1 will cause a
neck size growth Xi for I1x. At that. the total rate value in each point (xi' Ti) will be
dxl = 'tCL =C i
dt (xi,Ti) k=1
where c' is the corresponding numerical rate value. When approximating the first
derivative of the last equation by difference
:I(x. ,
"
T)
we obtain an expression that defines the corresponding time steps as follows
When we apply the last expression, the time dependence of a neck radius can be defined
with a set {ti}n obtained on the basis of the relation
t i =ti_1 +l1ti (i=1,2, .ns t; =0)
and added to the set {Xi}n' where M i is a function of a neck radius and of sintering
temperature, i.e.
I1t i = I1ti(x,T; A,B) .
The sintering process is carried out within time intervals ~t; t at temperature {T In '
i
stepwise heating, when both time and temperature steps
M; =t; -t;_1 . (t o =0)

I1Ti = Ti+1 - T,
62
0
0
c:i
or>
N
c:i
I
0
or>
c:i
I
or>
r--.
c:i
I
~O
0
~~
~I
0'
0
- ' or>
"!
"I
0
or>
"I
or>
r--.
"I
0
0
N
I
0 10 20 30 40 50 60 70 80
Time (min)
a)
-{).2 5 ~ --T -- ~ ~ T.~ J .

. _ _ L ~ ~ J I
J - - I 1 .. 1 . . . ,
l_ i - -:- ~-bl?"'rh--""& Ldl_~ ~ l_ I ~-
-{).75 I . 1 ' .j.... _ . 1 ,. I . I ' --1 -
j ....> 1- :- I I J ";" +- ~ ~ ~ I : '
.J
~ -1.00 - I I . 1- ..:-
I -~_ I- - I .r.: 1. .
1
: . I . . j . I
I -:- 1-
I
t- .' . ,. iI .
'. ! :
.:....
]i -1.25
J
I.
I
:.. 1 : 1- ';'"
. _ 1_ :- I .. . I
.-..
_.
~ '-
j . -r-
"'- J.... '

I
--r-
'
.,
1"
... I _ i- -:-
I 1- ' I .. . .
_)
- '-
I .: -L
I ,"
-1.5 0 I -: - .1 . . ' .' l.:....l -. 1.
...t .: I ~ -l
, I
-1.75 .1 I.
400
500 60
r: 600
el11 700 40 .~
'IJe"Clf. 800 20 e~'\
lI"e rO -<.'~
C)
b)
Figure 1. Neck growth kinetics during sintering of silver (a ~ 1011111) by stepwise heating.
T = 400-1000C , /'"T = 100C , /',,( ' = 2.5 , 10 and 20 min. (a) As 2D trajectory. (b) As 3D trajectory.
63
can be either changeable or constant. At that the time step f':..t ; is determined by the
expression
x,r -x1-
1
= dxl I '
A
uti !J.t t =
dt (z , T.) : (x t , T)
J
I ' J
unde r condition that tj_) < i, :s; tj (i, j = 1,2,...) .

The main characteristic of the above numerical method for determination of the neck
growth kinetic s is to take into account an arbitrary number of mechani sms and analyze their
simultaneous and succe ssive action . Not dimini shing the generality of this meth od, the
presumption is made in this paper , as in paper', that the six mechani sms contribute to the
neck growth during the sintering proce ss:
Sintering of silver by stepwise heating was simulated for the temperature inter val from
400 to 1000 0 e and for the con stant step !J.T = 1000 e within a constant time interval
Si" = 2.5 , 10 and 20 min . As is evident from Fig. 1, neck growth is characterized by a
(approximately) continual function of a parabolic type and the neck growth rate is inversely
proportional to a time interval St": the most rapid neck growth is obtained within the
shortest time interval.
3-D GRAPH
Grains can be approximated by spheres scattered throughout the material' s volum e.
Let us consider two spherical grain s denoted as S 1(R)_ rl) and S 2 (R 2.r2 ) , where R I and
R 2 are the corresponding position vectors of two spheres (Oxyz system), rl and r2 are
corre sponding radii , and d = deS). S2) is grain s centers distance . If it is taken that two
spherical grain s approach along y-axis then the basic equat ions of spheres S I and S 2 can be
written in the following form
x 2 + y 2 + z 2 = r,2 1\ x 2 + (y - d )2 + z2 = rr
By substituting the first Eq . into the second one, it can be obtained the equation of
intersection surface
2 2 2 2 2+ d 2)2
1j - r2
x +z =1j -
[ 2d
Figure 2. A two-sphere geometric model.
64
a) b)
Fig ure 3. 3-D graph for the model on Fig. 2. (a) Initial model. (b) After 76 min.
T
d
1
a) b)
Figure 4. An aggregate of spheres geometric model. (a) Initial state. (b) After sintering .
Thi s simple mathematical procedure enables estimation of shapes and values of

contact surfaces between two or more spherical grains, wherein the neck radiu s and its
contact surface are given by
2 2 2+d 2)2
r) - r2 2 rj 2 2d2+ d 2)2] .
- r2
r= rt -
( 2d
and Pes = 1f .
[rt - (
Spherical grain s ca n be shown also by polyhedrons with a great number of small
convex polygon s, N, thus when N ~ OCJ polyhedral shape of the grain is tran sformed into
65
the shape of spherical grain. In that case, grain shape corresponds more to real grains'
morphology, and the procedure for calculating contact surfaces values becomes numerical.
The accuracy level of the numerical procedure is directly determined by exactness of
polyhedral approximation of sphere i.e. depends on the value of N.
a) b)
Figure 5. 3-D graph for the model on Fig. 4. (a) Initial model. (b) After 76 min.
Using previous simulation method it can be computed (Fig. 1) that for At' == 20 min
characteristic kinetic values are (r,t) = (5.3 ~m,76 min) . Shown of Fig. 2 is the model
system of two spheres. If the starting 3-D model geometry is as in Fig. 3a, then after 76 min
new 3-D geometry would be as shown in Fig. 3b. Fig. 4 shows the initial model for the
sintering of an aggregate of spheres. Corresponding 3-D graph shown in Fig. 5.
CONCLUSION
In this paper the modeling and simulation of the sintering process concerning neck
growth have been given. For a first calculation, we defined functional dependence of
contact surface as a 3-D function of topological parameters for the model of two spheres. In
some cases polyhedral approximation is acceptable too, where the polyhedron can be
constructed as a 3-D graph. We also defined time dependent intersection of spheres.
Numerical integration of rate equations represents the basis of this method. Process
simulation could be done under conditions of either constant or changeable heating rate and
at constant or varying temperature.
Summarizing the results obtained, it can be said that the proposed numerical method is
suitable for both qualitative and quantitative determination and the following of neck
growth kinetics during the sintering process; also that the same can be used for the analysis
of experimental data and planning of experiment, i.e. prognosis of the sintering process.
REFERENCES
1. Z.S. Nikolic, R.M. Spriggs and M.M . Ristic, Contribution to investigation (If the sintering process from the
point of sintering diagrams, in: Sintering '85, G.c. Kuczynski , D.P. Uskokovi c, H. Palmour III and
M.M . Ristic, eds. , Plenum Press , New York (1987) 53 .
2. M.F. Ashby, A first report on sintering diagrams, Acta Metall ., 22:275 (1974) .
66
PHENOMENOLOGY OF SINTERING KINETICS USING UOz AS A MODEL
Maria Vesna Nikolic l and Stamenka M. Radic 2
IJoint Laboratory for Advanced Materials of the Serbian Academy of

Sciences and Arts, Knez Mihailova 35, 11000 Belgrade , Yugoslavia
2Institute of Technical Sciences of the Serbian Academy of Sciences and
Arts, Belgrade, Yugoslavia
INTRODUCTION
Investigations of sintering on models give basic information on the kinetics and

mechanism of the sintering process, though it cannot be directly applied on real systems.
Phenomenological principles enable the establishment of a functional connection between
parameters characteristic for a sintered sample and the sintering time. One of the basic
tasks is establishing a physical meaning for characteristic parameters of the defined
phenomenological dependence . In this case the equations of Ivensen, Ristic-Jovanovic and
Geguzin gave the best results.
V. A. Ivensen l described sintering kinetics based on the assumption of a constant
relative pore volume reduction during a certain time period independent of the starting
compact porosity
2
M. M. Ristic and S. Jovanovic analyzed the sintering kinetics from the viewpoint of
possible application of the general process equation . Their starting assumption was that the
process rate constant changed both with the temperature and time of sintering .
Ya. E. Geguzirr' observed sintering kinetics as a process characterized by a quasi-
stationary diffusion coefficient.
The sintering kinetics was also analyzed using the master sintering curve 4.5.
The purpose of this paper is to make a contribution to the use of phenomenological
theories in the analysis of the kinetics of the sintering process of real disperse materials,
using an experimentally obtained uranium-oxide (D02) powder.
EXPERIMENTAL
A D02 powder with fractions smaller than 63 11m and specific surface of 4.06 m2/g
was used in these investigations. This powder was pressed under pressures of 25-200 MPa
and the density of compacts obtained is given in table 1.
Advan ced Science and Technology ofSintering , edited by Stoj anovic et aJ.
Kluwer Academi c/Plenum Publishers, New York, 1999 67
Table 1. Density of UO z compacts
Pressure (MPa) Compact density (g/crrr') =

(l:1VNo)m.x I-poIPT*
25 3.68 0.6645
50 4.10 0.6262
100 4.69 0.5725
200 5.53 0.4969
. .
*PT- theoretical density, for U02 n is 10.97 g/crrr'
The compacts (0 8x4 mm) were sintered in hydrogen atmosphere at temperatures of 1473-
1773 K for 45-360 minutes . The densities of sintered samples are given in table 2.
Table 2 Density of samples sintered at temperatures of 1473-1773 K (in g/crrr')
Pressure Temperature time (min)

(MPa) (K) 45 60 180 360
25 1473 4.66 4.95 5.92 6.16
1573 5.82 6.08 7.10 7.30
1673 7.05 7.25 8.06 8.40
1773 8.12 8.35 8.90 9.18
50 1473 5.95 6.12 7.11 7.54
1573 7.10 7.25 8.09 8.57
1673 8.10 8.26 8.87 9.20
1773 8.95 9.04 9.50 9.65
100 1473 6.90 7.07 7.90 8.45
1573 8.01 8.15 9.00 9.25
1673 8.75 8.87 9.40 9.80
1773 9.64 9.75 9.95 10.04
200 1473 7.65 7.73 8.45 8.75
1573 8.47 8.60 9.21 9.46
1673 9.69 9.80 10.02 10.12
1773 10.04 10.08 10.21 10.33
DISCUSSION
Analysis of experimental results was performed using three different

phenomenological equations and the master sintering curve. All three phenomenological
equations model the volume shrinkage rate as a function of the sintering time (table 3).
Table 3 Phenomenological equations of sintering kinetics
Name Form* Definition of parameters

Ivensen' q, m - constants, which depend on the sintering
~V (~V)
V-= V- [1-(I+qmt)-lIm] temperature and compact properties
o 0 max.
Ristic- K - process rate constant, B - process parameter
Jovanovic
2 ~V =K(l-Be-''')(st)eX P(-l I2( p' ' ' - 1l describing the difference between effective
Vo
surface at the beginning and end of the sintering
process , s - standardization parameter, p = lito, to
- start of the domination of the sintering process
Geguzirr'
~V
-=1..
Vo
[AD
DI;v+-(I-exp(-qt))
q
] A,l:1D - constants, Dkv- quasistationary diffusion
coefficient, q - the process rate constant
*the volume shrinkage rate was defined as:l:1VNo=(p-po)/p, where: P - density of the sintered compact, Po-
compact density .
68
All three equations can be used to model the sintering process of U02. Values of
parameters obtained are given in table 4.
Table 4 Values of parameters obtained for the three analyzed phenomenological equations
p T Ivensen Ristic-Jovanovic Gezuzin

(MPa) (K) q m K B S ADk;v2 MD q
25 1473 0.Ql8 3.072 0.4056 0.8642 0.0143 4.237 0.0067 0.0174
1573 0.092 3.278 0.4992 0.5048 0.0146 9.424 0.0151 0.0326
1673 0.461 3.351 0.5655 0.2364 0.0100 14.0 0.0275 0.0537
1773 4.986 3.854 0.6008 0.1183 0.0091 9.37 0.0389 0.0687
50 1473 0.050 3.047 0.4676 0.5209 0.0094 20.1 0.0123 0.0320
1573 0.210 3.067 0.5317 0.2915 0.0077 20.05 0.0234 0.0520
1673 1.254 3.392 0.5581 0.1600 0.0083 12.5 0.0341 0.0668
1773 14.708 3.932 0.5773 0.0990 0.0102 7.23 0.0449 0.0816
100 1473 0.075 2.969 0.4595 0.4067 0.0070 24.0 0.0149 0.0415
1573 0.274 2.798 0.4972 0.2830 0.0109 12.0 0.0224 0.0497
1673 0.900 2.897 0.5330 0.1590 0.0101 4.0 0.0354 0.0750
1773 727.47 5.259 0.5332 0.0475 0.0056 3.54 0.0465 0.0894
200 1473 0.105 3.608 0.3760 0.3987 0.0082 15.9 0.0127 0.0408
1573 0.328 3.248 0.4181 0.2746 0.0105 12.1 0.0194 0.0519
1673 54.435 4.607 0.4528 0.0839 0.0128 4.36 0.0351 0.0802
1773 1505.6 5.437 0.4714 0.0522 0.0352 4.13 0.0502 0.1115
I the values for parameter p were very imprecise , which IS the reason why they are not given here
5
2 these values are 10.
The master sintering curve 4,5 (MSC) concept is based on the assumption that the
microstructure evolution depends on density and one diffu sion mechanism dominates the
sintering process. If E>(t, T(t is a temperature-time dependent function, and (p) is
considered a characteristic that quantifies the effects of the microstructural evolution on the
sintering kinetics as densification occurs, then :
(p) = E>(t, T(t)) (I)
where :
(p);:.L: (G(p j dp n (2)
-ao,
Po
3pr(p)
incorporating changes of both microstructure scale, G(p) and scaling parameter I'(p);
and:
(3)
where Q is the apparent activation energy; R the gas constant.

The MSC is obtained as the dependence of the relative density on E> (all points should
be on one curve).
The values of process activation energy were calculated applying the method
5
described by Johnson et. al. using data given in table 3 for all four pressures applied (table
5). These values were used to defined MSC curves for all four cases.
Figs. 1-4 show examples of the curves obtained using data given in table 2, the MSC
and the three defined phenomenological equations.
69
0.9
0.8
;:. 0.7
'w
c
Q)
"0
Q) 0.6
>
~
CO
~ 0.5

0.4
0.3
-34 -32 -30 -28 -26 -24
In(E
Figure 1. The dependence of density of sintered VO z on In(E for samples pressed with 25 MPa (MSC curve)
0.60
0.55
0.50

0.45
0.40

0
>
......
><1
0.35
0.30
0.25

0.20
0.15
50 100 150 200 250 300 350 400
t [min]
Figure 2. The change of AVN o with sintering time for samples pressed with 25 MPa using Ivensen's equation
70
Figu re 3. The change of /:,.VNo with sintering time for samples pressed with 25 MPa using Ristic-Jovanovic's
equation
0.60
0.55
0.50
0.45
0 0.40
>
-...
>
<]
0.35
0.30
1473 K
0 .25 1573 K
0.20 1673 K
'Y 1773 K
0. 15
50 100 150 200 250 300 350 400
t[min]
Figure 4. The change of /:,.VN 0 with sinteri ng time for samples pressed with 25 MPa using Geguzin's equation
71
Table 5 The activation energy obtained using the MSC and equations Ristic-Jovanovic and
Geguzin (kJ/mol)
Pressure (MPa) MSC Ristic-Jovanovic Gezu zin

25 360 27.328 89.843
50 310 14.523 61.549
100 300 11.052 59 .549
200 395 16.293 79.327
MSC
500
Geguzin
& Ristic-Jovanovic
400
300
-
~
o
E
J
=.. 200
W
100
o 50 100 150 200

p [MPa]
Figure 5. The dependence of the act ivation energy of sintering V0 2 on pressure applied
The values of process rate constants obtained for equations Ristic-Jovanovic (K) and
Geguzin (q) were used to determine the process activation energy (table 5) using the
Arr heni . 6
emus equation":
(4)
where E is the activation energy, R the gas constant and T is the sintering temperature.
A comparison of the values given in table 5 and literature data 78 shows that in all
cases the average process activation energy obtained is lower that the value given in
literature (::0440 kl/mol) .
The dependence of the process activation energy on the pressure applied (figure 5)
shows that in all cases analyzed this characteristic value decreases until the pressure of 100
MPa, and then increases. This undoubtedly indicates that according to all three methods
72
used a similar mechanism is responsible . However, the differences in values obtained for
phenomenological equations are a logical consequence of the different phenomenological
assumptions made on how the sintering process takes place . Thus, phenomenological
analysis of the sintering process objectively only has formal importance and limited value.
CONCLUSION
A phenomenological analysis of the sintering kinetics of a UO z powder was

performed, from the viewpoint of theoretical analyses formulated by V. A. Ivensen, M. M.
Ristic - S. Jovanovic and Ya. E. Geguzin . It has been shown that all phenomenological
principles defined only have a limited value and characteristic kinetic parameters a general
formal importance.
ACKNOWLEDGMENT
The authors would like to express their gratitude to M. M. Ristic for useful
discussions, which were lead during work on these problems .
This work was performed as part of the project "Prognosis of Materials Properties
from the Viewpoint of the Triad SSP (Synthesi s-Structure-Properties)" financed by the
Ministry for Science and Technology of Serbia and the project "Investigation of the
consolidation process of materials " financed by the Serbian Academy of Sciences and Arts.
REFERENCES
I. V. A. Ivensen, Fenomenologiya spekaniya, Metallurgiya, Moskv a, 1983 (in Russian)

2. S. Jovanovic, M. M. Ristic , Poroshkovaya metallurgiya, No.9, 102 (1956)
3. Ya. E. Geguzin , Fizika spekaniya, Nauka , Mo skva , 1967 (in Russian)
4. Hunghai Su, D. L. John son , Master sinter ing curve : a practical approach to sintering, J. Am . Ceram . Soc.
79 , 12(1996), 3211-17
5. D. L. John son, Hungh ai Su, The master sintering curve in: Advances in Powder Metallurgy and
Particulates - PM 2TEC 97 Intern. Can! Proc.(1997 )
6. A. K. Galway , M. E. Brown, A theoretical ju stification for the application of the Arrhenius equation to
kinetics of solid state reactions (mainly ionic crystals) , Proc. R. Soc. Land., A 450 (1995) , 501-512
7. P. Ram, H. S. Gadiyar, P. K. Jena , J. Less Comm. Metals. 10 (1960), 183
8. R. Lindmer , F. Schnitz, Z. Naturf. , 16a (1961) , 1373
73
CONTRACTION OF THE COMPLEX MODELS BY
THE STOICHIOMETRIC NETWORK ANALYSIS
Zeljko Cupic,' and Ljiljana Kolar-Anic'
lIChTM - Department of Catalysisand Chemical Engineering,

Njegoseva 12, 11000 Belgrade, Yugoslavia;
2Faculty for PhysicalChemistry,University of Belgrade,
P.O.Box 137,Studentski trg 16,11001 Belgrade, Yugoslavia
ABSTRACT
Contraction procedure of the complex chemical models with several

independent intermediates by the stoichiometric network analysis, as the very useful
method for such purposes, is demonstrated on the model for the hydrogen peroxide
decomposition in the presence of iodate and hydrogen ions. It is shown that after
reduction the model preserve main characteristics of the initial one.
INTRODUCTION
The complex models proposed for the complex chemical reactions can be
contracted by the procedure proposed by Bruce Clarke based on the stoichiometric
network analysis'<. Nevertheless, there is some uncertainty in this procedure related
with choosing the necessary reactions between obtained new ones, what about will be
discussed in the following. The problem and its surmounting is illustrated during
contraction of the model for the hydrogen peroxide decomposition into the water
and oxygen in the presence of iodate and hydrogen ions,
known as the Bray-Liebhafsky oscillatory reaction':'.
Adv anced Science and Technology ofSintering , edited by Stojanovic et al.

CONTRACTING PROCEDURE
In the model for the Bray-Liebhafsky oscillatory reaction,"?
103" + I" + 2H"

-- HIO+HIO z (Rl),(R-l)
----
+--
HIOz + I"+ H+ ----+ IzO+HzO (R2)
IzO+HzO +-- 2HIO (R3),(R-3)
HIO + 1"+H+ +-- Iz+HzO (R4),(R-4)
HIO+HzOz ----+ I" + O, + H++ HzO (R5)
IzO + HzOz ----+ HIO+HIO z (R6)
HIOz+HzOz ----+ 103" + H++ HzO (R7)
103" + H++ HzOz ----+ HIO z + O, + HzO (R8)
proposed in the given form with intention to simulate numerous experimental

phenomena.r" there is five independent internal species, I", Iz HIO, IzO and HIO z,
and eleven reactions (five irreverse and three reverse ones).5.9
Our aim has been to remove lzO species from the model. For this purposes,
the general method for simplifying chemical networks while preserving overall
stoichiometry in reduced mechanism is applied." By this method, if one internal
species ought to be eliminated from any model, the redefinition of the set of
reactions where this species take part, or corresponding submodel, must be carried
out.' Since, in our case, we intend to remove IzO, we need to analyse the submodel
consisting of the reactions (R2), (R3), R(-3) and (R6).
In the considered submodel, only IzO is the independent internal species. The
others, i.e. HIO z, HIO, Iz and 1-, are the external ones, since their participation in the
overall process is not restricted on the reactions involved in the submodel.
By the stoichiometric network analysis of this submodel, instead mentioned four
reactions we have found three new ones which are independent reaction pathways of
the sub model :
HIO z + I" + H+ ----+ 2HIO (R9)

HIO z + 1- + H++ HzOz ----+ HIO + HIOz + HzO (RlO)
2 HIO + HzOz ----+ HIO + HIO z + HzO (Rll)
Here, the external species of the submodel, which appear at the both sides of
same reaction, are only summed without cancelling. This is required by precise
contracting procedure, since the submodel is the part of the whole model and the
species mentioned really participate in the reactions where they take place in the
form indicated. In other words, the reaction (RIO) is catalytic and (Rll) is
autoinhibitory one. Any additional contracting procedure or cancelling the species
that appear at both sides of the same equation demand the additional analytical
examination of the model reduced.
76
Thus, in order to remove 120 from the model M(1-8), the submodel consisting of
reactions (R2), (R3), (R-3) and (R6) is replaced by last three reactions (R9), (R10)
and (Rll ). The new model M(1,-l,4,-4,5,7,8,9,lO,11)
---.
103- + 1- + 2 H+ +-- HIO+HI02 (R1),(R-1)
---.
IDO + I" + H + +-- 12+ H 2O (R4),(R-4)
HIO+H202 ---+ I + O 2 + H ++ H 2O (RS)
HI0 2+HP2 ---+ 103 + H ++ H 2O (R7)
103"+ H ++ H 202 ---+ HI02 + O 2 + H 2O (R8)
HI0 2 + 1-+H+ ---+ 2HIO (R9)
HI0 2 + I" + H ++ H 202 ---+ HIO + HI0 2 + H 2O (RlO)
2HIO+HP2 ---+ HIO + HI0 2 + H 2O (Rll)
has four independent internal specie and ten reactions (six irreversible and two
reversible ones).
Analysing three new reactions (R9), (RlO) and (Rll), we can see that the sum
of reactions (R9) and (Rll) gives the same stoichiometric relation as (RlO).
Therefore, we have examined separately two additional variants of the last model
which consist the reactions (R9) and (Rll) on one hand, or (RlO) on the other hand,
that is either M(1,-l,4,-4,5,7,8,9,11) or M(l,-l,4,-4,5,7,8,10).
Since the considered Bray-Liebhafsky reaction is the oscillatory one in
defined domains of pararneters.Y'":" the model offered, at least , must be capable to
simulate oscillatory evolution of the intermediates. Therefore, the stability of both
variants of the model for the Bray-Liebhafsky reaction has been examined. As the
model under consideration has four independent intermediates we couldn't do
anything other but apply the stoichiometric network analysis. 1
The stability of a steady state is analysed , as usually, by means of linearization
of the general equation of motion of a stoichiometric network about this steady state
In particular, the stability is defin ed by the sign of the real part of the eigenvalues of
the matrix
M = (diag h) S(diag Ej) KT

where diag h is a diagonal matrix whose elements are the reciprocal of steady state
concentrations, S is the matrix of the stoichiometric coefficients and K is the matrix
of the orders of reactions with its transpose ](F. Here, diag E j is a diagonal matrix
whose elements are the reaction velocities since v... = E j , where v... is the reaction
velocity vector, E is the matrix with columns consisting of all the extreme currents or
the routes of the overall reaction in the steady state and jis the current vector.
Usually, the first step in this procedure is the calculation of the matrix of
currents V(;) where
VCJ) = - S(diag Ej) KT
and calculation of its principal minors .
77
M
's
'tj
'0
S 1E-7
__
300 600
Time/min
Fig.1. The numerical simulations of dynamical behaviour of the Bray-Liebhafsky oscillatory reaction
presented by oscillatory evolution of intermediate iodide concentration for the model:
M(1.-l,4, -4,5,7.8.9.11}. [H 20 21 =0.35 mol dm", [10 3'1 =7.33 10-2 mol dm? and [H+1 =2.70 10'2 mol
dm? . The rate constants are taken from ref. 5.
Thus, by the stoichiometric network analysis where, beside others, matrix E

and VV) are calculated explicitly (Applying whole mentioned calculating procedure
on the both variants of the model) we have obtained that only variant M(1,-I,4,-
4,5,7,8,9,11) has the steady state which can be unstable under certain conditions. In
particular, the steady state is unstable when following instability condition
is satisfied. Here, [HIOL. and [HI0 2 L are the steady state concentrations at fixed
value of hydrogen peroxide concentration denoted as [H 202 L
and k, are the rate
constants of corresponding reactions.
The rate constants for three new overall reactions (R9), (RIO) and (R11) are
obtained constructing their rate laws by the steady-state approximation'. As the
initial set of parameters we used the one published in ref. 5. The result of numerical
simulation for the model M(I,-l,4,-4,5,7,8,9,11) is given in Fig.1. In this case , when
the instability condition is satisfied, the oscillations are obviously obtained whereas
this is not a case for the model M(l,-l,4,-4,5,7,8,1O).
Further contraction is also possible. First , we can drop some reactions from
the model preserving the ability of the model to simulate oscillatory evolution of the
intermediates, but loosing the ability to simulate variety of phenomena existing in the
real system. Second, we can transform existing single reaction steps having species
that appear at the both sides of same reaction. Simple cancelling of such species and
adjusting of the rate constants properly is not enough to preserve the oscillations. For
example, if such procedure is applied on the model under consideration M(1,-l,4,-
4,5,7,8,9,11), the oscillations disappear. Third, we can reduce next species with aim to
obtain the model as much as possible simple for theoretical analysis. Anyhow, after
any reducing step we need to examine stability of the main steady state and test the
obtained results by the numerical simulation of the overall process .
CONCLUSION
The contracting procedure of the complex reaction model is illustrated on the

hydrogen peroxide decomposition in the presence of iodate and hydrogen ions . The
78
surmounting of the problem that can appear in such systems, related with getting two
alternate but same stoichiometric networks, is presented.
ACKNOWLEDGEMENTS
We thank the partial support of the Fund for Science and Technology of
Serbia and Federal Ministry for Development, Science and Environment of
Yugoslavia.
REFERENCES
1. B.L.Oarke, Stability of complex reaction networks, in Advances in ChemicalPhysics, Vol XLIII, p.I,
I.Prigogine and S.A Rice, eds., J.Wiley, New York (1980).
2. B.L.Oarke, General method for simplifying chemical networks while preserving stoichiometry in
reduced mechanisms, J.Chem.Phys., 97: 4066 (1992).
3. W.C.Bray,A periodic reaction in homogeneous solution and its relation to catalysis, J.Am.Chem.Soc.,
43:1262(1921).
4. W.C.Bray and HA.Liebhafsky, Reactions involving hydrogen peroxide, iodine and iodate ion. 1.
Introduction, J.Am.Chem.Soc., 53: 38 (1931).
5. Lj.Kolar-Anic, Dj .Misljenovic, S.Anie and G.Nicolis, Influence of the reduction of iodate ion by
hydrogen peroxide on the model of the Bray-Liebhafsky reaction, Rcsct.Kinct. Cstsl.Lott., 54:35
(1995).
6. G .Schmitz, Cinetigue de la react ion de Bray, J.Chim.Phys., 84: 957 (1987).
7. Lj.Kolar-Anic and G.Schmitz, Mechanism of the Bray-Liebhafsky reaction: Effect of the oxidation of
iodous acid by hydrogen peroxide, J.Chem.Soc.Faraday Trsns; 88:2343 (1992).
8. Lj.Kolar-Anic, Dj .Misljenovic, D .Stanisavljev and S.Anie, Applicability of Schmitz's model to dilution-
reiniated oscillations in the Bray-Liebhafsky reaction, J.Phys.Chem., 94: 8144 (1990).
9. Lj.Kolar-Anic, Z .Cupie, S.Anic and G.Schmitz, Pseudo-steady states in the model of the Bray-
Liebhafsky oscillatory reaction, J.Chem.Soc.Faraday Trans. 93:2147 (1997).
10. M.Radenkovic, G .Schmitz and Lj.Kolar-Anic, Simulation of iodine oxidation by hydrogen peroxide in
acid media , on the basis of the model of Bray-Liebhafsky reaction, J.ScrlJ.Chem.Soc; 62: 367
(1997).
11. Z .Cupie and Lj.Kolar-Anic, Contraction of the model for the Bray-Liebhafsky oscillatory reaction by
eliminating intermediate 120, submitted for publication.
12. M.G.Peard, C.F .Cullis, A periodic chemical reaction. The reaction between hydrogen peroxide
and iodie acid, Trans.Faraday Soc. 47: 616 (1951).
13. H.Degn, Evidence of a branched chain reaction in the oscilating reaction of hydrogen peroxide,
iodine and iodate, Acta Chem.Scsnd. 21: 1057 (1967).
14. K.R. Sharma, R.M. Noyes, Oscillations in chemical systems . 13. A detailed molecular mechanism
for the Bray-Liebhafsky reaction of iodate and hydrogen peroxide, J.Am.Cbom.Soc.; 98:4345
(1976).
15. S. Anic, Lj. Kolar-Aaic, The oscillatory decomposition of H 202 monitored by the potentiometric
method with Pt and Ag+'S2- indicator electrode, Ber.Bunsenges.Phys.Chem. 90:1084 (1986), 91:
1010 (1987).
16. S. Anic, Lj. Kolar-Anic, The influence of potatium iodate on hydrogen peroxide decomposition in
Bray-Liebhafsky reac tion, Ber.Bunsenges.Phys.Chem. 90: 1084 (1986), 91: 1010 (1987).
17. S. Anic, Lj. Kolar-Anic, Kinetic aspects of the Bray-Liebhafsky oscillatory reaction,
J.Chem.Soc.Faraday Trsns.I 84: 3413 (1988).
18. S. Anic, D . Mitic, The Bray-Liebhafsky reaction. N . New results in the studies of hydrogen
peroxide oscillatory decomposition at high acidity, J.Serb.Chem.Soc. 53: 371 (1988) .
19. S.Anie, D.Stanisavljev, Z.Cupic, M.Radenkovie, V.Vukojevic, Lj.Kolar-Anic, The selforganization
phenomena during catalytic decomposition of hydrogen peroxide, ScienceofSintering, 30: 49
(1998).
79
Electron Structure ofYnhX 2(X=Si, P) Compounds
I. D. Shcherba, V.M. Antonov', I. M. Telychyn, , B. M. Jatcyk2,

L. O. Dobrianska, 1.1. Margolych
Department of X-ray Metal Physics, Lviv State University, Kyryla & Mefodiya Str.8, 290005 Lviv,
Ukraine
'Institute of Metal Physics, National Academy of Sciences of the Ukraine, Vemadsky Str.36,252141
Kyiv, Ukraine
2Ukrainian State University of Forestry and Wood Technology, Gen. Tchuprunka
str.103,290057 Lviv Ukraine
1. Introduction.
Many of the important physical and chemical properties of solids are related to their valence
electronic states. Compounds on the basis of d- and f-elements create wide class of crystalline
structures, which are distinguished for a great variety of the short range order co-ordination
polyhedrons in components atoms vicinity. In isostructural compounds the consequential
substitution of atoms in the first co-ordination sphere leads to the possibility of a local
influence on the atomic characteristics of a component as well as on the characteristics on the
whole compound. The most spread among rare earth intermetallic compounds R-M-X (R =
RE.E. ; M = d-element; X - sp-element) are compounds of the CeGa2 Ab (ThCr 2Sh; tI 10,
space group I4/mmm) structural type, which in fact is a superstructure of BaAl4 (tl 10, space
group I4/mmm) type [1-4]. In the recent publications [5,6] we presented results of X-ray
spectral investigations and the theoretical calculation of the total and partial densities of
electron states of RM2Sh compounds . Ternary phosphides were far less investigated up to
present, which is mainly due to the difficulties in obtaining of monophase samples. The results
investigations of magnetic properties was presented in [7,8] for some phosphides of ThCr 2Sh
structural type along with Moessbauer spectroscopic data. At the same time there is a lack of
results of systematic investigations by the means of high-energy spectroscopy and theoretical
calculations of the band structure of RM2P2 type compounds .
In the present work for compounds ofYNhX2 (X = Si, P)) we present our calculations of
the total and partial densities of electron states of Y, Ni and X by the linear MT-orbitals
method. For YNhX2 (X = Si,P) compounds we have obtained X-ray emission spectra of Ni
and X, which were matched with the theoretically calculated ones.
Advanced Science and Technology of Sintering, edited by Stoj anov ic et al.

Kluwer Academ ic/Plenum Publishers, New York , 1999 81
2.Experimental Details
The alloys with Si were prepared by melting pieces of the initial elements in an electric
arc furnace on a water-cooled copper hearth in an argon atmosphere. The purity of the initial
elements was not lower than 99,9%. Prepared alloys were homogenized in evacuated quartz
tubes at 800C for 750 h. The phase analysis of the alloys has been conducted by indexing of
powder diffractograms, obtained using a DRON 2.0 powder diffractometer and Fe Ka
radiation.
Initial materials for YNhP z sample preparation were powders of red phosphorus and
transition metals and ingots of rare earth. Nikel and phosphorus were ofa purity of99.98 wt.%
and rare earth metal higher than 99.7 wt. %. The transition metals and phosphorus were mixed
together with filings of the rare earth metal and pressed into pellets.
Samples of YNizPz compositions with total mass of I g were then sealed into evacuated
silica ampoules. These were heat treated at 1070 K during 500 hours with following
quenching in cold water without breaking an ampoules. For further investigation only single
phase samples have been selected. Total and partial DOS were calculated for 209 points(in the
case YNhSi z) and 244 points (in the case YNizPz) within a 1/16 Brillouin zone in a
semirelativistic approach using the linear muffin-tin orbital's method. The analysis of the
energy spectrum of a compound's valence electrons was carried out using the K- and L-
spectra of Ni and X-elements. The method concerning measurement of the spectra are
analogous to the described in Ref.5,!!.
3.Results and Discussion.
The theoretically calculated X-ray emission bands of the components and experimental
bands of Ni and Si(P.) are shown in Fig.1,2. Total and partial density of electron states of
compounds are display in Fig 3,4.As Y spectra have an extremely low intensity, they can be
obtained only with enormous exposition times. Actually, this means that the significance of
calculated data cannot be underestimated . The best accordance of the experimental and
theoretical curves is observed for the K- and L-bands of Ni. The presence of KI3" -satellite is
the characteristic feature ofKl3z.5 - band (4p.....,ls transition) of Ni; and its coincidence with the
main maximum F of the LII,JI!-band (3s.....,2p transition) of the X-elements indicates that there
is a considerable contribution of hybridised s-states of Si(P)of the Ni of KIh,5 -band.. It is
worth to notice that in YMv-band, which reflects the distribution of p-states, an intensive
maximum is observed at 15 eV. The experimental KI3! - band appeared to be wider than the
theoretical one. The maximum near the Fermi level, which in the case of binary and ternary
compounds [5,6,9-11] was connected with the influence ofd-states, in the experimental Si (P).
K 131 - band was less distinct than on the theoretical one.
Data about the relative contribution of atoms of different symmetry in the investigated
X-ray emission bands is presented in Table I .
The ratio of contributions of d3/z and d5/z states in the intensity of emission band is considered
as one of the most important characteristics of spin-orbital interaction in the valence band.
Without taking into account the spin-orbital interaction the ratio of intensities is: Id5!z/ Id3/z = 9.
As it can be seen from Table I, in both compounds, for which calculations were performed,
this ratio for Lm - band of yttrium practically does not differ. In our opinion, this can serve as a
sufficient reason not to consider spin-orbital interaction. The contribution of s-states in the
intensity of L m - band of Y is only slightly more than 5%. Unlikely, the contribution of these
states in the intensity ofNm - band increases approximately in 2.5 times. We should mention
that the contribution of s-states in L m - and Nm - bands of Y in YNhP z compound is
considerably less than in YNizSh compound. From Fig.3, where total and partial state densities
of YNhP z are shown, follows that the density of electron states of Y on Fermi level in all
82
, EF
rl
a /.J '\
i '1
i .I
.
Ii:
i /'\ \1
.
i / \ .I
( \ \
... . /
./ I
/ \
\
',\.
/ I \ ' '"
.... , I \ :
" \\ (I I ,
I'
I
I"~ \
j ,\
.,/ : ' .....
.....
-10 -5 -10 -5
Btl
b f
!
!
/
,"
""
-10 -5 -10 -5
c
g
""
..
-10 -5 -10 -5
Energy (eV)
Figure 1. Calculated (full lines) and observed (dash lines) X-ray emission valence spectra of the Y, Ni
and Si in YNi2Si2: YL 111 ( -.-.-.-) ,My ( ----- ) ,YNIII ( - - ) (a); SiKI3) (b); SiL l11 (c); NiKI32,5(e);
NiL lIl (f) ; NiMlIl(g).
83
a e
K/3 "
J,
-15 -10 -5
-15 -10 -5 -15 - 10 -5 o
-15 -10 -5 o -15 -10 -5 o
- 15 -10 -5 o - 15 -10 -5 o
Energy (eV)
Figure 2. Calcu lated (full lines) and observe d (dash lines) X-ray emissio n vale nce spectra ofY, Ni and P
in the YNizPz co mpound: YLII1(a);YMv(b); YN II1 (c); PKP) (d); PL II1 (h); NiKpz.s(e); NiL II1 (t) and
NiM111(g)spec tra .
84
Table 1. Contribution of electrons to the intensity of X-ray emission bands of YNizX2 . (%)
KI-band Llll-band Mill_band Nl wband

PI/2 P 3/2 SI/2 d3/2 dS/2 SI/2 d3/2 dS/2 S1/2 d3/2 dS/2
y 11.61 8.85 79.84
Ni 32.25 67.75 0.23 10.34 89.44 2,52 9.8987.59 33.41 14.31 52.2
Si 33.28 66.72 79.02 2.2418.73
Y 5.17 9.58 82.25 13.56 12.09 74.35

Ni 31.89 68.11 0.22 10.22 89.56 2.28 10.39 87.33 -
P 33.29 66.71 100
4 Y-total' Ni-tota l 1.5 I Si-total I

I 6
3 I 1.0 I
I 4
2 I
>:; 1
I 0.5
I>':
4 0.6
d
~J 0.4
"
g 2
u
"
<il 0.2
<Ii'
0
0 1.5 P
0.Q2 P
1.0
0.5
1.0
0.5
0.0 1.0 1.0 Energy, (Ry) 0.0 1.0
Figure 3. Total and partial densities of electron states of Yni-Si,
Table 2.Effective filling numbers of electrons (ene) in different bands of components inYNizX2
Compound Component s p d
Y 0.171 0.209 0.485
Ni 0.764 1.229 8.841
Si 1.227 2.375 0.632
Y 0,675 1,346 3, 129
Ni 0,403 0,547 8,706
P 1,438 2,831
85
40 75 r - - - - - - - , , - - - - ,
30 50
20
25
10
O. o
2
& 4 10
E
0 2
<;:i
~ 0
2
1) 10
V"
C/J' 5
0
0
0 o
I P
d I
50 10 I
'1/: I
I I'
_!riff,l _.>1-
0 o ,--,-,,'-'-"---'-''-''''-'''-'---'-''--'
0.0 1.0 0.0 1.0
Energ y (Ry)
Figure 4. Total and partial densities of electron states of Yni 2P 2
compounds is considerably higher, than in YNizSiz compound(Fig.4). The maximum of unfilled

d-states density is at +3 eV, s-states occupy 6-2 eV interval and slightly intersect with the p-
band, which is 2 eVabove. The effective filling numbers of electron states of components in
YNizP2 and YNizSiz compounds are shown in Table 2.
The number of valence electrons per atom was estimated from partial density of electron
states . Analysis of the results of calculations shown that the degree of occupation of spd-
orbitals of components varies and considerably differs from the number of external electrons in
isolated atoms. The inhabitancy of d-orbitals ofY in YNizP2 showed to be significantly greater
than in isolated state. The most interesting, in our opinion, is the analysis of external valence
sp-states occupation change dynamics, because it gives us possibility to estimate the
contribution of electrons of P in the chemical bond in YNizP2 compound . The electron
configuration ofP in compounds can be described as S1.4p2.8, which significantly differs from
S2 p3 (atomic P) . Thus, we can state that in the investigated compounds atom of P contributes
with 0.4-0 .5 electrons of s-symmetry per atom (in compounds of YNizSiz type atom of Si
contributes with 0.7-0.8 electrons per atom) .
Conclusions
The s-states of X-elements hybridise with the p-states ofY and the Ni and create the bottom of
the valence band. In the middle of the band p-states of the components are preoccupying, while
near the Fermi level d-states of transitive element dominate. YNizP2 compound are
characterised by the significant increase of the effective filling number of electron d-states of Y
compare with YNizSiz compound . Its can be connected with different methods of the sample
preparations. Compounds with P, which are received exclusively by method above described
can be very interesting objects for science of sintering.
86
References
1. E. Parthe and B. Chabot, in K A. Gscheidner, Jr. and L. Eyring (eds .), Handbook on the
Physics and Chemistry of Rare Earth, Vo1.6, Elsevier, Amsterdam, 1984, p. 113.
2. E.I. Gladyshevskii and 0.1. Bodak, Crystal Chemistry of Rare Earth Intermetallic
Compounds, Vyshcha Skola, Lvov, 1982 (in Russian).
3. A. Szytula, in KH.J.Buchow (ed .), Handbook ofMagn. Mat., vol.6, Elsevier,1991,p.85 .
4. W Jeitschko and B. Jaberg,1. Solid State Chern. 1980,35,312.
5. 1. D. Shcherba, V. M . Antonov, B. Va. Kotur, 1. of Alloys and Compo 242 (1996) 58-65 .
6. I. D. Shcherba et al. Phys . stat. sol. (b) 198,761 (1996).
7. M .Reehuis and W. Jeitschko, 1. Phys. Chern. Solids 51, No .8, 961-968 (1990).
8. E. Morsen , B. D. Mosel, W. Muller-Warmuth, M. Reehuis and W. Jeitschko. 1. Phys .
Chern. Solids 49, 785 (1988).
9. P.J .w. Weijs, M.T. Czyzyk, 1.c. Fuggle et aI., Z. Phys . B, Cond Matter, 78 (1990) 423 .
10. P. r.w. Weijs, H. van Leuken, PA de Groot et aI., Phys .Rev . B, 44 (15) (199]) 8195 .
11. I. Shcherba, Yu . Gorelenko, Va . Dutchak and M ..Ristic, 1. of the Less- Common Metals,
123 (1986) 85-88 .
87
COMPUTER GENERATION OF TWO - AND THREE - DIMENSIONAL
PACKINGS AS A BACKGROUND FOR NUMERICAL MODELING OF
SINTERING PROCESSES
V.V.Kartuzov, E.V.Kartuzov, I.V.Krassikov
Institut e for Problems of Materials Science, NAS of Ukraine , Kiev, Ukraine
SUMMARY
Models of ballistic packing of disks and spheres with a given distribution (unimod al, bi-
modal, Gauss, etc.) by radiuses and controlled compact density have been proposed .
Computer software, embodying the packing model as well as its characteristics and results
of calcul ation experiments with its involvement has been described .
INTRODUCTION
There are a lot of physical properties of material that are determined by its microstructure.
Subsequently, it is very important to learn how to predict and control material
microstructure and its evolution both in technological processes of material fabrication and
under different regimes of its operation in products . The most brightly microstructural
effect on physical properties is displayed in amorphous metals, amorphous glasses and
ceramic composite materials . Thus, in order to get understand ing of their unique
properties, the structural investigat ions by various methods of X-ray structural and electron
- diffraction analysis , EXAFS on neutron's dissipation. Of prime importance also are the
theoret ical methods of interpretation of structural data and their modeling.
Computer modeling of R&D technological processes in many cases makes possible to
avoid the conduction of costly power - and labor consuming experiments and along with
the development of computer technologies, plays more important role in research works.
The development of the models for R&D technological processes gets through the phases
of different detaliz ation: starting from continual represent ation of material as a sort of
some continuous media with isotropic and homogeneous properties up to the models,
Adva nced Science and Technology ofSintering, edited by Stojan ovic et al.
Kluwer Academic/Plenum Publishers, New York, 1999 89
accounting for structural material properties . Development of computer technologies
allows to switch to the models, representing material in technological processes as particle
ensemble .
Obviously, the first modeling phase of such detalization level is particles packing . In
conjunction with the fact that the initial phase of PM technology is filling, that is packing
with rather low density, then it is of an interest to develop the model of low dense
spherical particle packing with preliminary given their distribution by sizes. Problems on
packing modeling themselves are rather difficult mathematical task. Specifically, in the
case of polydisperse systems. The solution to this problem at different levels of system
complexity has been developed for many years. Intensive study on particle packings
dramatically grew up by the last third of XX century, when computer technologies
development made possible to switch from actual experiment (Finney works who studied
real packings of steel spheres up to 8000 pieces, became the classic ones in this field [1])
to computer modeling .
Computer modeling for microstructural evolut ion of polydisperse materials in sintering is
the youngest section of "sintering physics" science. The first works are referred to early
eightieth . These are works by Ross, Hare and group of investigators from the University of
North Carolina State [2], series of Anderson , Grest and Srolovitz works. In our country it
is worth noting the series of Kadushn ikov works published in "Powder Metallurgy"
journal [3,4] where the main scheme of computer modeling together with solutions to
some problems typical for sintering processes is given.
All existing models of microstructural changes in sintering can be reduced down to two
main types: based on two particle interactions and on evolution of topological structures .
As for the first case rather well developed methodology describing physical process of
interaction, that takes place between particles, through phenomenological equations of
sintering theory has been developed . Within this approach the simplest sintering models of
one-dimensional spheres (precisely two-dimensional variant disks with the same radius)
have been evaluated. For the second case, model topological structures, approximating
material microstructure by a set polyhedrons . Basing upon various first principles
(maximum entropy, equilibrium of two-faced angles, etc.), simulation models of grain
structure are studied by means of Monte-Karlo methods. These two types of
microstructural models explain quantitatively determined physical mechanisms of
sintering (local isolation, recrystallization) . Their main disadvantage is that the obtained
results describe only separate process phases. It does not allow for modeling sintering as
continuous phenomena, within the frames of common phenomenological approach. It
should be also noticed that the lack of packing models with controlled porosity limitates
possibilities of computer experiment. Typically packings are filled in by random
overswing of particles with similar radius . It is necessary to emphasize on the fact that all
investigators start with spherical models, but develop only two-dimensional variant with
disks, during which they are dependent on the possibilities of both computer technique and
applicable methodologies , number of particles (to be more precise: their low quantity in
representative volume), all the above said makes impossible to investigate local effects, as
for global effects they are roughly approximated .
INVESTIGATION METHODS
Design of materials with given properties , which becomes more essential nowadays,
passes through the compulsory investigation phase of designed materials - computer
90
modeling of technological processes for material engineering by scheme structure ~
property . Computer experiment is principal investigation method in such research work. It
comprises three components.
I) Modeling of particles filling - as the matter of fact this is the modeling of initial object
structure, being evoluted in a given way, forms the required physical and mechan ical
properties of designed material. The present work has reconsidered the approaches to the
design of algorithms for random dense packings suggested in. We stopped at ballistic
filling of spheres (disks in two-dimensional variant) with different distribution by radiuses
into the box .
2) Modeling of filling structural evolution during technological PM processes.
3) Structural investigation of modeled object in language of statistical geometry i.e. in
language of polyhedrons Voronoy and Delone simplexes. This is auxiliary software,
enabling to control structural parameters of material when evoluting from filling to
compact.
RESULTS AND DISCUSSION
The basic part of the results obtained in this effort is the investigation of filling generation
processes and study of filling properties by means of WPACK2 software [5]. Computer
software enables to generate random dense packings and fillings with different distribution
laws of disks by radiuses. The following implementations of distribution laws have been
considered in this work .
I . Unimodal law - to model random dense packings for atoms of amorphous metals and
filling of model powders ;
2. Bi-modal law - to model random dense packings for simple amorphous alloys and
fillings of two component ceramic powders as starting object in reaction sintering
processes;
3. Uniform law - to model random dense packings of amorphous metals and alloys (model
of soft spheres with narrow deviation of radius values) and complex amorphous glasses as
well as fillings of ceramic powders of commercial purity ;
4. Gauss law - second version for modeling of initial object state;
5. Experimental histograms - to model initial state of objects with preliminary determined
percentage contents of involved components.
Even with known distribution laws of particles by radiuses, packing density and structure
are often strongly dependent on external factors, which can be partially controlled . Thus
the controll ing parameter a was introduced into WP ACK2 software . Varying it within the
range O~a ~1f./2 we are able to model initial structure of investigated objects in a wide
spectrum of density changes .
Below see the illustrations to random packing generation with the following notations:
rj - radiuses of overswong particles ;
X,Y- box dimensions;
N- total number of particles in already generated filling;
a - governing structural parameter of filling ;
D - density;
m - average coordinate number;
Dr - dispersion of particle radiuses under Gauss distribution law.
Typically, the simplest idealized filling cases are the fillings with unimodal particle
distribution along the radius.
91
a) r= 12 ; La=O; X=1280; Y=800; N=1804; b) r = 12; L a =O.2; X=1280; Y=800; N=1643;
D=0.812; m=3. 99 D=0. 741; m= 3.36
Fig.! Unimodal particle distribu tion along the radiuses
O,90tD 4.50
m
0.80 \. 4.00
-,-, 3.50
0.70 -, -,
3.00
~
0.60
2.50
0.50
2.00
0.40 1.50
a a
0.30 1.00
0.00 0.40 0.80 1.20 1.60 0.40 0.80 1.20
Fig.2 Dependence of density and coordina te number versus structural parameter
a) r r=1 2; r 2= 20 ; La=O; X=12 80 ; Y=800; N=9 65; b) rr=1 2; r2=20 ; La=O.2; X= 1280 ; Y=800;
D=0 .8 12; m=3.94 N=880; D=0. 750; m= 3. 294
Fig.3 Bi-moda l particle distrib ution along the radiuses
92
0.90 4 .00
0 m
0 .80 3.50
0 .70 3.00
0 .60 2 .50
0 .50 2.00
0 .40 1.50
a a
0.30 1.00
0.00 0.40 0 .80 1.20 1.60 0.00 0040 0.80 1.20 1.60
Fig.4 Dependence of density and coordinate number versus structural parameter
a) r=16; Or=6; Lu=O; X=1280; Y=800; N=754 ; b) r=16; Or=6; La.--Q.2; X=1280; Y=800; N=391 ;
0=0.8' m=3.94 0=0.4' m=1.95
Fig.5 Gauss particle distribution along the radiuses
a) r l=12; r2=20; LCL=O; X=1280; Y=800;

N=lO03 ; 0=0.8; m=3.94
Fig.6 Uniform particle distribution along the radiuses
The given illustrations represent the possibilities of compl ex on packing generation. Value
N in these illustrations is of no import ance and stipul ated by the necessity to present the
information in form of figures. Varying structural parameter UE [O,7t/2] one can modify
initial packing density, 0, in a range from 0.2 1 to 0.84 . These limits are not strictly proven
but are the results of multiple computer experiments, conducted on the base of data
charged by actual tasks . Our goal was not to determine exotic cases for ultimate values 0 ,
but this work can be fulfilled . From the literature the maximum value, 0 for unimod al
packing out of spheres is (Om., = 0.634) and recently, more often one can find value of
DolO' = 0.84 for disks, howev er it is necessary to repeat that this is the value for dense
random disk packing but its maximum value has not been proven yet.
93
a) Unimodal distribution ; b)three-modal distribution, .
Fig. 7 Segments of three dimensional packing
Generation of three dimensional fillings with controlled density based on the same
algorithm of ballistic overswing of randomly appeared on the upper cover spheres, falling
in continuos viscous media and in continuously weak gravitation field (disregard the
processes associated with collision). Each act of sphere overswing leads to the fact that
each sphere occupies the place where its potential energy is characterized with local
minimum . Software developed for processor Pentium 133 generates the filling of 10000
spheres for 8 minutes.
Generated fillings are in a good agreement with experimental fillings for wide spectrum
PM technological processes of ceramic materials and are the basic ones for simulation
modeling of sintering and compaction processes .
REFERENCES
I. Finney J.L. Ph.D.Thesis - University of London , 1968.

2. H.J.Leu,T.Hare and R.O.Scattegood Computer simulation method for particle sintering , Acta metal.
Vol. 36,Vol. 8, pp.1977-1987 (1988) .
3. Kadushnikov R.M., Skorochod V.V. Investigation of zonality by means of computer simulation at
sintering process of powder materials. Powder Metallurgy , 1991, Vol. 7, pp.3l-37.
4. Kadushnikov R.M., Alievsky D.M., Alievsky 8 .M. Computer simulation of microstructure evolution of
poly-dispersion materials at sintering process. I. Principal issues. Powder Metallurgy , 1991, Vol. 2,
pp.18-24.
5. Skorochod V.V., Kartuzov V.V., Krasikov LV., Kartuzov E.V. Computer simulation of particle packing
(two-dimensional case) published in the book Some models of mathematical physics and the methods of
their investigation , Kiev 1997, pp. 155-170.
ACKNOWLEDGMENTS
This work was supported in part by Fund of Fundamental Investigation, Ukraine (Contract
No. 4.4/658) and by the Government Science and Technology Program.
94
Part II. NANOSTRUCTURED POWDERS
SCIENTIFIC AND TECHNOLOGICAL PROBLEMS IN NANOSTRUCTURED
MATERIALS SCIENCE
Rostislav A.Andrievski
Institute for New Chemical Problems

Russian Academy of Sciences
Chernogolovka, Moscow region 142432, Russia
INTRODUCTION
In recent years there has been increased interest in nanostructured (nanocrystalline,

nanophase, nanoscale, etc.) materials (NM) which are normally characterized by a grain
size in the range of 5-100 nrn. The great interest enjoyed by NMs everywhere is connected
at least with two reasons. Firstly, this is caused with a hope to realize unique physical,
chemical, and mechanical properties in the nanocrystalline (nc) state. Secondly, this topic
revealed many gaps in our understanding of the features of this state and also in the
preparation methods of its realization. The development of NMs emerged as an important
step in creating a new generation of materials. So foregoing circumstances gave rise to
many investigations, Conferences, and publications. For example, four specialized
NANOConferences (Cancun'92 , Stuttgart'94, Hawaii'96, Stockholm'98), three NATO ASI
(Spain'92 , Greece'93 , Russia'97) , and numerous MRS-, TMS-, EF - meetings have been
taken to say nothing of different related events (e.g. [1-7]). Total their annual quantity is
about 20-25 for a period of 5-7 years. Since 1992, the Journal "Nanostructured Materials is
being published in USA. Some comprehensive reviews and collections must be also
mentioned (e.g. [8-14]). So the information on the NM preparation and properties is very
wide. However, a number of problems remain unsolved. The discussion of them seems to
be interesting and topical.
PROCESSING
There are many of methods for the NMs preparation [5]. Table I shows the main of
them with some versions. Such variety of methods enlarges the technical possibilities for
obtaining different kinds of NMs and at the same time this variety creates some
competition. The powder technology methods seem to be more universal but the presence
of residual porosity often stands in the way. Films, coatings, and materials obtained by
crystallization from amorphous state can be prepared without porosity in the dense state but
Advan ced Science and Technology of Sintering , edited by Stojan ovi c et 31.
Table 1. Main methods for preparation ofNMs.
Group Main versions Subject
Gleiter's method
(gas condensation processing
and vacuum compaction)
Conventional compaction
and sintering Elements,
Hot pressing and HIP alloys,and
Powder High-energy technique compounds
technology - hot forging and extrusion
- electro-discharge compaction
- high static pressures and high
temperatures
- high dynamic pressures (shock
compaction, etc.)
Plastic Torsion straining

severe Equal channel angular pressing Metals and
deformation Phase strain hardening alloys
Controlled Crystallization under ordinary

crystallization conditions Amorphous
from amorphous Crystallization under high solids
state pressures
CVD Elements,
Film and coating PVD alloys,
technique Electroplating compounds
Sol-gel processes
their ranges of compositions and sizes are not so wide as in the case of particulate NMs.
Such situation takes also place for severe plastic deformation methods which can best be
applied only for ductile subjects. It should be noted that in many cases all these methods
and their variations not only compete but mutually complement also. Nevertheless, there are
many zones of overlapping between different methods and the necessity of their
comparison seems to be very topical. It is clear that such comparison must consider not only
properties ofNMs and their stability but economic efficiency, environment and so on.
The purpose of all preparation methods of NMs is not only an obtaining full dense
specimens and components but also the development and retention of a nc structure as
well. This problem is considered to be essential in NM preparation because intensive
recrystallization assisted densification of particulate materials, deposition of films and
coatings as well as crystallization from amorphous state. In many cases recrystallization
provides a conventional structure with a grain size of about I urn and larger. In this
connection high-energy consolidation and low-temperature methods such as high pressure
sintering, shock compaction, hot forging, magnetron sputtering and so on seem to be the
most useful for NM preparation. However, in many cases the detail information on optimal
regimes for these processes with special attention to recrystallization is absent As applied
to nc TiNffiB2 bulks and films, the development of a nc structure has been partly
investigated previously [14-19]. Preparation of another NMs based on metals and alloys
(Ni, Cu, Pd, Fe, Ti, Fe-Cu, etc.), intermetallics (NiAI and NbAb), oxides (Ti0 2, AhO), and
Zr02), and hard alloys (WC-Co) has been also partly described (e.g. [1-14]). Nevertheless,
in this field only first steps have been taken and further efforts seem to be necessary and
warrant
98
STRUCTURE AND PROPERTIES
The variety of the NM preparation methods results in many types of the NM structure .
Fig. 1 shows some different types of a nc structure of specimens obtained by high pressure
sintering, magnetron sputtering, and controlled crystallization from amorphous state[18-20].
a b
c d
Figure I. Fracture surfaces of the TiN bulk obtained by high pressure sintering (a) and melt quenched Fe-Si
alloy (b [20]) as well as three-dimensional AFM image of the TiN film (c) and dark field TEM (d) and HREM
(e) micrographs of the TiB z film obtained by magnetron sputtering.
99
The various methods such as XRD, TEM, SEM, SAED, and AFM analyses are used
for characterization of the NM structure. Unfortunately, in some cases the agreement
between results obtained by different methods is not so good (Table 2)
Table 2. Crystallite size of TiN high pressure sintered specimens[17].
This difference is considered to be connected with both some specific features of

measuring method and effect of texture and so on. Comparison of the ranges in mean grain
size estimates obtained by several XRD methods (Warren-Averbach and Scherer
approximations) has also revealed different results for nc Pd, Ag, and Cu [21]. It must be
taken in consideration when results of different authors are compared and discussed. It
should be noted also that in the case of films there are often two kinds of grain boundaries
such as intercolumnar (see Fig. I, c) and transcolumnar (see Fig. 1, d) ones. This seems to
be very important at discussion of the size effect nature. No doubt that effect of grain size
on properties of NM and nature of grain boundary in these subjects are the main scientific
problems (e.g.[8-12]). In this connection, the adequate characterization of NM by several
independent methods is considered to be very important and needs further clarification.
Undoubtedly hardness measurements are most popular for NM characterization because
of the ease of realization and the usefulness of the information. However, in some case the
interpretation of these results is not so easy with respect to the known high structural
sensitivity of hardness and its dependence on load as well as the test method used. Fig. 2
shows the hardness dependence on grain size has been determined experimentally in many
NMs. Fig. 2 shows some these results for specimens crystallized from amorphous solids
and ones deposited by cathodic arc evaporation [12, 22]. The similar behavior of hardness
with grain size has been also observed for NMs obtained by another methods (e.g. [3, 6,
l O, 14]). As evident from Fig. 2, for the Fe-Si-B and Fe-Cu-Si-B nc specimens, the well-
known Hall-Petch relationship asserts for a grain size larger than 25 nm. The pure Se yields
two distinct relationships in the intervals of 9-15 and 15-25 nm. For the Fe-Mo-Si-B and
NiZr2 subjects, the normal-to-abnormal Hall-Petch transition exists with a different critical
size (accordingly of about 47 nm and 19 nm). At last Ni-P alloy reveals anti - Hall - Petch
for the whole investigated grain size interval. The hardness of the TiN coating (the
thickness varied from 20 to 25 urn) increases linearly with decreasing grain size. In latter
case, it should be recorded that not only crystallite size can affect hardness but the N
content and residual compressive stresses also do and they are not constant in all
specimens. The physical reason of the different relationships in Fig. 2 is not clear. From the
above it is seen that the situation with size effect interpretation is not so simple. Many
attempts have been made in order to explain the hardness results (e.g. [2,3,6, 10, 12,23]).
However, a comprehensive explanation, as in the case of other physical, mechanical, and
chemical properties [23], invites further investigation.
There are another interesting unresolved questions in the NM problem such as nature
of homogeneous and unhomogeneous deformation, defects and stability of nc state, phase
equilibrium in nc solids and so on [8-12, 18, 23].
100
12.5
10.0
10 7,5
a..
S2.
> 5.0 NiZr2
I
2.5
S8 (x 10)
0
0,0 0,1 0,2 0,3 0,4
(r ' /2 (n m-1/2)
a
2100
..- 2100
....
Ie
-e01
lIl::
2400
til
til
W
Z 2200
C
a:
c(
:t:
0
a: 2000
o
i
1100
1100
CRYSTALLITE SIZE ( nm )
b
Figure 2. Hardness as a function of crysta llite size for different nc specime ns crystallize d from amorphous
state (a) [12] and TiN coating prepared by arc deposition (b) [22].
CONCLUSIONS
Some unresolved scientific and technological problems in nanostructured materials

science are cons idered and discussed in brief. Knowledge of NM nature is still incomplete,
requiring intense studies in order to determine the best strategies for future technologies.
101
ACKNOWLEDGMENTS
Sincere thanks should be presented to Dr. G.V. Kalinnikov and Dr. V.S. Urbanovich
for their active assistance. The supports from the INTAS (grant No 96-2232) and
INTEGRAnON (grant No 855) Programs are much appreciated.
REFERENCES
1. Proc. 2-nd Intern. Confer. Nanostructured Materials, Stuttgart 1994" H.-E. Schaefer, R. Wurschum ,
H. Gleiter, and T. Tsakalakos, eds., Nanostruct. Mater. 6:3-1021(1995).
2. Proc. 3-rd Intern. Confer. Nanostructured Materials, Hawaii 1996, M.L.Trudeau, V. Provenzano,
R.D. Shull, J.Y. Ying, eds., Nanostruct. Mater. 9:3-771(1997).
3. Mechanical Properties and Deformation Behavior ofMaterials Having Ultra-Fine Microstructures,
M. Nastasi, D.M. Parkin, and H. Gleiter , eds ., Kluwer Academic Publishers , Dordrecht (1993) .
4. Nanophase Materials. Synthesis - Properties - Applications, G.C. Hadjipanayis and R.W. Siegel, eds.,
Kluwer Academic Publishers, Dordrecht (1994) .
5. Nanostructured Materials Science & Technology, G.-M.Chow and N .!.Noskova,eds., Kluwer Academ ic
Publishers, Dordrecht (1998) .
6. Processing and Properties ofNanocrystalline Materials, C. Suryanarayana, J. Singh, and F.H.Froes,
TMS , Warrendale (1996) .
7. Nanophase and Nanocomposite Materials 1/, S. Komarneni , J.C. Parker, H,J. Wollenberger, eds.,
MRS, Pittsbu rgh (1997) .
8. H. Gleiter, Nanostructured materials: state of the art and perspectives, Nanostruct. Mater. 6: 3
(1995) .
9. R.W. Siegel , What do we really know about the atom-scale structures of nanophase materials?
1. Phys. Chern. Solids 55:1097 (1994) .
10. C. Suryanarayana, Nanocrystalline materials, Int. Mater. Rev. 40:41 (1995) .
11. M. Mayo, Processing of nanocrystalline ceramics from ultrafine particles, Int. Mater. Rev. 41 :85 (1996) .
12. K Lu, Nanocrystalline metals crystallized from amorphous solids : nanocrystallization, structure,
and properties, Mater. Sci. Eng. R16: 161 (1996) .
13. Nanomaterials: Synthesis, Properties and Applications, A.S. Edelstein and C. Cammarata, eds.,
Institute of Physics Publishing, Bristol (1996) .
14. R.A. Andrievski, State-of-the-art and perspectives in particulate nanostructured materials, in:
Advanced Materials and Processes. Yucomat JJ. D.P.Uskokovich, S.K Milonijch, and D.I Rakovich ,
Trans Tech Publications LTD, Switzerland (1998) .
15. R.A. Andrievski, Possibility of powder technology in processing advanced nanocrystalline materials, in:
Advances in Powder Metallurgy & Particulate Materials, T.M. Cadle and KS . Narasimhan, comp.,
MPIF , Princeton (1996) .
16. R.A. Andr ievski, G.V. Kalinnikov, and V.S. Urbanovich, Consolidation and evolution of physical-
mechanical properties ofnanocomposite materials based on high-melting compounds, in: Nanophase
and Nanocomposite Materials JJ. S. Komarneni, J.C. Parker , and H,J. Wollenberger, eds., MRS,
Pittsburgh (1997).
17. R.A. Andrievski, Physical-mechanical properties ofnanostructured TiN, Nanostruct.Mater.,9:607(1997)
18. R.A. Andrievski , The-state-of-the-art of nanostructured high melting point compound-based materials ,
in: Nanostructured Materials. Science & Technology, G.-M. Chow and N.!. Noskova, eds., Kluwer
Academic Publishers, Dordrecht (1998) .
19. R.A. Andr ievski, G.V. Kalinnikov , and D.V. Shtansky, Physical properties and structure of
nanostructured high-melting point compounds, Nanostruct. Mater. 10: accepted to publ , (1999) .
20. A.M. Glezer, Melt quenched nanocrystals, in: Nanostructured Materials. Science & Technology, G.-M.
Chow and N.!. Noskova, eds., Kluwer Academic Publishers , Dordrecht (1998) .
21. G.W. Nieman, J.R.Weertman, and R.W. Siegel , Mechanical behavior of nanocrystalline metals,
Nanostruct. Mater. I : 185 (1992) .
22. J.A. Sue, Development of arc evaporation of non-stoichiometric titanium nitride coating, Surf. Coat.
Technol.61: 115 (1993) .
23 . R.A. Andrievski and A.M. Glezer, Size effects in nanocrystalline materials, Phys. Metal. Metallogr. 87:
accepted to publ, (1999) (Engl. transl.),
102
AEROSOL SYNTHESIS OF NANOSTRUCTURED
MATERIALS
Olivera B. Milosevic
Institute of Technical Sciences of

the Serbian Academy of Sciences and Arts,
INTRODUCTION
The scientifical and technological interest in nanostructured materials is currently

tremendously increasing. I ) The basis of this interest is related to the extraordinary
properties that powders and materials at the nanometer or subnanometer scale exhibit,4.6
Such properties result from their structure that distinguish them from conventional
polycrystalline materials by the size of the crystallites that compose them as well as a large
volume fraction of interface and grain boundaries. The nanostructured materials research
efforts emphasize the synthesis routes for the generation of ultrafine powders with control
over particle size, shape, composition and morphology as the key issue in advanced
materials synthesis. I The aerosol synthesis route enables the generation of new
nanoparticles and nanomaterials either as coatings or powders as single, complex metal
oxides, nonoxides or metals by adjusting the precursor chern istry .i The starting-point of the
aerosol synthesis of nanostructured materials is the generation of discrete droplets of the
starting solution (aerosol) and control over aerosol decomposition in a high temperature
tubular flow reactor.8 9 The successive processes of solvent evaporation, drying, solute
precipitation and decomposition proceed through heterogeneous gas-liquid/solid reactions
in dispersed system ensuring high surface reaction and limiting any compositional
segregation to the droplet leve1. 9 By controlling the precursor solution chemistry,
processing parameters and mechanisms of particle formation through either the surface or
volume precipitation of droplets it is possible to tailor the powder size, morphology,
chemical and phase compositions . The condition for aerosol generation ultrasonically with
special emphasis on the various particle morphology synthesis is reviewed in this paper.
The importance to model the phenomenon of mass and heat transfer occurring during the
Ad vanced Science and Technology of Sintering, ed ited by Stojanovic et al.

Kluwer Academic/Plenum Publishers, New York. 1999 103
evaporation/drying stage is discussed from the viewpoint of the parameters leading to a
certain particle morphology. It is demonstrated that aerosol synthesis of nanostructures can
be realized in a controlled manner by adjusting the aerosol droplet size and precursor
chemistry.
NANOSTRUCTURED MATERIALS-SYNTHESIS,
STRUCTURE, PROPERTIES RELATIONSHIP
Nanophase materials are characterized by ultrafine metastable structure that contains

great concentration of defects either as point defects or disclocations, grain boundaries,
interfacial boundaries etc. Those materials differs structurally and propertywise either from
amorphous or crystalline state of the same chemical composition. It has been already shown
that nanocrystalline materials, nanoglasses, alloys with ultrafine structure and
nanocomposites are of special scientifical as well as applicative interest. Submicronic
materials, with grain sizes between 100 and 1000nm exhibiting properties deviating from
those of micron sized materials, represent the subject of intensive research too . Quanum
dots or quantum crystallites (semiconductor crystallites in the range between 1 to l Onm that
4
show three dimensional quantum size effect) also have a growing research interest.
In accordance to the proposed atomic structure of nanocrystalline materials, they are
composed of numerous small crystals less than 100nm in diameter, forming the crystalline
component and the network of boundaries. I The boundaries exhibit a broad spectrum of
interatomic spacings, ranging from 15 to 40% . It was shown that the atomic density is
reduced up to 30% in the boundary regions , in relevance to the neighboring crystals . I
Consequently, nanocrystalline materials are characterized with a high content of grain
boundaries (50%) and with the different grain boundaries structures inside one boundary,
that do not appear in the coarse grained materials. I This unique structure results in very
special and extraordinary properties they exhibit and indicates that nanostructures will gain
in great importance in the near future .
Research in the field of nanophase materials have seen a tremendous increase in
academic and industrial interest in the last decade as the consequence of their potentially
useful physical and chemical properties.' For instance, it is evident higher electrical
conductivity in ceramics and magnetics; increase in hardness and strength of metals and
alloys; 10 increased ductility and formability of ceramics ; II quantum-dots effects in
semiconductors; significantly modified magnetic behavior as well as superparamagnetism,
spin-glass behavior and magnetic viscosity, revealed in nanocomposite magnetic
s
materials . , 12 Decreasing the Curie temperature) by 40K in nanostructured (",70nm) nickel,
3
enhanc ing the diffusivity':' by a factor of 10 for nickel and alumin ium with grain sizes
between 70 and 30nm, increasing ductility of brittle ceramics, permitting large plastic
deformations at low temperatures.l" hardness and chemical resistivity observed for the
ceramics generated in the nanocrystalline form, high-temperature stability of Si3N4/SiC
micro/nano-composite'' represent several examples of the modifying characteristics for
nanophase materials. In the case of nanophase Ti0 2 with grain sizes between 2 - 20nm ,
enhanced ductility, sinterability, plastic deformation and high atomic diffusivities have been
observed. IS Significant changes in thermal expansion coefficient, magnetiic susceptibility,
saturation magnetization, superconducting properties are also associated with
1O
nanocrystalline solids. Although the mechanisms responsible for such behavior are far to
be clearly understood in all details, they are possible the consequence of the higher
boundary area in nanophases implying the structure importance in designing and modifying
the properties. Certain materials structure responsible for nanostructures behavior appears
104
during materials synthesis procedure through powder generation as well as sintering
process . This implies that the demands in synthesis of nanostructures are directed to such
structure tailoring that results from the synthesis-structure-properties relationship.
NANOPHASE PARTICLES GENERATION
One of the basic problems that has to be solved in order to permit the technological
application of materials with ultrafine to nanometer-sized grains is the availability of their
synthesis. In addition, in order for nanophase materials to be commercially viable , the
production route must be controlled and reproducible. Several methods has been currently
used in nanophase particle synthesis such as mechanical attrition," various chemical
methods like sol-gel or coprecipitation' " as well as aerosol synthesis. In aerosol synthesis
two approaches to powder preparation can be roughly distinguished: gas-to -particle route
and droplet -to-particle roote .'
Gas-to-particle refers either to the gas phase reaction'f or to the gas-condensation
associated with a chemical reaction in aerosols. 19 These methods, although often need high-
energy sources like plasma, sputtering, ion, electron or laser beams offer several
advantages for powder synthesis. It is possible to generate small particle size, either in
micronic to nanometer range, narrow size distribution, high purity particles etc. However,
some disadvantages relate to the generation of multi component systems.
Droplet-to-particle route refers to the heterogeneous gas-liquid/solid chemical reactions
in dispersed systems (aerosols). Such mechanism enables high surface reaction,
stoichiometric retention as well as segregation suppression to the droplet scale. It was
already shown that great variety of materials, including multicomponent ones, can be
obtained in accordance to this method, often called as ultrasonic spray pyrolysis."
The process involves formation of descrete droplets of precursor solution in the form
of aerosol and control over their thermally induced decomposition and phase
transformation?OAerosol is most frequently formed ultrasonically, using high-frequency
(lOOKHz- lOMHz) ultrasonic beam" directed to the gas-liquid interface. Liquid
atomization and aerosol formation occur for the certain values of the acoustic waves
amplitude, where the average droplet size depends mostly on the solution properties
(viscosity, surface tension, density etc.) as well as the ultrasound frequency . It was already
shown that this technique is suitable for the aerosol formation with the narrow size of
droplet distribution. In the same time, the average aerosol droplets can be kept small
enough (around or bellow 2 urn for the aerosol frequency of2.5MHz ),20 enabling synthesis
of submicronic as well as nanosized particles.
The aerosol is carried out by the flowing gas stream into high-temperature tubular flow
reactor. The flow rate of the carrier gas represents one of the most important process
parameters enabling the supporting atmosphere as well as the aerosol flow rate and the
droplets residence time to be controlled. During the process, aerosol droplets undergo
evaporation, drying and solute precipitation caused by the mechanisms of heat and mass
transfer inside the droplets and between the droplets and surrounding gas. Dried particle
decomposes consequently in a single step process and through heterogeneous reactions in
dispersed system. Depending on the process parameters - temperature and residence time,
either amorphous or crystalline particles can be obtained . (figure 1). It was shown that
proper adjusting of the mentioned parameters enables synthesis of nanophase,
polycrystalline or single - crystal particles by controlling over the mechanisms of grain
growth and sintering," Figure 2 a represents typical composite nature of ZnO particles, the
average particle size of 200 nm, derived ultrasonically (ultrasound resonant frequency 2.5
105
Sing le crys tal
Polycr ystalline _
- .....
...
0 ...
Amorp ho us
Nanophase
.
~ Dri ed particle
E--~
~ :.
.g ~ t dm/dt=F(D,L\p, L\T, 0)
dT/dt=<p(D. L\T . 0 )
E ~
~~ Aeroso l d roplet
~~
....._----------+
Residence tim e, t
Figure 1. The opportunities of ultrasonic spray pyrolysis in various particles synthesis
MHz) from dilute nitrate solution. Prolonged residence time implies crystallization of ZnO
particles (figure 2b). Another example is obtaining fully dense, spherical, crystalline silver
22
particles from nitrate solution for prolonged residence time, providing particle further
densification and decomposition.
The crystallinity of the aerosol derived particles depends upon the precursor choice
too, as shown for the case of Fe203 particle synthesis for magnetic application.i'' The
composite particle nature is observed for the nitrates - derived spherical particles, with the
average size less than 200nm in contrast to the monocrystalline character of y- Fe203
chloride-derived particles.
Nanophase particles can be generated in accordance to this method by properly
controlling over the initial aerosol droplet size, the mechanisms of the droplet collision and
coalescence as well as by suppressing the excessive grain growth and grain coarsening. As
a result, it is possible to obtain either nanoparticles directly from nano-sized droplets or to
obtain submicronic sized particles, that offer a composite nanograin particle structure?4,2S
Nanocomposite structure of various examined ultrasonically derived particles are revealed
for oxide fuel cells" as well as for manganese, copper and nickel oxide particles prepared
by low pressure aerosol spray pyrolysis.r" Submicronic single - phase manganese - ferrite
particles (with particle size less than 200 nm ) are obtained in accordance to aerosol spray
pyrolysis for the aerosol droplets of around Illm.27 The particles exhibit nearly bulklike
magnetic properties and multi domain particle structure. Single-phase polycrystalline
structure of particles ranging from 100-1OOOnm is observed also for strontium ferrite
powders,28 comprised of crystallites <100nm. The choice of precursors, their thermal and
decomposition behav ior play an important role in nano particles synthesis. In the case of
nitrate derived iron oxide , composite particle structure is formed where the secondary
particle is comprised of 6nm sized primary particles. However, for Fe(III)-acetylacetonate
as precursor, it was proved nano-sized particles synthesis directly .f In the case of Sn02
particles synthesis ultrasonically (ultrasound resonant frequency 1.7MHz) from tin sulfate
as a precursor solution, the microstructure hierarch y in composite particle formation,
including nanoparticles appearance, is clearly proved by detailed TEM, XRD and SEM
106
Figure 2. Composite (a) and single-crystal nature (b) of ZnO particles obtained ultrasonically at 2.5MHz
from nitrate solution concentration of 0.004 mol/l
observation.i'' Namely , the material includes primary crystallites, the mean size in the range
10-100nm gathering together into clusters-grains , ranged 100-200nm in diameter. These are
themselves gathered into spherical agglomerate s, or so called "secondary particles" the
mean size of around 1000nm.
CONTROL OF PARTICLE MORPHOLOGY AND MODELING
From the viewpoint of the application of the as-generated particles, either as powders
or precursor material s for advanced materials synthesis, particle morpholog y is of great
interest. Aerosol synthesis in accordance to ultrasonic spray pyrolysis enables synthesis of
various particle morphology , either as hollow or dense spheres. It is presumed that certain
particle morphology are formed during the evaporation/drying stage.i" Namely, the
following physicochemical phenomena are encountered during evaporation/drying stage:
evaporation of the solvent , diffusion of the solvent and solute away from the droplets and
inside the droplet, respectively, changing in droplet temperature and crust formation. They
are governed by the basic laws of heat and mass transfer so several models describing the
above mentioned phenomena are developed and can be applied in prediction of particle
morp hoogy.
I 20"303 1 Depen d'mg on eit
. her th i ute concentration
e so rormed im the
' gra dilent IS c.
droplet or not (figure 3), the solute can precipitates either mostly at the droplet surface or in
7
the droplet interior. As a result of the solute precipitation at the droplet surface, the
precipitate crust is formed, leading to the formation of diffusion barrier. Depending on the
crust properties , either hollow or fragmentary porous particles are formed as presented at
figure 3a for ZnO particles derived from nitrate precursor. Obviously, core shell particles
morphology are the result of salt surface precipitation where as-obtained Zn-nitrate core is
107
rigid enough to pass the gaseous products of nitrates decomposition. This leads to pressure
built-up inside the particle and to the formation of exploded particles for such droplet
geometry. Similar particle morphology can be also obtained if the conditions for droplet
32
collision and droplet coalescence are fulfilled . In accordance to the previously
reported,30,32,33 the droplet collision can be suppressed if the droplet number density are
below 107/cm3 as proved in the case of ZnO, BaTi03 as well as Bi-Pb-Sr-Ca-Cu-O
powers,
d generated Wit . h vanous
vari aeroso I fl OW rates .33 '34
The appearance of surface precipitation is the case for the most inorganic salts, if the
obtained core is rigid enough and if the relationship between the droplet geometry-
residence time is not properly adjusted. However, it is possible to obtain solid particles even
from inorganic solutions.r'' such as nitrates or chlorides by enabling suffic ient residence
time for decomposition as well as gases diffusion and particle shrinkage . Proper adjusting
of the droplet geometry as well as the residence time lead to solid particle formation, as
presented at figure 4, for the case of nitrate -derived ZnO particles from a.Smolll solution.
The problems regarding droplet collision and consequently droplet coalescence or
agglomerated particles formation are often associated with ultrasonic spray pyrolysis, since
7
reducing droplet size significantly increases the probability for collision. Agglomerated
particles are undesirable especially for afterwards sintering purposes, causing hard
agglomerates formation and inducing local grain growth and inhomogeneity. Figure 3c
represents agglomerated particles in a multicomponent Bi-Pb-Sr-Ca-Cu-O system where
the mechanisms of sintering and neck formation are obvious. However, those agglomerates
are formed in the process of droplet-to-particle transition followed by liquid phase
formation and liquid binding model agglomeration during thermolysis."
I. One particle per one droplet
r., concentratio=-l
gradient
Surface precipitation Volumeprecipitation
A) B)
t II. Droplet collision
L>ropletcoaUescence
Agglomerated
C) ~ particles
Figure 3. Schematic of the control of particle morphology during ultrasonic spray pyrolysis
108
Figure 4. Nitrate -derived solid ZnO particles synthesis by ultrasonic spray pyrolysis at 2.5MHz.
On the contrary of the reports on the mechanisms of particle formation from inorganic
salts, solid particles are often generated from metal alkoxides or organic solutions if they
undergo Rolymerization process . Several examples relate to the synthesis of microporous
zirconia, 1 spherical Sn02 as well as TiOi Sn02 particles in the range from 200-800nm
from SnCl 4 and TiCl 4 - SnCl 4 aqueous solutions.i" respectively and BaTi03 particles
obtained ultrasonically from TiCI4-BaCI 2 alcohol/water solution ." The mechanism for solid
particle formation is proposed through polymerization - gelation process of the precursor
salts during evaporation / drying stage, leading to the formation of three- dimensional
network , volume precipitation and solid particles . Particularly, in the case of BaTi0 3 , the
mechanism is discussed in term of Ti(lV) ions hydrolysis in droplets during evaporation
and consequently BaCl2 precipitation on such obtained three-dimensional network . The
obtained particles are spherical , with smooth surfaces and with the mean particle size of
about 500nm (figure 3b).
Another feature that strongly alter the particle morphology is transferring ions into gas
phase in the case of volatile precursors." In this case the particles are formed both from gas
as well as liquid (solid) phase, leading to the broad size of particle distribution and to the
differences in particle morphology. From the viewpoint of difficulties for the stoichiometry
retention in the case of multicomponent systems, this feature has to be controlled carefully .
AEROSOL GENERATION OF FILMS
Aerosol synthesis has been widely used in various films generation, either as droplet
and particle deposition or aerosol assisted CVD technology. It was shown that coating s and
films can be obtained in various systems , like superconductors, metal oxides , nonoxides ,
38
metals, composites etc. and on various substrates, like glass, ceramic, metal, alloys etc.
Especially in the case of aerosol assisted CVD (Pyrosol process) , the process involves
deposit ion of droplets containing evaporative reactants and subsequently evaporation and
reaction on the substrate surface." The materialsconcemed for film formation in the latter
case are metals (noble and transition metals), sulphides (eg. ZnS, CdS) as well as various
oxides ." It was shown that high quality of deposits, the thickness from IOOnm to several
microns, that are widely used as sensors, capacitors, films for optics and magnetics ,
transparent electrodes as well as biomaterials can be obtained in accordance to aerosol
synthesis .39, 40
109
CONCLUSION
This paper reviewed various approaches for the nanostructured materials synthesis with
special emphasis to aerosol synthesis . The method of ultrasonic spray pyrolysis is discussed
from the viewpoint of the ability to synthesis of various particle morphologies . Recent
developments in synthesis of particles and films are discussed. The mechanisms of particle
morphology are focused with the special emphasis to the materials and precursor chemistry
involved.
ACKNOWLEDGMENT
This work is realized through the project "Prognosis of materials properties from the
viewpoint of the synthesis- structure-properties relationship", financed by the Ministry of
Science of Republic Serbia as well as through the collaboration with RBI, Instruments and
measures, Meylan , France. The influence and support of academician M .M.Ristic are very
much appreciated . The assistance of Prof. I. Arsentyeva and Prof. Lj. Zivkovic in
providing TEM and SEM analysis is gratefully acknowledge .
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111
PREPARATION OF FINE, SPHERICAL, COMPOSITE POWDER BY
SPRAY PYROLYSIS
Radenka Marie', Takeh isa Fukui l , Satoshi Ohara I , Toru Inagaki/,

Hiroyuki Yoshida' , Jun-ichi Fujita2, Kazuhiro Miura
1Japan Fine Ceramics Center, 2-4-1, Mutsuno, Atsuta-ku, Nagoya, Japan

2Technical Research Center, The Kansai Electric Power Comp any, Inc.
11-20 Nakoji 3-chome Amagasaki, Hyogo 661, Japan
Kanden Kako Co., Ltd., 3-95 Showa-dori , Amagasaki, Hyogo 606, Japan
INTRODUCTION
Spray pyrolysis (SP) is an advanced method which enables spherical powder to be

prepared through the pyrolysis or hydrolysis reaction of the atomized droplet containing the
precursor. 1-3 To date most reactor systems have been designed such that the thermolysis and
sintering processes overlap. Overlap of these processes in a single droplet could significantly
affect densification of the particles. Therefore, a special separate reactor has been recently used
in JFCC , see Fig.l , to obtain maximum control of the evaporation, thermolysis and sintering
processes and because of this the time temperature conditions are significantly different. Most
of the studies4-6 emphasized the compositional flexibility for synthesizing ceramic powders
but there have been few attempts to understand or model the processes and factors that affect
the production of particles with controlled size and morphology. Recent achievements in the
field of the synthesis of powder by powder processing have shown that chemical and physical
properties of ceramic materials are highly dependent on the morphology and chemical
composition of the starting powder. 7 ,S Therefore , various properties of ceramic materials are
expected to improve by controlling the morphology and composition of the starting powder.
We have been applying the following powders: LaosSrozMn03 -YSZ, Lao6Sro4Co03-
Alz03, (CeOz)os(SmOls)oz-NiO (SDC-NiO) and Lao.9SrOIGaosMgoz03-NiO (LSGM-
NiO) prepared by SP as an electrode material for solid oxide fuel cells (SOFCs), The unit cell
of SOFCs consists of two porous and gas diffusion electrodes ( cathode and anode) separated
by a dense electrolyte. As it is well known, the starting composition and microstructure of the
electrodes have an influence on the total number of the electrode grains that occupy the
Ad vanced Science and Technology ofSintering. ed ited by Stoja nov ic et al.

Klu wer Academic/Plen um Publishers. New York. 1999 113
electrolyte surface during operation of SOFC. In general, the smaller the grains at the
electrode/electrolyte surface, the larger the area involved in the reaction and the higher the
currents that can be drawn through the electrode.
The goal of this study was to synthesize composite powder with controlled morphology
by the spray pyrolysis method in order to obtain high-performance anodes and cathodes.
EXPERIMENTAL
The composite powders included in the present investigation were Lao.sSro.2Mn03-YSZ,

Lao .6Sro.4Co03-Alz~, (CeOz)o.s(Sm01.5>o.z-NiO (SDC-NiO) and
LaO.9SrO.l GaosMgo.2D.3-NiO (LSGM-NiO) .
Lao.sSro.2Mn03-YSZ and LaSrCo0.3-Alz03, have been used as a cathode material for
SOFe. (La, Sr) Mn03-YSZ composite particles were prepared from YSZ sol ( 8-mol% yttria-
stabilized zirconia sol), and (La, Sr) Mn0.3 derivatives by the SP technique. Laz03, SrC0 3,
and MnOz were dissolved together in an aqueous nitrate and hydrogen peroxide, and pure
water. YSZ sol solution was added to the solution. To obtain A site defect type (Lao.s
SrQ.2)o.9Mn0.3, the molar ratio of La, Sr, and Mn in the solution ( 0.1 mollL) was La:Sr:Mn
= 0.72:0.18: 1. (Lao.s Sro.2)o9Mn03 :YSZ = 50:50 (mol%) was applied to the initial
composition. Similarly, Laz0.3, SrC03, and CozD.3 were used to make LaO.6 SrO.4 Co03 and
Alz 03 sol solution was added to the solution. The ratio of LaSrCo03 :Alz03 was 80:20
vol% .
Mixed conducting oxide particles, samaria-doped ceria (SDC) and oxide ion conductor
particles, doped lanthanum gallate, were employed as the anode material utilizing highly
dispersed noble metal catalyst Ni. For one cell, ceria is partially reduced in the reducing
atmosphere at the anode side of a fuel cell and becomes a mixed conductor to both electrons
and oxide ions. The use of the mixed conducting oxide anode results in an enlarged
electrochemical reaction zone beyond the physical triple-phase boundary. (Ce02)o.s(Sm01.5)
(SDC)-NiO composite particles were
obtained from solution, which was
prepared from Ce(N0.3h , SmzD.3 and
Ni(CH3COO)z'4HzO raw materials. The
volume ratio of the SDC to NiO was
50:50 . Lao .9Sro .l Gao .sMgO .Z03 -N iO
composite particles were prepared from
LazD.3 , SrC0 3, and Mg(CH3COO)z'
4H zO raw materials and were dissolved
together in Ni(CH3COO)z4HzO. The
volume ratio of the LSGM to NiO was
50:50. These initial solutions were
atomized with an ultrasonic vibrator
operated at 1.7 MHz. Droplets were
Fig . 1. Spray pyrolysis equipment.
transported to a reaction furnace using air
as a carrier gas with a fixed flow rate of 3
Umin. The reactor consisted of four independent heating zones. The temperatures of each
heating zone- zonel, zone2, zone3, and zone4- were set at 200, 400, 800, and l000C,
respectively. The particles from the furnace outlet were collected using an organic filter. After
SP the powder was calcinated at temperature of l000C for several hours. X-ray diffraction
(XRD) analysis was used to identify the phases of the as-synthesized and calcinated powder.
The morphology and microstructure of the composite powder were studied using scanning
114
electron microscopy with an energy dispersive analysis of X-ray . TEM was employed to
investigate the crystallite size distribution and using dark-field images we were able to measure
the size of the crystals.
As shown in Fig. 2 a spherical particle morphology has been obtained by SP processing

for cathode powder. It is clear from this figure that the shape of the particles is equiaxial and
uniform . TEM observation of powder was carried out in order to evaluate the microstructure
Fig . 2. SEM micrographs of a) Lao.gSro.2Mn03-YSZ, and b) Lao.6Sr0.4Co03 -Al203 synthesizedpowder after

SP.
of the particles in details. Figure 3 shows a TEM photograph of (La,Sr)Mn03-YSZ particles

embedded in an epoxy resin, prepared by ion beam milling. It is obvious that dense particles
consist of fine crystallites smaller than
100 nm. TEM-EDS analysis showed that
the fine crystallites contained either the
elements La-Sr-Mn-O or Y-Zr-o. The
particle morphology of (La, Sr)Co0)-
AIz03 is shown in Fig. 4 and one can see
that the particle consists of many
crystallites about 100-200 nm in diameter.
As presented by G.L. Messing el al.9
there are a number of possibilities for
synthesizing multicomponent and
composite particles with a unique range of
microstructure characteristics. The
morphology of the particles can be
predicted from the model calculations of
the solute concentration gradient and the
simple criterion for solid particle
formation. High initial solute Fig. 3. TEM bright -field image and diffraction pattern of
concentration inside the droplet is suitable Lao.gSrO.2Mn03-YSZ composite powder prepared by sr.
for the volume precipitation which leads to
solid particle formation . For SDC-NiO
anode powders , particles formed by SP are composed of crystallites substantially less than 100
nm in diameter, Fig. 5(a). After calcination of SDC-NiO powder the particle morphology
remains spherical and particles are composed of many crystallites about 100 nm in diameter,
115
Fig. 5(b). To conform the size of the
crystallites an X-ray diffraction pattern of
the SDC-NiO powder obtained after SP
and calcination has been used, Fig. 6.
The crystallite size of the powder
obtained after SP has been calculated
from an X-ray diffraction peak
broadening by Scherror formula and for
SDC and NiO crystallites were 15 and 20
nrn, respectively. During calcination the
crystallite sizes of both components
increased and for SDC and NiO after
calcination attained values were about 85
and 100 nm, respectively . For LSGM-
NiO amorphous particle structure has
been observed after SP, Fig. 5(c).During
calcination crystallites formation occurred Fig . 4. TEM image of Lao.6Sro.4Co03 -Al203 powder.
and particles were composed
of many crystallites as shown in Fig. 5(d). A TEM bright field and diffraction pattern of the
LSGM-NiO particles conform that particles have been completely amorphous, Fig. 7(a), after
Fig. 5. SEM micrographs of a) (Ce02k>.8(Sm01.5k>.2-NiO (SDC-NiO) after SP, b) SDC-NiO after calcination,
c) Lao.~ro.IGao.gMgo.2~ -NiO (LSGM-NiO) after SP and d) LSGM-NiO after calcination .
116
after calcination
after spray pyrolysis
;>0-
....f--
U LI
CI) NiO NiO
zW
f--
....Z SDC
SDC
30 40 50 60 30 40 50 60
28 (degree) 28 (degree)
Fig . 6. X-ray diffraction patterns for SOC-NiO powders after a) SP, and b) after calcination.
SP. The TEM micrographs in Fig . 7(b) show that calcination of this powder at IOCX)"C brings
a crystalline structure and if the powder produced by SP consisted of hollow spheres that
hollow spheres will also remain during calcination. As shown in Fig . 6(b) the particle consists
of a uniform mixture of 90 nm NiO and 75 nm LSGM crystallites. One of our attempts is to
explain morphology of the powder formed during SP processing. Based on precipitation
theory, Leong 10 reported that the degree of supersaturation influences the size and number of
the crystals formed in the droplet. Solutes with a high degree of supersaturation tend to form a
large number of nano-meter sized crystallites, and , thus, the shape of the particles is spherical.
Conversely, when the degree of supersaturation is low, the nucleation rate is small relative to
the growth rate, and therefore only a few large crystals and in some cases, even single crystals
are formed. The size and number of the crystals determine the size and size distribution of the
pores. In some big particles of LSGM-NiO a hollow structure has been found, Fig . 7(a) . The
reason for this morphology can be attributed to the fast nucleation rate of the precursor from the
outer part of the droplet or the difficulty in degassing the residual gas .
O.51J m
Fig. 7 . The bright field images and the corresponding diffraction patterns of Lao.9SrO.IGao.sMgo.2ClJ-NiO
(LSGM-NiO) powder a) after SP and b) after calcination at lOOO'C for 2 h.
117
Cathode microstructure with a narrow particle size distribution and homogeneously
distributed long three-phase boundaries are essential, both for electrochemical reactions and
for homogeneously current flow in the electrolyte. For SP prepared (La, Sr)Mn0.3-YSZ
cathode, the cathodic polarization was about 20 mV for applied current density 300 mA/cm z at
operation temperature of l000C. Cathodic polarization and ohmic loss of the cathode
materials have been discussed in more details in a previous study.! I Application of SDC-NiO,
and LSGM-NiO as an anode material for SOFC significantly lowered the operation
temperature of the cell due to its high oxide ionic conductivity . Since polarization
characteristics of the anode depend strongly on powder microstructure, good electrical contact
of the consisting particles (Ni to Ni, Ni to SDC , and SDC to SDC) is important. The
morphology of this anode after cell operation is shown in Ref. 12. The lowest anodic
polarization at the 8OOC operation temperature for LSGM-NiO has been 85 mV for current
density 300 mA/cm 2 at sintering temperature 1300e. In general, the immigration of feed gas
and product depends on the electrode morphology, and the exchange of the charge depends on
the length of the three phase boundary and the activity of the electrode materials. Therefore,
the overall efficiency of SOFC is greatly controlled by the morphology of the electrodes.
CONCLUSIONS
It was shown that the spray pyrolysis technique can be successfully applied to the
fabrication of composite powder. The mean particle size of Lao.8SrOZMn0.3-YSZ,
Lao.6Sro4Co0.3-AIz0.3, (CeOz)o8(Sm015)02-NiO (SDC-Ni) and La09SrO I GaO.8MgOZG.3-
NiO(LSGM-NiO) has been about lum. As confirmed by X-ray , elemental analysis, SEM, and
TEM the particles consist of many crystallites, and for (La, Sr)Mn03-YSZ and (La,Sr)Co0.3-
Alz0.3 the mean crystallite size was about 100 nm. SDC-NiO consisted of many fine
crystallites of SDC and NiO about 20 nm in diameter. In the case of LSGM-NiO an
amorphous structure has been formed and after calcination turns to be crystalline. We obtained
that these composite particles will improve the electrochemical performance of the electrodes in
SOFes.
REFERENCES
1. Y. Kano and T . Suzuki, 1. Mater. Sci . 21, 3067 (1988) .

2. N.Tohge, M.Tatsumisago, and T. Minami, J. Am . Ceram . Soc . 14, 2117 (1991) .
3. T . Fukui , T. Obuchi, Y. Ikuhara, S. Ohara, and K Kodera ibid. SQ, 261 (1997) .
4. D.M . Koy and S.O. Oyefesobi, 1. Am . Ceram. Soc . 60,178 (1977).
5. T .P.O'Holleran, R.R. Neorogaonkar, D.M. Roy and R. Roy, Am. Ceram. Soc . Bull.51,
459 (1978) .
6. O.Sakurai, M. Miyauchi, N. Mizutani, and M.Kato, 1. Ceram. Soc . Jpn . 91.,398 (1989).
7. M. Watanabe, T . Saegusan and P. Stonehart, J. Electroanal. Chern. ill, 213 (1989).
8. T .H. Estell and S.N. Flengas, ibid . ua 1890 (1971).
9. D.W. Sproson and G.L. Messing, in Ceramic Powder Science, edited by G.L. Messing,
KS . Mazdiyasni, 1. W. McCauley, and R. A. Haber , American Ceramic Society,
Westerville, OH, 1987.
10. K.H. Leong, J. Aerosol Sci. .llt 527 (1987).
11. R. Marie et. aI., in Proc . Processing and Properties of Advanced Engineering Materials
edited by T. Kobayashi , M. Umemoto, M. Morinaga, ISAEM-97, Toyohashi, 1997, p. 319 .
12. R. Marie, T . Fukui, S. Ohara, and T. Inagaki to be published in Elec. Solid-State Lett..
us
SYNTHESIS OF SUBMICRONIC OXIDE POWDERS
BY AEROSOL SPRAY PYROLYSIS: MODELING OF
THE EVAPORATION STAGE
Joze Vodnik' and Olivera Milosevic/
1 Instituteof Nuclear Sciences "Vinca",

Laboratory for Thermal Engineering and Energy,
Belgrade, Yugoslav ia
2Institute of Technical Sciences of SASA,
ABSTRACT
The morphological control is one of the major concerns in fine submicronic, spherical
particle formation during aerosol spray pyrolysis . The process involves aerosol formation
(the ultrasonic aerosol generator operated at 800 kHz, 1.7 and 2.5 MHz) from the initial salt
solutions and control over aerosol decomposition in the temperature range from 400 to
1173 K. With the presumption that certain particle morphology is formed during the first
stage of spray pyrolysis - the solvent evaporation and drying, mathematical model of
evaporation from droplet s containing dissolved solids is developed and applied for various
precursor solutions (Zn(NO)36H20, CoCh6H20, CO(N03)26H20 , MgCh6H 20) and the
droplet geometry in the range from 1 to 101lm. The influences of various parameters of
precursors solution (the precursor solution concentration, the diffusion coefficients of the
solvent vapors and the specific heat of drying solutes) on solid particl e formation were
analyzed . It was shown that the developed model describes well the phenomena of mass
and heat transfer occurring for the examined aerosol droplet geometry and can be applied
for the prediction of particle morphology.
INTRODUCTION
Aerosol spray pyrolysis represents a process commonly used to produce a wide variety
of powders and films!" . The process involves aerosol formation from the precursor solution
ultrasonically and consequently solvent evaporation and intraparticle thermally induced
drying and reactions. The physicochemical phenomena encountered during droplet to
particle transition has to be modeled in order to predict the particle size and morphology .
Advanced Science and Technology ofSintering , edited by Stojanov ic et al.

Although the period of evaporation (drying is at the dominant influence on various particle
morphology formation), only the few studies are addressed to the modeling of single droplet
evaporation during aerosol spray pyrolysis':". Physically realistic model of droplet
evaporation, described by Nesic and Vodnik6 is applied in this paper. This model assumed
five stages of droplet evaporation, with defined stage transition criteria. The same basic
laws of heat and mass transfer govern all five stages of droplet evaporation (initial heating
and evaporation, quasi equilibrium evaporation, crust formation and growth, boiling and
porous particle drying). Thus a single set of differential equations describing changes in
droplet mass, temperature, size, concentration, density, rate of crust growth etc. can be used
to model the evaporation process and the stage transportation criteria. In order to keep the
model reasonably simple and appreciative for this droplet geometry ( droplet size in the
range from I to l Oum, as obtained in accordance to ultrasonically synthesis"), some
assumptions are imposed? Based on the model of droplet evaporation a computer program
was written in FORTRAN 77 language.
The influence of various parameters of drying agent (temperature, velocity and
humidity) on drying kinetics for different materials (Zn(N03h6H 20 , CoCI26H20 ,
Co(N03h 6H20 , MgCh 6H20 ) were already analyzed and reported? Therefore, main goal
of this paper is to show the influence of various precursors solution parameters ( the
diffusion coefficients of the solvent vapors and the specific heat of drying solutes) on
kinetics of solid particle formation.
RESULTS
The kinetics of the evaporation process for different materials (Zn(N03h6H20,

CoCh6H20, Co(N03)2 6H20 , MgCh 6H20) are presented at Fig.I .. Note that, the initial
droplet diameter and drying regimes were identical for all numerical experiments.
Previous papers? analyzed and discussed influence of initial concentration of precursor
solution on kinetics and first stage of spray pyrolysis processes (drying / evaporation). Third
stage in used model, period of crust formation and growth, which begins when surface
solids concentration reaches or exceeds a critical value, is most important period in this
1.0
~ C WJi .
---
0.8
c o ~1
.S: 0.6 ... + . ... ~2
~c x ~3 i
~ 0.4 0 Q::(!'O)i1 !-
. ..
e 6 ~2
]02 v ~3 :
c-
...o
Q
rlR(%)
Figure 1. Drying kinetics of examined materials (drying agent: air, v = 0.02 mis, x = 0.014kglkg, t. = 90 C;
initial droplet radius, R =2.25 um)
120
process. Solid separation in the form of crystalli zation or agglomeration begins, forming a
crust. The crust thickens towards the interior of the droplet, while the evaporation front
withdraws to the inner surface of the crust. Hence the resistance to heat and especially mass
transfer increases, reducing the evaporation rate temporarily. This again causes
proportionally more of the transferred heat to be used for heating rather than for
evaporation, so the temperature of the droplet rises rapidl y as the crust thickness. The
dynamics of this stage depends primarily on the crust permeability for vapor diffusion 6 .
Using solid phase balance it can be calculated:
(I )
Solving for crust thickness, 0:
0= Re[l-( m~mdm )0.33] (2)

me mdm
The values for crust thickness, obtained according to equation eq. 2. for
Zn(N03h-6H zO are shown in figure 2.
I C rust thickness

2

..
~

.
~
..

.,i1
:g
'"
E
u
o-t-......,...-~---r--......-"T"""-...-~-_--1
Initial droplet radius ( J.lm)

Figure 2. Crust thickness vs initial droplet radius ( precursor solution: Zn(N03)26H20 , c=0.50 kg/kg, drying
agent- air:t.=90C, v = 0.02 mis, x = 0.014kg/kg)
It is necessary to identify the beginning of crust formation, since the resistance to mass
transfer can change significantly, usually resulting in a steep increase in droplet
temperature. It can be expected that the surface concentration of solid phase at the surface ,
cs, constantly increase due to the evaporation of the liquid phase. When it reache s
saturation, crust formation begins . It is very important to be able to determine at what point
the surface concentration c, reaches the saturation point Csat. in order to provide our second
to third stage transition criteria. This stage transition criterion is especially important as it
marks the end of low temperature and the beginning of the high temperature period of
evaporation. In order to find the surface concentration cs, one can solve the diffusion
equation for the solid phase within the droplet, bearing in mind the assumptions we have
121
made about spherical symmetry. The transient one dimensional diffusion equation in
spherical coordinates is':
(3)
with the boundary conditions at the droplet surface,
c(t,R) = cs ; [Dc]
41tR2 D -
I Or
4
= -1tC
3 s
dR-
-
3
d.
(4)
r=R
at the center of the droplet:
[8OrC]r=O = 0 (5)
Time of crust formation on surfaces is very important for process definition, because
after, it could be talk about influence the diffusion coefficients of the solvent vapors and the
specific heat of drying solutes on kinetics of solid particle formation.
In order to using model, calculation for crust time growth has been carried out.
Comparison between obtained data of crust formation time and drying time are shown in
figure 3, for ZnO (with three different initial solvent concentration of Zn(N03)z 6H20) .
2),.------r----r-----.
15 E;
..c
~
" 10 10 ~
.; .;"
'&
Q
!)l)
c
5 5
-
'"
=
U
Droplet diameter
Figure 3. Drying time and time for crust formation vs initial droplet radius (precursor solution:
Zn(N03)2"6H20, R =2.4 JIDl, cl=0.I2 kg/kg, c2=0.23 kg/kg, c3=0.50 kg/kg; drying agent-air: v = 0.02 mis, x
=0.014kg/kg, ta = 90C.
However, for more precisely process calculation, it is necessary to know values for the
diffusion coefficients of the solvent vapors and the specific heat of drying solutes . Values
for these parameters can be found in literature just for limited materials. Therefore, initial
values for these parameters were assumed on the basis of previous experiments and some
122
similarity between materials. For Zn(N03)2, it was accept, that Dc=1.5 e'7m 2/s. It was shown
that particular used values describe well the phenomena of heat and mass transfer. In order
to estimate, in which range this parameter can be changed and what kind of influence is
caused by those changes, values for D, are changed in the range of DclQ,1 to DclQI in the
case of Co(N03k6H 20. Results for those numerical experiments are shown in Figure 4.
For many materials it is very difficult to find out the values for specific heat (especially
for materials used in these experiments). Therefore, it was made similar procedure like with
defining values for diffusion coefficients of the solvent vapors . It was accepted value for
cp=800 kJ/kgK 6, and this value was changed in the range of 50% to 200% of accepted
value . Numerical experiments are made for all regimes with Co(N03h6H20 and
MgCh6H20. Results of this analysis are shown in Figure 5. for Co(N03h6H20 .
1.br---...... -r---T"""-......,r-----r---........,..._---.
o ; Ccf1.5e1m21s
o i Ccf1.5e-7 m21s
c 6 Ccf1.5e-8 m21s
o
-
:;:;
~
c
Q)
o
c
o
o
20 40 60 1 0
rlR(%)
Figure 4. Change of droplet concentration during process vs change of droplet size (precursor solution :
Co(N03)r6H20, D c1=1.5 1O.6m 2/s, Dc2=1.5 1O,7m2/s, D c3=1.5 1O,8m2/ s , c=0.0535kglkg, R=2 .25f!m, cp=800
JlkgK; drying agent-air: t.=90C, v=0.02 mis, x=O.O14 kglkg ).
12 r-.......-.,.-........,........-"T"""--.----,r---..,.---,
to
c:
~ 0.6
E
C
t 0.4
c:
...o
... 02
C.
E
Q OO~
' 0 ....~::--......~:-'.....* . . . .__:!::---'""""::-......~12:>
Figure 5. Change of droplet concentration during process vs change of droplet size (precursor solution :
CO(N03)26H20, c=0 .0535 kglkg, R=2.25f!m, Dc=1.5 10,7 m2/s Cpl = 400 kJlkgK, Cp2 = 800 kJlkgK, Cp3 = 1600
kJlkgK ; drying agent -air: t.=90C, v=O.02 mis, x=O.O14 kg/kg .).
123
CONCLUSION
Physically realistic mathematical model of evaporation of droplets containing solutes

is used to express the particle morphology during aerosol spray pyrolysis. The model is
applied for the various precursor solutions and for the droplet geometry in the range from 1
to l Oum. The common characteristic for all examine materials is that the influence of
various parameters (the diffusion coefficients of the solvent vapors and the specific heat of
drying solutes) on kinetic of solid particle formation is different and depend on initial
solution concentration . Reason for this is in fact that during the process of droplet
evaporation some periods have different timing. If initial solute concentration is small
enough, the second period of process - period of quasi-equilibrium evaporation is dominant
and presents almost all the time of process of droplet evaporation. In this case, the
influences of various examined parameters are irrelevant. If initial solvent concentration is
close to the critical concentration, the third period - period of crust formation and growth, is
primary period in the process. In this case influence of the diffusion coefficients of the
solvent vapors and the specific heat of drying solutes on droplet evaporation is expressive.
Time of the process was different for 5-10%, but predicted particle morphology
characteristics ( particle size and crust thickness) have to irrelevant changes (less than 2%).
It was shown that used model describes well the phenomena of mass and heat transfer
occurring for the examined aerosol droplet geometry (up to 10 urn) and can be applied for
the prediction of particle morphology, even of diffusion coefficients of the solvent vapors
and the specific heat of drying solutes are not well defined.
NOMENCLATURE
c concentration; cp specific heat; Dc diffusion coefficient; m mass;

x air humidity; r spherical coordinate; R initial droplet radius; v velocity;
ACKNOWLEDGEMENT
This work is financially supported by the Republic of Serbia Science Foundation

through the project 02E12.
REFERENCES
1. A.Gurav, T.Kodas, T.Pluym and y'Xiaong, Aerosol processing of materials, Aer. Sci. Techn., 19
: 411 (1993)
2. G.L. Messing, S-C. Zhang and G.V. Jayanthi, Ceramic powder synthesis by spray
pyrolysis, J.Am.Ceram.Soc., 76, 11 : 2707 (1993)
3. Y.Xiong and T.T.Kodas, Droplet evaporation and solute concentration during spray pyrolysis,
J.Am.Sci., 24,7 : 893 (1993)
4. G.V.Jayanthi , S.C.Zhang and G.L.Messing, Modeling of solid particle formation during solution
aerosol thermolysis, Aer.Sci.Tech., 19: 478 (1993)
5. O.Milosevic, V.Gagic, J.Vodnik, AMitrovic, Lj .Karanovic, B.Stojanovic and Lj . Zivkovic,
Synthesis and deposition of ZnO based particles by aerosol spray pyrolysis, Thin Solid
Films, 296 : 44 (1997)
6. S.Nesic, J.Vodnik, Kinetics of Droplet evaporation, Chem.Eng. Sci., 46, 2 : 527 (1991)
7. J. Vodnik, O. Milosevic, Mathematical modelling in spray pyrolysis process, The First
European Congress on Chemical Engineering - Proceedings 2, Italy, Florence (1997) .
124
NANOSTRUCTURE COMPOSITION OF DIAMOND-WC-Co
I.Uvarova, T.Babutina, I. Konchakovskay, I.Timofeeva, A.Petuchov
Frantsevich Institute for Problems of Material Sciences NAS of Ukraine
INTRODUCTION
The properties of ultradispersed and nanostructured materials with average grain or

particle size below 100 nm be different from those of conventional materials that have on a
coarser size scale [1, 2]. In the previous paper [3] we have reported that the conditions of
carbidization and the size of tungsten carbide particle depend from tungsten dispersivity.
The influence of the tungsten dispersivity and the properties of carbonised component on
the conditions of carbonisation and the size of tungsten carbide particle in simple and
composite systems was studied in this work. From composite system WC-Co-diamond is
more interesting. It is compared the processes of tungsten carbidization in the present of
cobalt in different gas mediums by the carbon in solid phase and from gas. As a carbonised
component in solid phase we were choused carbon black and explosion carbon.It has been
earlier shown [4,5], the mixture X-ray amorphous carbon and diamond, called explosion
carbon, can be formed by high temperature (3500-5000 K) impact compression of carbon.
The crystalline size in these mixture is varied from a few tens to a few hundreds nm and
carbon, which is the impurity to diamond, is X-ray amorphous phase. As shown in [6], the
high temperature impact compression of carbon was used for production of molybdenum
carbide simultaneous with a diamond. The present paper focuses on the use high depression
and defected state of the explosion carbon for acceleration of tungsten carbidization and
decrease of temperature of this process in order to produce the nanophased mixture hard
alloys with diamond. The conditions of reduction and carbidization of CoW04 + W0 3 by
carbon black and explosion carbon was studied in this work and proved the possibility of
diamond keeping in the mixture with hard alloys at reduction and following carbidization
by explosion carbon.
EXPERIMENTAL
The tungsten of different dispersivity, tungsten tree-oxide and hard alloys fragments
wasters were studied in this work. Tungsten was prepared by reduction in hydrogen, or in
low temperature reduced plasma. The hard alloys fragments wastes were oxidised in air
with using a shake. As a wastes were used the fragments of drills and dispergrinding plates.
Ad vanced Science and Technology ofSintering, edited by Stoja novic et al.

The reduction of oxides were performed at different temperature by hydrogen, carbon
black and explosion carbon is solid phase and carbon from gas phase. The different
mediums as a reduced so inert were used. The phase composition of powders on all stages
of processes was studied by using X-ray diffraction. The specific surface of powders was
measured by nitrogen thermodesorption chromatography.
RESULTS AND DISCUSSIONS
We have earlier shown [7] that preparation of the powders with specific surface to 2-3
2/g
m was possible at low temperature reduction of tungsten from tree-oxide. The process of
carbidization of powers with different dispersivity, prepared by reduction of tungsten from
oxide, plasma tungsten and tungsten-cobalt intermetalic compounds was studied in this
work. The dispersed composition of tungsten, prepared by different methods, is presented
in Table 1.
Table 1. The properties of reduced tungsten powders

Method of preparation S, O2 Granulating composition, % size fraction, nm
and temperature stage m2{g mas.
of reduction, 0 C %
0- 0,5- 1,0- 1,5- 2,0- 2,5- >
1,5 1,0 1,5 2,0 2,5 3,0 3,0
Reduction: 500-900 0,5 0,14 1,8 12,7 16,9 16,4 17,1 9,1 12,2
500-600-900 0,8 0,05 9,3 13,8 14,1 17,9 16,4 15,7 12,7
550-900 0,8 0,38 7,5 12,7 13,9 22,2 16,9 13,1 13,5
650-900 0,8 0,37 14,6 14,4 18,0 21,9 14,8 9,8 6,6
900 0,2 0,12 5,7 16,9 21,1 19,1 14,5 9,7 13,2
900-1200 0,2 0,05 4,7 17,7 22,8 18,7 13,1 3,5 19,6
1200 >0.1 0,07 5,0 11,3 21,1 25,S 16,2 7,0 14,1
530 -630-840 2,7 0,26 - - - - - - -
Wplasma 2,4 2,10 69,3 21,2 9,5 - - - -
W plasma after 1,5 0,4 - - - - - - -
reduction at 900
W industrial 1,3- 0,3 - - - - - - -
d=O,16-0,26 mkm 2,3
W industrial 0,2 0,18 - - - - - - -
d=O,21 nm
W industrial >0,1 0,05 - - - - - - -
d=O,66nm
As can be seen from this data the most dispersed tungsten may be prepared by low
temperature tree-stage reduction on hydrogen upon small layer of powder. the plasma
tungsten had such dispersivity, but without heat treating it had the big impurity of oxygen
(to 2-3%).
Let us compare this data with data upon reduction of mixture CoW0 4 +W03 (first
case) and complex salt [Co(NH3)4C03hH4W7024 (second case) (Table 3). In according with
the thermodynamics [8] CoW0 4 may be reduced by hydrogen with the formation series
intermediate complex oxidised compounds, which in future will be converted to
intermetallic compounds W-Co with a different proportions of components. The reduction
of CoW04 by hydrogen in temperature interval 425-1000 cwas studied by Bracconi P.
and Dufour L.c. [9] X-ray analysis of the intermediate reduced phase have shown unstable
C04W2.SO and C0 3W30 4 compounds [10]. Excess tungsten is formed P-W in dried
hydrogen. In future X-ray amorphous phase is formed and then intermetallic compounds.
126
Intennetalic compound C0 3W is formed at the low reduction temperature or C0 7W6 - at
more high temperature.
The influence of cobalt to the mechanism and carbidization conditions in the system
W0 3+C0 30 4+C at temperatures 900-1000 cwas studied in the works [9, 10]. It has been
C0 7W 6, C0 3W3 and Co has been established by authors of paper [10] under reduction
CoW0 4 at the temperature 900 "c in the mixture H2+2,50/0CH4. The degree of carbidization
decreases in the presence of intennetallic compounds, or increases in the presence of pure
cobalt. It has been established, that the carbidization et the temperatures II 00-1300 cof
mixture C0 7W6+W or C0 3W3+W by carbon or H2+CH4leads to formation of C0 3W3C+WC
and then the mixture WC +Co .
The X-ray data upon reduction of mixture CoW04+W03, prepared by oxidised of
hard alloys fragments wastes and mixture of oxides C0 30 4+W0 3 (first case) and complex
salt [Co(NH3)4C03hH4W7024 (second case) are shown in Table 2 and Table 3,
respectively.
Table 2. X-ray data of the fmal phases, which was obtained, under reduction of mixture
COWOd+WO~ with a specific surface 2,5 m2jg
The reduction temperature, c I X-ray phases I Snecific surface, m7./f!
350 COW04+W03
450 CoW04+W03
550 CoW04+W03
650 w02+PW+F-phase' 8,4
750 W+PW+F-phase' 6,4
850 W+C0 7W6 (W)" 1,4
950 Co,W,+W 0,9
OF-phase -X-ray amorphous phase

00 (w) -week line
Table 3. X-ray data of the products, prepared under reduction of mixture C0 30 4+W0 3 (1)
and complex salt [Co(NH3)4C03hH4W7024 (2)
1.
The initial
composition I temperature,
Reduction
650
c I
S,
m2/g
3,9
I 2'
mas.%
6,35
I X-ray phases after
reduction
W02+COw
2. 8,4 10,36 W02+W
1. 750 1,1 0,92 W+C0 7W6w
2. 6,4 1,53 W
1. 850 0,5 0,15 W+C0 7W6w
2. 1,4 0,45 W+C0 7W6w
1. 950 0,34 0,10 W+C0 7W6w
2. 0,9 0,25 W+Co,W....
Thus CoW0 4 is very stable compounds and its reduction must be carry out at
temperature 900-1000 0c.
It is well known that the main difficulty of the tungsten carbidization in the presence
of cobalt is the loss of carbon, which don't provided the reaction equation [12]. The reason
of carbon loss may be the reactions, catalysed in the presence of cobalt
C +2H 2=CH4
C + CO2 =2CO
In order to compare the possibility of tungsten carbidization in the presence of
cobalt we have study the loss of carbon in different gas atmosphere. It is expected that the
loss of carbon will bee less in inert atmosphere in composition with hydrogen. In our
127
experiment (Tab. 4) we actually were observed, that the loss of carbon in inert gas
atmosphere was ",,10%, but in hydrogen ""60. Carbidization temperature was 950 C. It is
evident (Tab. 4) that the loss of carbon in hydrogen is very large and deficit in carbon do
not permit to receive the stoichiometric compounds we.
Ta ble 4. The products of reduction and carbidization by carbon black

Product of
reduction
I Atmo sphere of
carbidization I carbidi zation
%0 before
2
I S (m<j g)
I
Loss of
carbon %
I bond
Carbon
free
W+C07W6 H2 0,35 0,87 ",60 3,8 -
W+C0 7W6 Ar 0,4 0,87 ",15 5,6 0,2
The data of tungsten carbidization at temperature 1100 c in hydrogen and inert

atmosphere are summarised in Table 5. For carbidization it is used the products of
reduction, represented in Table 3 and plasma tungsten.
Ta ble 5. The composition of carbidized products

Product after
reduction
. in hydrogen in argon in H2 + CH4
X-ray C,mas.% X-ray phases C,mas.% X-ray phases C,mas.%
I
pases
loss I bond loss I bond loss bo
nd
1-850 WC 15,7 4,8 WC+ 0,7 5,0 WC - 5,2
W2Cw 8
2-850 WC+ 14,0 4,5 WC 1,1 5,4 WC - 5,5
W2Cw 9
1-950 WC 8,3 4,8 WC 0,6 5,6 WC - 5,3
4
2-950 WC 11,6 4,5 WC 0,9 5,8 WC - 5,6
PlasmaW WC+ 5,9 5,0 WC - 5,9 WC - 5,3
W,C w 3
1-850 and 1-950- the mixture W+C07W6 , prepared under reduction of mixture
C030 4+W0 3 2-850 and 2-950 - the mixture W+C07W6 , prepared under reduction complex
salt [CO(NH3)4C03hH4W70 24.
As can be seen from data, given in Tab. 5, the phase of WC is formed at the
temperature 1100 c under carbidization in all cases, but the loss of carbon in hydrogen is
very big.
Such principle we used under the study and production the composite powder
systems based on tungsten. Let us examine the possibility of production the nanophased
systems WC-Co-diamond at the expense of use oxidised hard alloys WC-Co fragments
wastes and explosion carbon. The different gas mediums were studied for decrease the
temperature of carbidization and increase dispersivity of reaction products.
Our knowledge about tungsten and tungsten oxide reduction and carbidization was
used for study the processes of production of composite systems based on tungsten. Let us
consider the possibility of preparation of the composite system WC-Co-diamond at the
expense of use of reduction and carbidization on different systems based on tungsten (Tab.
6).
As can be seen from data given in Tab. 6, the tungsten does not carbidized by
carbon at the temperature 850 C in nitrogen. At the same conditions in atmosphere of high
hydrocarbon X-ray analysis was established the week line of W2C at carbidization without
128
1 tzatiIOn
1 raction and specmc surface the products 0f reduc t'IOn an d car bidi
Table 6. X-ray diff
Reagent I t ("C) I r (h) I X-ray phases I The medium I S (ml/g)
W+C 850 0,5 W nitrogen -
W 850 0,5 W+W 2CVW high hydrocarbon 0,55
W 1100 0,5 W+W 2C V.W. high hydrocarbon 0,38
W+C 850 0,5 WC+W 2C high hydrocarbon 3,7
W+C
W+C
. 1100
1100
1,5
2,5
W+W 2CV.W.
WC
high hydro carbon
high hydrocarbon
1,96
0,7
W0 3 850 0,5 W02 high hydro carbon 5,7
W0 3 1100 1,5 W+W0 2 high hydrocarbon 1,75
CoW04+W03+C: 1150 2,5 WC+W02 hydrogen 0,84
CoW04+W03+C 900 2 W+C nitrogen -
CoW04+W03+C' 1100 2 WC+W W nitrogen 0,9
CoWO.+W0 3 1100 1,5 C0 3W3C high hydrocarbon 1,75
CoW04+W03+C 850 0,5 WC high hydrocarbon 3,4
CoWO.+W03+C 1100 3 WC high hydrocarbon 1,7
CoW04+W03+C" 900 3 WC+C0 3W3C+ hydro gen 16,1
W2CW + diamond
CoW04+W03+C
...
CoW04+ W0 3+C.. 1100
1000
1,5
3,5
W2CW+ diamond
C0 3W3C+W+
hydrogen
nitrogen
-
-
diamond
CoW04+ W03+C.. 850 0,5 WC+C03W3C+ high hydrocarbon 59
CoW04+W03+C
.. 1050 0,5
diamond
WC+C0 3W3C+ high hydrocarbon 38,5
diamond.e.,
-carbon black
.. -explosion carbon
carbon and the lines of WC+W2C in the present of carbon black. At the increase of
temperature and time of carbidization in atmosphere of high hydrocarbon only X-ray line of
WC was founded. Attention is drawn to the fact that the specific surface at the same
temperature 1100 c in the presence of two phases (I, 96) is smaller than if one phase (0, 7)
is. With the increase of temperature the specific surface already decrease. Let us compare
the carbidization of titanium and its oxide at the same conditions. W0 3 without carbon at
the atmosphere of high hydrocarbon reduced to W0 2 at the temperature 850 C and to
W+W2C at the temperature 1100 0c. The specific surface in this case is higher than at
carbidization of titanium.
It's very interest that the reduction and carbidization of CoW04+W03 in atmosphere
of high hydrocarbon are taken place at lower temperature and more quick. Without carbon
the phase of C03W3C is formed at the temperature of 1100 c for 1,5 hour. In the presence
of carbon black the phase of WC is formed at the temperature of 850C for 0,5 hour. The
2/g.
specific surface is 3,4 m At the temperature of 1100 c the specific surface decreases to
2
1,7 m /g.
In order to receive a nanophase composite WC-Co-diamond we used the fra~ment
wastes and explosion carbon. The specific surface of explosion carbon was 135 m /g in
2/g
compare of 10,5 m for carbon black. The explosion carbon is a mixture carbon and
diamond (50:50). Therefore, we will expect that the temperature and a time of carbidization
of explosion carbon will be such as a previous case or below and diamond will not be
reacted with tungsten. Actually, as shown in Tab. 6 in this case, the WC is formed at 900-
1000 "C in hydrogen, and diamond is kept. The specific surface was 16,1 m2/g such as the
case of carbon black in the presence of higher hydrocarbon the phase of WC is formed at
the temperature of 850C after 0,5 hour. In this case the specific surface was 59 and 38,5
129
m2/g at the 850 and 1050 DC, respectively. The diamond is kept, but at the temperature of
1050 DC its content decreased . can be supposed that the presence of C03W3C phase is bond
with deficit in carbon . In the presence of high hydrocarbon the equilibrium of reaction
direct to the side of formation tungsten carbide. The use of amorphous carbon in
carbonising atmosphere permitted to decrease the temperature of interaction between
tungsten and to prepare nanophased composite system WC-Co-diamond with the specific
2/g.
surface to 30-50 m
CONCLUSION
We have early shown that the temperature of process is determinable for dispersivity
of chemical reaction products. In this work we have sown the possibility to control the
temperature of the chemical interaction between tungsten and carbon at the expense
dispersivity of tungsten, carbon and gas atmosphere. It have established that the nanophase
composite system WC-Co-diamond can be prepared under carbidization by explosion
carbon in hydrogen and in the presence of high hydrocarbon .
REFERENCES
1. H.Gleiter, Prog.Mater.Sci., 33 ( 1989) pp.223-23I

2. R.W.Siegel, Nanostructured Materials, 4, NI (1994) pp.121-138
3. A.S.Petuchov, I.V.Uvarova, V.P.80undarenko and so on Poroshkovaya metallurgy 10 (1992), pp.31-35
4. V.I.Trefilov, G.I.Savakin, V.V.Skorochod, J.M.Solonin, A.F.Cherinko DAN SSR 239, No 4 (1978)
pp.838-841 (in Russian)
5. G.I.Savakin, Almazu i cverxtverdue materilu 4(1981) pp.I-2 (in Russian)
6. G.I.Savakin, V.V.skorochod, J.M.Solonin, V.I.Trefilov DAN SSSR 270, Nol (1983) pp.92-96 (in
Russian)
7. I.Uvarova, Neorganichesky materialu 34, N7 (1998) pp.I-13 )in Russian)
8. J.D.Holliday, F.H.Hause, F.K.Sale, Ind.Therochemical Data Proc., Univ. Surrey, sept. 11-13 ( 1979)
London ( 1980) pp.291-300
9. P.8racconi , L.C.Dufour, Met.Trasaction 78 (1979) pp. 32 1-327
10. N.Sconberg, Acta Chem.Scand., 8, N6 ( 1954) pp.932:94I
11. V.I.Tretiakov, V.K.Sentchichin, N.K.Vasevich, Porochovaya metallurgiya Noll (1990) pp.32-36 (in
Russian)
12. A.N.Zelikman, L.S.Nikitina, Volfram M., "Metalurgia" (1978) 270p (in Russian)
130
PEQULIARITIES OF FINE-DISPERSION SiC AND Si3N4 POWDERS
OBTAINED FROM TITANIUM-MAGNESIUM PRODUCTION WASTE
Marina V. Vlasova, Vladimir A. Lavrenko
Institute for Problems of Materials Science

National Academy of Science of Ukraine
Kiev 142, Ukraine
INTRODUCTION
The use of metallurgy waste is an important ecological task for nowadays.

In this paper the fabrication of fine-dispersion SiC and Si)N4 powders from the Ti-Mg
production waste was considered. Nitriding and carbidization of this waste open the wide
possibilities for obtaining of cheap ceramics powders and parts on their base.
EXPERIMENTAL PROCEDURE
The waste is a powder which composition is presented in Table 1. Sspec.~ 5 m 2j g. The

silicon is a base of this powder.
Table 1. Content of impurities in waste of Ti-Mg production as well as as in products of

their carbidization and nitriding.
C, % mass.
Sample Si Fe AI Ti Ca 0 CI C N
Waste 62,2 2,3 1,1 1,13 1,25 13,9 12,3 1,2
Carbidization
Ttreal.= 1773 K, 68,2 0,35 0,25 0,1 0,63 0,1 0,25 29,8
ttreal.= 60 min.
Nitriding
Ttreal.= 1573 K, 59,9 1,9 0,37 0,15 0,06 8,5 0,15 0,7 28
ltreal.= 60 min.
For the SiC powder synthesis we added the carbon black (Sspec.- 11 m2j g) with 5% C
excess. The Si)N4 powders were obtained using a straight nitriding of waste in a nitrogen
Advanced Science and Technology of Sintering, editedby Stoja novic etal.

Kluwer Academic/Plenum Publishers, NewYork, 1999 131
flux, and SiC - in argon flux, the temperature treatment being in a range of 373-1773 K, at
constant temperature with an exposure from 15 to 480 min .
For an investigation of structure and powder composition a Comebax SX 50 EPMA-
device was used . XRD analysis was carried out using DRON -2 (Cu Ks-radiation). IR-
spectra were obtained using a Specord M-80 device , and EPR ones - using a SE/x 2547
radiospectrometer (3 - em range) at room temperature, Mass-spectrometric study of
composition of gaseous products was carried out using a MI-1201 installation.The chemical
and spectral analyses of samples were fulfilled using the standard procedures.
RESULTS
Waste characteristics
These were obtained using the experimental data . The waste is, mainly, the silicon
particles. The size of large particles achieves 10-50 urn while for small ones - less than 1
urn. The latters are consolidized in the aggregates which, sometimes, contain the melted
inclusions of ferrosilicon. The surface of Si particles is friable one, and on it the CI, AI, Fe
atoms are placed. The latters are partially removed in air medium and almost entirely
removed under low-temperature treatment up to 873-1073 K in any gas environment. The
Ch, AIC!), and FiCh are the revealed gaseous products. When the friable deposition layer is
removed from the surface of Si particles, the IR-spectra contain the Si-O bonds absorption
bands at u -1100 and 450 em" (Fig. 1.1, the curves a and b). Obviously, on the Si particle
surface there is an oxide film connected with CI and chlorides.
a 1 2
a
1200 1000 800 600 400 1200 1000 800 600 400
v (cm') v (em")
Figure 1. IR absorption spectra at carbidization (1) and nitriding (2) of waste. a - initial waste, b -
T lrea,.= 473, c - 1073, d - 1273, e -1473, f - 1573, g - 1773 K. a-f - t lreal.= 60, g - 120 min.
132
Carbidization of waste
During a subsequent temperature treatment a further purification of Si-containing

product occurs (see Table 1). A weakening of IR-bands intensity at 1100 and 450 em"
points out to partial removal of oxide layer whereas an appearance of band at u - 900 ern'
can be interpreted as Si-O-C bonds formation (Fig.1.1, c and d curves).
The Si, FeSi 2 (u-leboite), small-ordered Si02 (a-quartz), and a-SiC are the main crystal
phases which have been identified. The content of SiC became more while other phases less
with a rise of temperature and time treatment (Fig.2,a and 3,a). A some increase of FeSb
content at Ttreat.-1473K is caused by transfer of ferrosilicon particles with the least Si
content to this phase state on the account of Si diffusion.
The transformation ofIR-spectra with a Ttreat . growth (Fig.1.1, e, f curves) shows that
the SiC continuously formed (the band is in the u - 900-800 region). Herein e spectrum
corresponds to amorphous silicon carbide whereas at Ttreat.~1573 K - to crystalline one .
After Ttreat.= 1073-1773 K the EPR spectrum which is a superposition of C signals
belonging to the two-diment ion carbon structures of different sizes in registered 1,2. The
variation of spectrum width and g-factor (FigA ,a) points out to a deterioration of carbon
black particles in two-dimention structure 2. A diminution of this signal intensity after T treat
~ 1573 K (Fig A,b) shows that namely such carbon states take part in carbide formation 3.
After Ttreat. = 1773 K from a mixture the fine-dispersion system forms from aggregated
SiC particles (size less than 1 urn),
120 a 120 b
4
100 100
c 80 80
:J
.ci
....
-
(\3
60 60
~
'cw
.....cQ) 1
40 40 1
>__, e_e-e"",
/3 .
e-
20
0
f_~:~ :~
- - - --- ~ ---_ .-.
'\
e
'--- .~:
20
0 2
'~''''
/ e
400 800 1200 1600 400 800 1200 1600

Ttreat (K) Ttreat (K)
Figure 2. Relative variation of crystall ine phase content at carb idization (a) and nitriding (b) of
waste on dependence on treatm ent temperature. a - t_, = 60, b - 120 min . I - Si, 2 - FeSi 2, 3 - Si0 2,
4 - SiC,S - u-Si 3N 4, 6 - I3-Si 3N 4 , 7 - Si2N 20 .
133
, . . . - - - - - - - - - - - - , 500
14 a 60 b
12 400
50
10
c: 300 40
:J
...co
.0 8

30
~
'iii 6 200
-
c:
Q)
c: 20
4
100
2 /

10
O-+'-_-f'-=-r---,r--r-.,....-'''III--r---r---.-'
20 40 60 80 100 120 o 50 100 150 200 250
Ttreat (min) Ttreat (min)
Figure 3. Relative variation of crystalline phase content at carbidization (a) and nutriding (b) of
waste on dependence on tretment time at 1773 K (a) and 1673 K (b). Numbers curves as in Fig. 2.
I I I
- 2.6
.~ a b
40

10 3 -
~-~ - 2.5

\ - 2.4 30
\.
C
I- 10 2 - :J
co
a
'Of
.0
- ro
I
2.3 iii'
-
s:
""'.'.-.-.-
u -: 20
., .- .--.
j.
0_
'0 (J)
c:
~ 2.2 Q)
10 C
2
3~-----.
10
.
. ......... - . - 2.1
~
..
"-
< . _- - - -

/
"
/
1 2.0 0
400 800 1200 1600 800 1200 1600
Ttreat (K) Ttreat (K)
Figure 4. Change of width, g-factor (a) and intensity (b) EPR carbon signal under waste
carbidization. tu-eal'= 60 min. I - wide signal, 2 - narrow signal, 3 - g-factor. Measurements in
vacuum.
134
Nitriding of waste
Up to T treat-"? 1273 K, similarly to a carbidization, a purification of waste from

impurities takes place, the formation of oxide layer occurring (Fig.I.2, curves a-c). At the
temperature rise the friable deposition layer on the particles surface appears ones more, the
Si particles beginning to grind . At low temperatures an appearance ofIR-absorption band in
the range of 900 em -I can be interpreted as the Si-O-N bond formation, while at Ttreat.>
1073K the formation of a wide band with minimums at u - 1100 and 990 cm- I testifies
about existence of the small-ordered amorphous SiOxNy and Si 3N4 phases (Fig.I.2, curve
d). The chemical analysis confirms an increase of N" content beginning from this
temperatures.
The a-Si)N4, I3-Si 3N4, and SizNzO are the main crystalline phases in the waste being
nitrided . Herein the content of free Si, SiOz and FeSi z becomes less (Fig. 2,b and 3,b).
Starting from Ttreal'~ 1473 K the al3-Si3N4 is the main phase . The increase of I3-Si 3N4
content in the high-temperature range is associated with a~13 phase transformation (Fig.
2,b, 3,b). The preferencible formation of a-Si)N 4 is fixed also in IR-spectra by bands at
500 em" (a-phase) and 450 cm-I (l3-phase) (Fig. 1.2, curve e).
At temperatures in the range 1573-1673 K the fine-dispersion system consisting of
nitride particles with a size less than I urn forms . They forms the aggregates; besides , there
is a small number of filaments of 5-15 um length.
DISCUSSION
Taking into account the friable surface layer, reveal of gaseous Clz and chlorides ,
purification of Si particles under heating with simultaneous appearance of oxide layer, one
can come to conclusion that on the Si particles samples there are the Cl- and Me-Cl-surface
complexes formed by the modified SiOz-type 4. The removal of Cl- and MeCl- groups has
to be accompanied by a formation of reaction-active Si-O- groups being united with the free
C bonds or joined nitrogen. The formation of SizNzO phase according to such mechanism
is the most probable. In the temperature range about 1473 K when the breaking out of
surface SiO- complexes takes place, the probability of Si-C and Si-N bonds formation is
very possible. Herein the formation of Si3N4 and SiC occurs as well. The revealed gases
transferring the carbon black particles into the two-dimension fragments lead to formation
of free carbon bonds 3.
In the region of FeSiz melt appearance (about 1480 K) the carbide and nitride
formation is intensified due to a partial Si dissolution and N diffusion. Herein the quantity
of FeSiz becomes less.
At Si melting (melting point is about 1740 K) the main carbide-formation process
takes place . The registration of EPR carbon signal in SiC powder obtained at 1773 K
pointed to a presence of C nuclei in carbide particles Z,3.
The prefefiable a-Si3N4 formation up to 1673 K is explained by presence of Si nucleus
in the nitride particles 5,6. At its melting the a~13 phase transformation is easily realized .
CONCLUSION
The waste of Ti-Mg production consisting of Si particles of different size can be

successfully used for low-temperature synthesis of fine-dispersion SiC and Si)N 4 + SizNz 0
powders. The main process of carbide- and nitride-formation is realized at an appearance of
135
both FeSi 2 and Si melts. The specific surface defect structure of Si particles being a source
of the active SiO- bonds plays the main role at the ShN20 formation.
REFERENCES
I. V.M. Samoylov, A.S. Kotosonov, and B.G. Ostronov, Study of peculiar ities of molecular
structure of carbonized carbon materials, using EPR method, Chemistry ofSolid Fuel.
3:135 (1985). (In Russ.).
2. M.V. Vlasova, D.P. Zyatkevich, N.G. Kakazei, and G.S.Oleinik, Structure of silicon carbide
powders produced in interaction of silica with carbon black, Powder Metallurgy 7:47
(1992) . (In Russ.)
3. M.V. Vlasova, L.T. Domasevich, and N.G. Kakazei, Effect of the initial state of synthesis
components in the reaction of carbothermal reduction of silica on the structure of silicon
carbide particles . I. Aerosil - carbon black system, Powder Metallurgy 7:54 (1993) .
4. G.V. Lisichkin, G.V . Kydriavtsev, A.A.Serdan, S.M.Stariverov, A.Ya.Uffa Modifi ed Silica in
Sorption, Catalysis and Chromatography, G.V. Lisichkin, ed., Chimiya,Moscow (1986).
(In Russ.).
5. P.V. Pavlov, Structure of silicon nitride sintesed by nitrogen ionic implantation and resonance
mechanism transformation from a to J3 form under annealing, Krystallography 24:481
(1979) . (In Russ.).
6. T.S. Bartnitskaya, M.V. Vlasova, and Yu.L.Galchinetskaya, Properties of silicon powders,
prepared by grinding in liquid nitrogen, Neorgan . Mater . 29:894 (1993). (In Russ.).
136
SINTERING OF NANOCRYSTALLINE ZIRCONIA-BASED CERAMICS
Vladimir V. Srdic l.2, Markus Winterer 1 and Horst Hahn l
'Darmstadt University of Technology

Materials Science Department, Thin Films Division
Darmstadt, Germany
2 University of No vi Sad, Faculty of Technology
Department ofInorganic Technology and Materials Science
Novi Sad , Yugoslavia
ABSTRACT
Chemical vapor synthesis provides crystalline, non-agglomerated, nano-powders of

zirconia and zirconia doped with alumina with narrow size distributions and average grain
and particle sizes between 3 and 5 nm. The sintering of these materials into dense.
nanocrystalline ceramics of uniform microstructure is investigated. Grain growth
inhibition is observedfor zirconia doped with 5 mol% alumina compared to pure zirconia.
INTRODUCTION
During the past few years the interest in nanocrystalline zirconia-based ceramics with
grain sizes less than 100 nm has increased as their properties are often significantly different
and considerably improved in comparison to conventional zirconia ceramics with coarser
grain structures!" . Nanosized zirconia-based powders can be synthesized by various
techniques but the obstacle of consolidation into fully dense ceramics without significant
gra in growth still remain s unsolved . The most limiting factor for sintering of many ultrafine
powders is the pre sence of agglomeration. The agglomerated powders densify at high
sintering temperatures and long sintering time, resulting in exaggerated grain growth. Even
with high quality, weakly or nonagglomerated powders special efforts have to be undertaken
for complete densification in order to suppress grain growth . Usually, the grain growth can
be hindered by reducing the grain boundary mobility, for example by impurities, pores or
second phase particles.
In the pres ent paper the sintering behavior of nanocrystalline pure zirconia (n-Zr02) and
zirconia doped with 5 mol% alumina (n-Zr02/ 5mol% Ah03) is invest igated The powders
are prepared by a novel gas phase process called chemical vapor synthesis (CVS) . Inherent
Advanced Science and Technology of Sintering, edit ed by Stoja nov ic et al.

Klu wer Academic/Plenum Publi sbers, New York , 1999 137
advantages of the CYS process are the formation of nanocrystallites from molecular or
atomic species in a completely homogeneous state (vapor), a well defined reaction zone in
which temperature, pressure and mass flows are controlled and reproducible .
Inhomogeneities, usually observed when various dopants or second phase particles are
introduced into zirconia are minimized by mixing the alumina and zirconia precursors in the
gas phase prior to decomposition in the CYS reactor.
Nanocrystalline n-Zr02 and n-Zr02/ 5mol% Ah03 powders are prepared by chemical
vapor synthesis. More details of the powder synthesis are described elsewhere':' .
Metalorganic precursors (zirconium-t-butoxide and aluminum-s-butoxide) are bubbled with
helium as carrier gas, mixed with oxygen and delivered to a hot wall reactor. During the
short residence time in the hot zone individual precursor molecules are decomposed and
reacted at a temperature of 1000 DC and a pressure of 1000 Pa forming small pure or doped
zirconia particles . The nanoparticles are separated and collected from the gas flow by
thermophoresis.
The as-synthesized powders are uniaxially pressed and pressureless sintered in vacuum
(0.5 Pa) at different temperatures up to 1000 c for I hour. The pressed and vacuum
sintered pellets are characterized by density measurement (from the geometry and the mass
of the sample), X-ray diffraction using a Siemens D5000 instrument with Ni-filtered CuKa.
radiation, nitrogen adsorption measured by a Quantachrom Autosorb-3B instrument and
high-resolution scanning electron microscopy (HRSEM) performed with a HRSEM Philips
XS 30 operating at 20 kY.
The as-synthesized CYS pure n-Zr02 powder consists of the mixture of tetragonal (77
vol%) and monoclinic zirconia (Fig. la) with average crystallite sizes of 4.6 and 6.1 nm
calculated from X-ray line broadening using Scherrer formula. The powder is nonagglorne-
20 30 40 20 30 40
2 Theta 2 Theta
Figure 1. XRD patterns of as-synthesized powder, pressed and vacuum sintered pellets of: a) pure n-Zr0 2
(left) and b) zr0 2! 5 mol% Al203 (right) (m monoclinic zr0 2, t . tetragonal zr0 2) .
138
_ 200 ,.............--..--.~..,........"'"'""T'"-,........,
-2' .g0.20
E 150 " Zr9z
ZrOi AlP3 5 O.l5 - '~
'"
~
...........
ZrOz/A1z03
<C 100 <l)
<l)
u
\ ,.
0.10
~
:::J 50 z-o; (5
>
Vl ....
<l) 0,05
a
tu CL
co o 200 400 600 SOO WOO o 200 400 600 SOO 1000
Sintering Temperature (0C) Sintering Temperature (0C)
Figure 2. a) specific surface area (left) and b) total pore volume (right) of pure and alumina doped zirconia
as a function of sintering temperature.
rated with very narrow particle size distributions. The average particle size of 4.6 nm was
4
confirmed by multi-point BET and 5.7 nm by TEM
The as-synthesized CVS doped powder is also nonagglornerated" and has completely
tetragonal symmetry (Fig lb) with the average crystallite size of 3.2 nm estimated from
XRD data and the average particle size of 3.2 nm calculated from BET. The higher fraction
of tetragonal phase in the doped compared to the pure powder can be explained by
57
formation of solid solution of alumina in zirconia, already mentioned in the literature .
During compaction the fraction of tetragonal zirconia decreases considerably in both
samples, however, the phase composition remains almost constant during vacuum sintering
up to a temperature of 1000 DC (Fig . 1).
The initial and intermediate stages of sintering are investigated by nitrogen adsorption
measurements. Fig. 2a shows that the BET specific surface area of both samples decreases
continuously with increasing temperature, but there are no changes in the total pore volume
at low temperatures (Fig . 2b) . The pore size distributions, evaluated from the desorption
isotherms, according to the BHJ theory are presented in Fig. 3. The pore size distribut ions
of the pressed pellets are slightly bimodal. It is believed that the bimodal size distr ibution
with the extremely small pore sizes is not due to presence of agglomerates, but because of
very small crystallites of similar sizes with spherical and nonspherical morphology'
During vacuum sintering at 550C for Ih smaller pores disappear but no pore growth is
observed . The considerable changes in the pore size distribution, the continuous decrease of
the specific surface area and the constant total pore volume during the initial stage of
vacuum sintering (T<600 DC) reveal that microstructural changes take place at temperatures
below those necessary for densification. At higher temperatures, during the intermediate
stage of vacuum sintering, the continuos elimination of the remaining pores takes place,
without changing the average pore size. According to nitrogen adsorption measurements
(Fig. 2 and 3), the n-ZrO z and the n-ZrO j/ 5mol% Ah03 samples behave similarly, but
densification starts in the pure n-Zrfr, at somewhat lower temperatures, the elimination of
the pores is faster and transition from open to close pores is observed at 850 DC, which is 50
DC lower than for the doped sample.
The density change as a function of the sintering temperature is shown in Fig. 4
Relative densities were calculated taking into account the alumina content and relative
amounts of tetragonal and monoclinic phases presented in the samples . The following
density values are used for the calculation: 5.82 g/cnr' for monoclinic ZrO , 6.10 g/cm' for
139
-
-- ....- ...-.- --- .
Ol
;;;- 00 2 850 0C/lh
E
u ~
""0 :0 1-_ _ . _._900

_~Cllh
-
Ol Ol
~> ..2
>
Cl Cl 700 0CIlh
- -- e
.sa. 1
c c
.g 1 fI
a.
.... .,
~ 0 ~~ _Jl!!!!~ .
~ OL.......~""':-~~_~"'-' (1)
~1 Cl 10 100 1000
Pore Diameter (nm)
Figure 3. Evolution of pore size distribution of a) pure n-Zr02 (left) and b) n-ZrOi 5mol% Ah03 (right).
tetragonal Zr02 and 3.4 g/cm' (corresponding to the density of transitional alumina) for the
alumina phase. The pure n-Zr02 has a lower green density than the doped sample, because
different pressures (500 MPa and 800 MPa respectively) have been applied during
compaction. Nevertheless, the pure n-Zr02 sample densities faster at lower temperatures
and the full density is reached after vacuum sintering already at 950 0c. The density of the
doped sample also increases continuously up to 99.1 % at 1000 "c It is important to note
that transparency observed in the green pellets is preserved during the whole sintering
process, even in the completely dense pellets .
In Fig. 5 the HRSEM micrographs of the pure and the alumina doped zirconia samples
vacuum sintered at 1000 cfor I h are presented displaying uniform microstructure with
very small grain sizes . Considerably smaller grains are found in the doped sample indicating
that presence of alumina successfully inhibits grain growth of zirconia . Grain sizes measured
from HRSEM micrographs and estimated by X-ray line broadening are shown in Fig. 6 as a
function of relative density. Grain growth in the pure n-Zr02 sample is pronounced
especially at densities higher than 90%, when the pinning by pores becomes less efficient.
However, there is no exaggerated grain growth, and the fully dense sample has a grain size
of approximately 60 nm. It can be clearly seen (Fig . 6) that grain growth is suppressed by
the addition of alumina, decreasing the grain size to 40 nm in fully dense sample .
In both samples fast densitication without considerably grain growth is observed at very
low temperatures. This can be explained by the excellent characteristics of the CVS
powders, namely no agglomeration, very small crystallite size and narrow size distribution.
Additionally, the vacuum sintering process is beneficial due to a positive sintering pressure
by removal of air from the pores, enhanced particle repacking during particle coarsening and
enhanced diffusivity pronounced by oxygen vacancies created in vacuum at high
temperatures.
The mechanism of grain growth inhibition in alumina doped zirconia is unknown.
However, it is assumed that the alumina which is thermodynamically unsolvable in zirconia
is homogeneously distributed in the grains of the as-synthesized powder. During sintering a
segregation in the Zr02 nano-grains takes place forming alumina rich grain boundaries
which limit the further grain growth of the Zr02 grains because the diffusion of zirconium
ions through alumina is slow . Thus , ultrafine grained ceramics of uniform microstructure can
140
z;-
.~ 0.8
Q)
Cl
~
.~ 0.6
v
0:
.- '/
0.4 . .- -
o4 0 600 800 1000
Sintering Temperature (0C)
Figure 4. Density change of pure and alumina doped zirconia as a function of sintcring temperature.
a b
c
Figure 5. HRSEM micrographs of pellets vacuum sintered at 1000 "/l h: a) pure n-Zr02 ' and b) n-ZrOcl
Smol% Ah03 - fresh fractured surface and c) It-zrOz/ Smol'Y.Ah03 - polished surface .
- Zr0 2IAlP3
60 l
E Z,02
r/
-=-4S / ,/
."
Q)
N
Vi 30 ./ . 6-
c
'r'!
<..!:l
IS
G . . . ....
-~
'1
e- .
0.4 0.6 0.8 J.O

Relative Density
Figure 6. Grain size of pure and alumina doped zirconia as a function of relative density .
141
be obtained if the starting material is homogenous and the segregation takes place on the
nanometer level.
CONCLUSIONS
Non-agglomerated, ultrafine n-ZrOz powder synthesized by the chemical vapor

synthesis method is sintered in vacuum at 950C to a fully dense, transparent ceramic, with
an average grain size of about 60 nm. Grain growth is additionally suppressed by alumina
addition . Thus, the almost fully dense zirconia doped with 5 mol% Ah03 vacuum sintered at
1000 c is also transparent having an average grain size of 40 nm.
Acknowledgments: The authors would like to thank the Alexander von Humboldt
Foundation for the research fellowship for Vladimir V. Srdic and the Deutsche
Forschungsgemeinschaft for financial support.
REFERENCES
1. MJ. Mayo, D.C. Hague , and OJ. Chen , Processing nanocrystalline ceramics for applications in
superplasticity ,Mater. Sci. Eng., A 166: 145 (1993) .
2. G. Skandan, Process ing ofnanostructured zirconia ceramics, Nanostruct. Mater ., 5: 111(1995).
3. MJ. Mayo, Thennomechanical stability ofnanocrystalline microstru ctures and their role in enh ancing
superplastic deformation, in: Superplasticity in Adv anced Materials, S. Hori. M. Tokiyane and N.
Furushiro, ed ., The Japan Society on Superplasticity (1991) .
4. V.V. Srdic , M. Winterer, and H. Hahn, Sintering behavior of nanocrystalline zirconia prepared by
chemical vapor synthesis, 1. Am. Ceram. Soc., submitted (1998) .
5. V.V. Srdic , M. Wint erer, and H. Hahn , Synthesis ofnanocryst alline ZrOzlAh03 by chemical vapor
synthesis method , 1. Am. Ceram. Soc., subm itted (1998).
6. O. Yamaguchi , M. Shirai, and M. Yoshinaka, Formation and transformation of cubic zrO z solid solution
in the system ZrO z-Al z03, 1. Am . Ceram. Soc., 71: C-510 (1988) .
6. M.L. Balmer, F.F. Lange, and C.G. Levi, Metastable phase selection and partitioning for Zr(l-xlAlxO(z-xlz)
materials synthesized with liquid precursors, 1. Am. Ceram. Soc., 77 : 2069 (1994 ).
142
ANALYSIS OF THERMAL TREATMENT OF ZoO
DERIVED BY THE FREEZE-DRYING METHOD
Natasa Nikolic,' Zorica Zakula,' Olivera Milosevic,' Tatjana Sreckovic'
'Institute of Technical Sciences ofthe Serbian Academy of Sciences and

Arts, Knez-Mihailova 35, 11000 Belgrade, Yugoslavia
2Center for Multidisciplinary Studies, Belgrade University, Kneza Viseslava
la, 11000 Belgrade, Yugoslavia
ABSTRACT
The development of advanced materials eventually leads to an expansion of new

methods for the synthesis . Freeze-drying as a cryochemical method for the synthesis of high
purity oxide powders with specific microstructures was presented. ZnO powders derived by
this technique were characterized by X-ray powder diffraction analysis and scanning
electron microscopy method . Consolidated submicronic ZnO powders were thermally
treated under nonisothermal conditions at different heating rates using dilatometer. An
analysis of densification and microstructural evolution was performed. The obtained results
were discussed in order to establish a correlation in the triad synthesis-structure-properties.
INTRODUCTION
Zinc oxide, as a nonstoichiometric oxide used in numerous applications (ZnO-based

varistors, components in electronic devices, mixed catalysts, etc.), was investigated because
of the evident interest for the application of ZnO-based materials with ultradispersed
structures. The freeze-drying method', as a novel cryochemical technique for the production
of fine powders with the controlled microstructure, is often used. The principle of freeze-
drying is based on the rapid freezing ofa solution of precursors followed by the sublimation
of the solvent under vacuum. Dehydrated salt is decomposed to oxide according to a
previously determined procedure that includes the application of various atmospheres and
temperature regimes. It is well known that the powder morphology has a very important
influence on the sintering behavior. Hence, the preparation route has a significant influence
on the sinterability of a powder.
Advanced Science and Technology ofSintering, edited by Stojanovic et al.

The aim of this work was to establish the parameters for ZnO powder synthesis as well
as the appropriate method for the consolidations of powders obtained by the freeze-drying
method.
EXPERIMENTAL
Zinc nitrate hexahydrate (Merck, purity 99%), dissolved in distilled water (Irnol/dm')
was used as a precursors solution. An aerosol made by the twin-fluid atomization system
was frozen using liquid nitrogen (figure I) and dehydrated using a freeze-dryer (type
LGA05) which operated at temperatures from -30C to 20C and vacuum from BPa to
20Pa. Powders obtained by sublimation of the solvent were calcined in the horizontal
furnace (LENTON tube furnace LTF) in air at 275C for two hours and after that quenched
in air. The obtained ZnO powders were characterized by X-ray powder diffraction method
(XRPD) using a PHILIPS PW-1820 diffractometer with CuK a l /2 radiation and graphite
monochromator and scanning electron microscopy (ISM 5300-JEOL). ZnO powders, with a
small amount of ethanol as a binder, were uniaxially pressed to obtain compact samples .
Dilatometry measurements were performed using a dilatometer (Bahr Geratebau GmbH
type 702s) with the heating rate of 10C/min up to II OOC.
Figure 1. Schematic of aeroso l freezing (I-twin-fluid atomizer; 2-solution; 3-flow meter ; 4-manometer;
5-valve ; 6-compressor; 7-nitrogen; 8-liquid nitrogen for droplet freezing)
DISCUSSION
X-ray powder diffraction analysis (XRPD) revealed the existence of only a hexagonal
crystal ZnO-phase at 275C. The average spherical crystallite size of25.9nm was calculated
using X-ray line-broadening analysis', while the aerosol average droplet size was 68.661lm
and was calculated using equation Nukiyama-Tanasava'. With the presumption that one
particle is formed from one droplet, the average particle size was estimated to be 19.71 um",
This value agrees well with the SEM analysis (figure 2) implying that the obtained powder
is composed of hard agglomerates, the dimensions in the range 15-20llm. Interparticle
sintering evident inside the agglomerates indicates that the as-prepared powder is highly
reactive. Thus, it's quite evident that wet chemical routes as well as high temperature
synthesis methods lead to the formation of a powder with agglomerates or aggregates.
Agglomeration of particles was also confirmed during consolidation since it was
necessary to apply high pressure (686 MPa) to achieve a compact sample (78.5% PJ .
Additional nonisothermal treatment of a green sample with agglomerates arranged in this
way, which was performed in dilatometer, showed some unusual effects : there was not an
evident change in sample density and only thermal expansion occurred.
144
Figure 2. SEM microphotograph offreeze-dried ZnO (275C, 2h)
SEM microphotographs of ZnO thermally treated in a dilatometer up to 1100Cfor 2h

are presented at figure 3 (sample A) and figure 4 (sample B). It can be concluded that both
compacts are very porous, implying that thermal treatment further increased the level of
closed porosity initially achieved during the compaction stage. Also, the freeze-drying
synthesis route, that results in obtaining specific microstructures, can be assigned for the
possible difficulties in obtaining the full density of compacts. Further more, the influence of
crystallite size on densification of compacts formed from ultrafine powders is also quite
significant. Improved sintering of such powders could be achieved using processing
technique that enables control of the heating rate during the sintering process (e.g. rate
control sintering), which was not performed during these experiments.
Figure 3. SEM microphotograph of ZnO compact isothermally treated at 1100C for 2h (sample A)
145
Figure 4. SEM microphotograph ofZnO compact isothermally treated at I 100C for 2h (sample B)
CONCLUSIONS
The freeze-drying method, as a cryochemical technique for preparing fine,

homogeneous ZnO powders from aerosols, is presented. ZnO powders were synthesized
from a nitrate solution (lmol/dm') using a twin-fluid atomization system for aerosol
formation. The optimal powder synthesis parameters (temperature and pressure of
sublimation, decomposition temperature) were established. It was shown that the as-
prepared powder is highly reactive causing the occurrence of sintering simultaneously
during decomposition into oxide. This implies that the obtained ZnO composed of primary
nanocrystallites, 25.9nm in size, is hard agglomerated. The obtaining of fully dense ZnO
was probably inhibited by the agglomeration of powders formed during freeze-drying
process.
ACKNOWLEDGMENT
This work was financially supported by the Republic of Serbia Science Foundation
through the project "Prognosis of Materials Properties from the Viewpoint of the Synthesis-
Structure-Properties Relationship". The authors would like to express their gratitude to
Prof. M.M. Ristic for helpful suggestions.
REFERENCES
1. Yu.D. Tretyakov, N.N. Oleynikov and O.A. Shlyakhtin, Cryochemical Technology ofAdvanced Materials,
Chapman & Hall, London (1997).
2. B. Marinkovic, Z. Zakula, S. Djuric, N. Nikolic, O. Milosevic, Lj. Zivkovic, T. Sreckovic, M.M. Ristic,
Line profile analysis of nanostructured Zno powders obtained by freeze-drying method, 6th European
Powder Diffraction Conference, Budapest, Hungary, 22-25 August 1998, Book of abstracts: 278 .
3. S. Nukiyama, Y. Tanasava, Trans. Soc. Mech. Eng . Japan , 18:136 (1939) .
4. T.Q. Liu, O. Sakurai, N. Mizutani and M. Kato,J. Mat. Sci., 21:3698 (1986)
146
THE EFFECT OF SHOCK-WAVE TREATMENT ON THE STRUCTURAL
CHARACTERISTICS OF SYNTHETIC DIAMOND POWDERS
M. A. Vasylkovska, Va. V. Zaulichny, V. I. Kovtun, M. V. Vlasova
Institute for Problems of Material Science

of the National Academy of Sciences of Ukraine,
3, Krzhizhanovsky Str., 252180 Kyiv, UKRAINE
ABSTRACT
Special features of the shock-wave effect on the structure of valence bonds and
substructural characteristics of diamond powders depending on their grain size have been
found. Research was done by electron paramagnetic resonance (EPR), X-ray emission
spectroscopy and X-ray structural analysis.
1. INTRODUCTION
The shock-wave compacting of diamond powders is one of the advanced sintering

processes. Powder sintering is a function of physico-mechanical properties and substructural
characteristics that could be defined by electron structure. This factor effects to CK,. band
shape of X-ray emission spectra. The paper seeks to study the shock-wave treatment effect
on the diamond powder electron structure from changes of X-ray emission CK,. bands.
2. EXPERIMENTAL PROCEDURES
It have been studied synthetic diamond powders with various granularity : 200/160,
60/40, 7/5, subjected to shock-wave treatment in the range of pressures from 6 to 18 GPa.
The powders were placed into the keeping matrix to except mutual interaction between
diamond particles. In this way, crushing and joining of the particles by sintering due to their
moving have been avoided. It was used the loading pressures, GPa: 6 (PI)' 12 (P 2) , 18 (p )).
Diamond powders were tested for granularity. EPR, X-ray emission spectroscopy and X-ray
structure analysis studied the powder features. Emission CK,. bands were obtained by X-ray
spectrometer RSM-50 with concave diffraction grating (R=6021 sm) and grating constant
P = 600 ruling/mm. Systems vacuum was about 10,6 mm Hg by free-oil pumping. Carbon-
hydrogen vapours were frozen additionally near by anode-placed specimen by nitrogen trap
Advanced Scienc e and Technology ofSintering, edited by Stojano vic et 31.

within 10-mm distance to the specimen. Carbon-nitrogen vapor coating has been avoided by
this means, so it could measure CK" band by the factor 7-8. Diamond particles were
impressed into indium matrix to rise heat removal. Measure-independent results were
averaged.
Energy place of CK" spectra was measured about Cr-LL reference line with second
diffraction degree. Energy of all spectrum points was determined to an accuracy of 0,1 eV.
Equipment distortion of spectra shape wasn't in excess of 0,3 eV. Selective absorption of
CK" band was avoided by means of SKEM-6 with CsI photocathode . Diffractometer UM1
was used for X-ray analysis with Cu-K, monochromatic emission (program package GSD
[6]). EPR spectra have been read by radiospectrometer SEx2547 at room temperature and
various powers, so it makes possible the separating of signals of nitrogen impurity atoms (N-
centers) from mechanical paramagnetic centers.
3. EXPERIMENTAL RESULTS AND DISCUSSION
X-ray spectra of treated synthetic diamond powders were brought together to unit
energy scale. CKa band of starting diamonds of 2001160 grain size is the most different from
those of natural diamonds in both shape and place (Fig. 1a). The shape of band peaks is
almost identical with those by shock-wave treatment. Low-energy outlines of CKa band
starts to shift to high-energy direction (0,2-0,3 eV), that is, to natural diamonds. In this case
"a" influx is weak resolved, as for starting powder . Energy place and intensity of "b" influx
shift to natural diamond direction. It can see the most changes in high-energy branch of CK"
bands. "E" and "d" influxes of starting diamond powders are closed in intensity and energy,
so it forms the wide two-humped subband. "D" influx corresponds to abrupt growth of both
width and intensity due to displacing of short-wave outlines to direction of energy, when
I<Imax /2.
Shock-wave treatment in PI' P 2 pressure conditions approaches 2001160 powders
energy place and shape of CK" band to those of natural diamond. "A" influx resolution is
rising. Low-energy outlines of treated powders shift to high energy by 1,0-1,2 eV and
approach to those of natural diamond until the complete alignment, as for "b" influxes. These
outlines have in part the energy place about 0,1-0,5 eV below that of natural diamond. The
diamond powder CK" bands of P2 , P 3 pressure conditions are a very closely for high-energy
zone and agree substantially with those of starting powders under "e" influx level.
Fig. Ib demonstrates the brought together to unit energy scale CK" bands of shock
wave treated diamond powders. The outlines behave similarly to above-mentioned ones. The
"a" influx resolution becomes like those of natural diamond, but considered energy outline is
below by 0,5-0,8 eV. The studied outlines are very closely as for low- so and for high-energy
zone. For low energies, the outlines are closely to those of natural diamonds. It was observed
the post-treating outlines shift to natural diamond direction even under PI conditions . The
outlines shape is kept constant under further pressure increasing.
Fig. 1c demonstrates the brought together to unit energy scale CK" bands of shock
wave treated diamond 7/5 powders. In this case, it can observe a good agreement in CK"
bands of 7/5 powders and natural diamond. Shock-wave treatment of studied powders leads
to the rising difference in the bands with pressure increasing.
It was shown [1] the substantial departures of investigated powder CKa bands from
natural diamond ones takes place for large-grain diamond 200/16Opowders. We correlated
this result with the fact of some nitrogen atoms that substitute carbon in diamond lattice. It
causes distortion of tetrahedral clusters from faulty amorphous layer at diamond particle
surface. The bond distortion of the layer causes the energy valence Cp-states distribution such
as for amorphous diamond-like films [2, 3]. Shock-wave treatment facilitates the distorted
clusters failure with the loss of nitrogen atoms. It agrees with EPR data (Fig. 2). This fact
148
corresponds to the intensity increasing of "d" influx; energy by which decreases III
something
....
~
'/ 1
..~:~.3";1
270 280 E,eV 270 280
(a) (b)
Figure 1. X-ray emi ssion CKa hands in various

powder granularity:
200/160 (a); 60140 (h) ; 715 (c);
by shock loading pressure, GPa :
P,=5 (~ ; P 2=12 (- - - - ); PJ =18 (-.-.-);
- natural diamond;
.. .- starting diamond powder.
280
(c)
like 1 eV compared to with unloaded diamond powders. It causes by energy decrease of

electron states of C-C and C-N bonds as result the interaction with electrons of diamond
particles. The shorter bonds elongate; it leads to shift of long-wave outlines to high energy. It
is to note two accompanied processes taken place under shock loading of large-grain size
diamond powders. The first of them corresponds to above-mentioned failure of the weakest
C-C and C-N bonds. The second one causes by the energy level localization in failed
orbitals. It shows as abrupt contraction of "a" influx, and the result is contraction of CKll
band in general. Most of the carbon atoms with located energy levels become to interaction
with diamond nuclear, when shock-wave pressure rises. Therefore, the levels splinted to
subbund cause additional broadening of CKll band top. The more abrupt experimental shift
of diamond powder low-energy outlines to those of natural diamond (Fig. la) is a fact of
perfect C-C bonds increasing.
149
Figure 2. Intensity of nitrogen EPR signal dependence on shock wave
treated diamond powders of various granularity: 1-7/5; 2 - 60/40
Like processes take place for shock loaded diamond 60/4Opowders . The most effect
was reached by PI pressure conditions (5 GPa). Subsequently shock pressure increasing has a
low effect on the changes. However, it can see the more clear "a" influx and its good
correspondence in shape to those of natural diamond. It was pointed the high level of orbital
Sp3 hybridization by shock loading.
The easier shock-wave effect to the 60/40 powder could be caused by more little
contribution of distorted tetrahedral clusters on diamond nuclear surface to diamond
structure forming. However, it is shown (Fig.Ib) "e" influx remains in high-energy zone
after shock-wave treatment. Essential distance is conserved between high-energy outlines of
high-pressure treated powders and natural diamonds. Since restriction of "e" influx is
concerned with the carbon broken bonds localization of energy levels [4, 5], it should be
assumed that vacancy and other faults are formed along with above-mentioned diamond
nuclear growth by shock loading. It leads to the bond failure and electron state localization at
the base height of a valence zone. This effect is stronger in CK,. bands of shock wave treated
diamond 715 powders. CK,. bands of both starting 715 powders and natural diamond are in
close agreement. It could be by lack of faulty layer of distorted tetrahedral clusters [I]. Shock
treatment contributes to powder structure many faults. The effect rises by shock pressure
increasing (Fig. l c). It can lead to some deformation of bond length in case fault increasing.
It takes effect in a bit low-energy shift of long-wave outlines of treated powders CK,. bands.
1.6
1.2
.0;
'0
:; 0.8
0.4
(a) (b)
Figure 3. Diamond powder substructure features dependence on shock wave treatment: a - coherent scattering
ranges, L, A; b -lattice microdistortion Sa/a by various powder granularity : 1-7/5; 2 - 60/40; 3-
200/160 .
150
Above-mentioned fault increasing in diamond 60/40 and 7/5 powders due to shock-
wave treatment has a good correlation with X-ray structure analyses (Fig. 3). It can observe
largely microdistortion rising and crushing of coherent scattering ranges by PI and P2
pressure treatment for studied powders. Large-grain diamonds powders loss nitrogen atoms
and increase the fault structure by PI shock loading (Fig. 3). The higher shock pressures
cause the further loss of nitrogen atoms and diamond nuclear growth that decreases the
distortions slightly (Fig. 3). X-ray study shown the shock wave treatment of diamond 60/40
and 7/5 powders facilities the nanometrical subgrain substructure.
4. CONCLUSION
Study of X-ray emission CK a band shown the shock-wave treatment effect on valence
electron energy distribution of diamond powders is dependent on both granularity and shock
compression pressure.
CKa bands, X-ray study and EPR comparison furnishes an explanation of C-C and CoN
bonds break-down of distorted tetrahedral clusters and further formation of diamond faulty
structure by shock loading .
Increase of shock pressure makes CK a band outlines of large-grain 2001160 diamond
powders more likely in shape to ones of natural diamond.
Shock-wave treatment of small-grain diamond powders leads to the substructure
faultability, caused the chemical bond distortion that rises internal energy and facilitates
powder sintering.
REFERENCES
1. Zaulichny Ya.V. , Vasylkovska M.A., Kovtun V.1. Sverhtverdye mater. (in Russian), to be
published.
2. Strel 'nitsky V.E., Zaulichny Ya.Y. , Zhurakovskij E.A. Sverhtverdye mater. (in Russian), 9 (1991)
17.
3. Strel'nitsky V.E., Zaulichny Ya.V., Zhurakovskij E.A. Diamond and Related Materials , 1 (1992)
341.
4 . Zhurakovskij EA, Trephilov V.I., Zaulichny Ya.Y. , Savvakin G.I. , Dokl. Akad. Nauk USSR (in
Russian), 284 (1985) 1360.
5. Kurmaev s.z., Shamin S.N ., Kolobova K.M. and Shulepov S.V. Carbon, 24 (1986) 249.
6. Akselrud I.G ., Gryn Yu.N. , Zavalii P.Ya . at al. 12thEurop. Crystallogr. Meet. Collect. Abstr., M.
v.3 (1988) 155.
151
STRUCTURAL PROPERTIES OF ULTRADISPERSED
Bi-Pb-Sr-Ca-Cu-O PARTICLES SYNTHESIZED
FROM AEROSOL
Lidija Mancic', Zorica Zakula' and Olivera Milosevic'
(Institute of Technical Sciences ofthe Serbian Academy

of Sciences and Arts, Belgrade, Yugoslavia
2Center for Multidisciplinary Study, University of Belgrade,
ABSTRACT
The aerosol synthesis method was applied for submicrometer ceram ic Bi-Pb-Sr-Ca-
Cu oxide powder preparation. The aerosol was generated from nitrate precursor solution
using ultrasonic atomizers operated at 2.5 and 1.7 MHz . Control over the particle structural
properties is established by adjusting the solution and process parameters. Improved
compositional homogeneity, as well as, particle size and shape uniformity is provided by
higher surface reaction and an absence of coalescence process during spray pyrolysis. The
phenomenon of funicular agglomeration in ultradispersed multicomponent powders was
explained by the mechanism of particle formation in the presence of liquid phase. The
interparticle sintering observed for the prolonged thermal treatment is a result of highly
reactivity powders obtained.
INTRODUCTION
Regardless what configuration and type of ceramic materials is required as a final

product, the preparation of precursor powder is always the first step aiming tow ard the
product design. The composition, homogeneity, particle size and shape determine the
properties of finished sample. Spray pyrolysis, as a dispersion phase powder processing
method is capable to produce powders that satisfy these criteria. The process involves
aerosol formation from the precursor salt solutions and control over aerosol decomposition
in a high temperature flow reactor. The stoichiometry, composition, and final particle size
of the produced powder are determined by the type of aerosol generator, precursor solution
characteristics, and therefore can be controlled. Assuming that precursor mixing level
persisted in the final particles, conversion of staring to final material is complete, resulting
in facilitated synthesis of multicomponent system. Additionally, continuity of the process
offers distinct advantages for large-scale powder production.
Ad vanced Science and Technology ofSintering , edited by Stojanov ic et al.

Kluwer Acade mic/Plenum Publishers, New York , 1999 153
The spray pyrolysis method was already used for Bi-based superconducting oxide
ceramic powder synthesis'<. This system is attractive because of two high temperature
phases coexistence, 2212 (BhSr2CaCu20x) and 2223 (BhSr2Ca2Cu30x) and their further
applications in electronic devices operating at liquid nitrogen temperature. It is also known
that 2223 phase formation is enhanced by addition of lead3. However, complexity of this
system has not yet allowed a complete understanding of 2223 phase formation process and
reproducibility in obtaining nearly single phase product. With respect to the above
mentioned, the main goal of this work is to demonstrate that the spray pyrolysis method is
an promising technique for the preparation of superconducting powders with dominant
content of 2223 (Bil.sPbo.2Sr2Ca2Cu30x) phase, as well as, controllable particle size and
morphology for defined and optimized preparing conditions.
EXPERIMENTAL
An aqueous solution to be sprayed was prepared by dissolving the appropriate

amounts of corresponding metal nitrates [Bi(N03)3xSH20, Pb(N03h, Sr(N03hx4H20,
Ca(N03hxH20 and Cu(N03)3x3H20] in S% nitric acid, in order to obtain 1M solution.
Characterization of prepared solution included measuring pH value, surface tension, density
and viscosity. The precursor solution was sprayed using the ultrasonic generators operated
at 2.5 and 1.7 MHz. The experimental set-up employed to study Bi1.8Pb0.2Sr2Ca2Cu30x
synthesis process for the atomization at 2.5MHz was described in previous paper", while
details of the second apparatus are presented here. The powder generation system consists
of an aerosol generator operated at 1.7 MHz, twin-zone reaction furnaces and a membrane
filter where produced particles are collected. The furnaces contained a 1.7m long, 3.2cm
diameter quartz tube. The carrier gas was N2 with a flow rate 1 drrr'rmin, and the aerosol
droplet density was 8.28x107 droplets/em'. The heated region of the furnaces was 1.3 m,
and the temperature profile was increase-humped. The maximum temperature in the first
reaction zone was 3S0oC and 840C in the second one. The filter temperature was
maintained above 100C to avoid condensation process. The droplet velocities were 0.02
mls. For the case of the aerosol formation at 2.SMz the established values of the processing
parameters were maximum reaction temperature - 8S00C; gas flow rate - 0.5 dm3/min;
droplet velocity -0.006 mis, aerosol droplet density - 1.73xl07 droplets/ern' . Prolonged
thermal treatment of powder obtained at 1.7 MHz was done at 84SoC, 4h in oxygen
atmosphere.
Investigation of formation process and determination of temperature regime were
done judging from differential thermal analysis (DTA) curves. DTA experiments were
performed at Shimadzu DTA-SO using platinum crucible and nitrogen as the purging gas.
During the measurements the temperature was increased from room temperature to 900C
at a constant heating rate of 10C/min. The composition and particle morphology in
produced powders were investigated by x-ray diffraction (XRD) and scanning electron
microscope (SEM) analysis. XRD were taken on Philips PW 1710 with CuKa graphite
monochromatized radiation, while semi-automatic image analyzer (Videoplan, Kontron)
connected with SEM was used for particle size, perimeter form factor (for an ideal sphere is
equal to one) and morphology determination .
The DTA curves of dehydrated precursor mixture and powder prepared at 1.7 MHz
were rresented on figure I. According to the obtaining results and previously published
data': , it can be concluded that after nitrate decompositions at 280C, CaO and CU20
154
DTA
mV.
1. dehydrated nitrates mixture
2. Bi-Pb-Sr-Ca-Cu-O powder
2
o oxides crystallization
nitrates decomposition
-\00
o 400 0 600 800

Tem peratur a C
Figure 1. Differential thermal analysis (DTA) curves for dehydrated precursor mixture and powder obtained
by spray pyrolysis at 1.7MHz
begin to crystallize around 480C. The first reaction occurring in investigated system is
formation of Ca2Pb04 at 590C, and after that BhSr2CuOx (2201 phase) begins to form in
the same temperature range. The small endothermic peak at nooc implies 2212 formation,
while broad endothermic peak above 820C is attributed to the melting of Ca2Pb04 and
2201 phase and further formation of2223 phase from 2212 and liquid phase.
Above 840C starts liquid formation due to the eutectic reaction and decomposition
process.
The appearance of endothermic peak on the DTA curve attributed to as-prepared
powder in the temperature range above 570C implies Ca2Pb04 formation from liquid,
while 2223 phase forms in consecutive process up to 830C. Above 860C the most of
present phases in investigated system melt. In accordance to the obtained data it can be
concluded that the appearance of liquid phase during synthesis process increases the contact
area of the particles and accelerate 2223 phase formation process, but insufficiently to
enable recording of the 2223 phase (Bi18Pbo.2Sr2Ca2Cu30x) formation process itself.
XRD patterns of as-prepared powders (obtained at 1.7Mz) and powder submitted to
further thermal treatment (at 845C, 4h in 02) are presented at figure2. It can be seen that
all of peaks can be assigned to the 2212 and 2223 phase. Relative intensity of peaks implies
better crystallinity and dominant content of 2223 phase in thermally treated powder. Basic
phone detected on all patterns is a consequence of amorphous sample holder.
Diffractograms of powders produced at 2.5 and 1.7MHz looked similar, only some peaks of
the powders prepared at 1.7 MHz were broadened with respect to those of powders
prepared at 2.5MHz. This can be result of lower crystallinity as a consequence of the
shorter residence time, namely, higher droplet/particle velocity established for the case of
atomization by 1.7MHz.
155
~- as-prepared
powder
i...'"
e'"
'"oo
28
10 20 30 40 50
Figure 2. XRD patterns of as-prepared powders (obtained at 1.7Mz) and powder submitted to further thermal
treatment (at 850C, 2h in O 2) from the Bi-Pb-Sr -Ca-Cu-O system
On the SEM photomicrographs of powders derived at 2.5MHz, predominantly

spherical, presumably dense and relatively smooth particles are visible, figure 3a. The
particle size distribution, presented at figure 3b, indicates the most particles are in the range
from 0.4 to 0.6flm, with the mean particle size of 0.46flm. The appearance of particle
agglomeration visible as a finest network, can be explained as a consequence of the reaction
mechanisms during the formation of the 2223 phase. The smooth surface of particles and
continuos network of liquid interspersed with air indicate melting of certain phases, causing
the formation of pendular and funicular states of agglomeration. The mentioned states
produce cohesion through interfacial forces and capillary suction, and can be defined as
initial stage of sintering4 .
The salient features of the powders prepared at 1.7 MHz, presented on the figure 4a,
are the follows: particles are hollow with very thin core (conditions for surface precipitation
were fulfilled in the evaporation/drying); spherical and honey-comb structure can be seen
as dominant particle shapes; and the mean particle size is 300nm. SEM photomicrograph of
Bi-Pb-Sr-Ca-Cu powder, submitted to further thermal treatment (at 850C, 2h in 0 2)
implies coherent structure formation and interparticle sintering figure 4b. The higher
content of 2223 phase (determined by XRD analysis) is probably related to the 2223 phase
growth from quenched particles contained 2212 phase.
156
30
25
'$.
d 20
w
c:::
u. 15 .
.J 10
w
c:::
5 .
0
0 .3 0 .35 0 .42 0 .5 0.55 0 .65 0 .7
FERET X
Figure 3. SEM photomicrograph (a) and particle sizes distribution (b) of Bi-Pb-Sr-Ca-Cu-O powder obtained
at2.5MHz
Figure 4. SEM photomicrographs of Bi-Pb-Sr-Ca-Cu-O powders: a) as-prepared at I.7MHz b) treated at

850C. 2h in O 2
Based on droplet and particle size relations? and theirs application to investigated
system4,8, it can be concluded that collision of droplets has not great influence for the
estimated droplet number density values. Because of that, a base principle of the applied
method, that one particle is formed from one droplet, is confirmed. Predicted particle
diameter value, as a function of applied atomization frequency and precursor solution
characteristics, was 0.726 urn (for the 2.5MHz) and 0.937 urn, (for the 1.7MHz). The
discrepancy between estimated and calculated values for particle diameters, is probably the
consequence of the assumptions used during calculations, owning to the absence of data
related to the precursor properties.
CONCLUSIONS
The ultrasonic spray pyrolysis method was applied to the direct preparation of
superconducting fine powders in the Bi-Pb-Sr-Ca-Cu-O system. It was found that spherical,
uniformly distributed submicron powders with the dominant content of 2223 phase were
obtained. The results imply possibility of powders morphology and size control by
optimizing preparation conditions. Particle formation can be considered as the case when
one particle is obtained from one droplet, without the droplet coalescence effect. High
reactivity of the particles and appearance of the liquid phase produce pendular/funicular
agglomeration stage as well as interparticle sintering and coherent structure formation. All
of these confirm that features of obtained powders meet the requirements of the starting
powders for sintering.
157
ACKNOWLEDGEMENTS
This research was financially supported by the Republic of Serbia Science Foundation
through the project "Prognosis of materials properties from the viewpoint of the synthesis-
structure-properties relationship". The autors would like to express their gratitude to
academician Momcilo M. Ristic, for his assistance during research presented here.
REFERENCE
1. N. Tohge, M. Tatsumisago,T. Minami,M.Adachi,Y. Kousakaand K. Okuyama, Preparation conditions
and morphologyof superconducting fine particles in the Bi-Sr-Ca-Cu-Osystem prepared by spray
pyrolysis, J.Am.Ceram.Soc., 74,9 : 2117 (1991)
2. K. Okujama, T. Seto, M. Shimadaand N. Tohge, Size-dependence of propertiesof superconductingBi-Sr-
Ca-O fine particles prepared by a spray pyrolysis method, J.Mat.Sci.:Materials in Electronic, 5
210 (1994)
3. M. Takano, J. Takaeda, K. Oda, H. Kotaguchi, Y. Miura, Y. Ikaeda, Y. Tomii, and H. Mazaki,
Superconductorwith Toequal 117K in the Bi-Pb-Sr-Ca-Cu-O system, Jpn.J.Appl.Phys., 27: 1041
(1998)
4. L. Mancic and O. Milosevic, Morphologyof multicomponentparticles in the Bi-Pb-Sr-Ca-Cu-O system
prepared by the spray pyrolysismethod as a functionof aerosol characteristics, J.Sci.Sint. , 30, I :
73 (1998) .
5. G. Zorn, B. Seebacher, B. Jobst and H. Gobel, Investigation offormationreactions in the system Bi-Pb-
Sr-Ca-Cu-Ooxide system starting from oxides and carbonates, Physica C, 177 : 498 (1991)
6. J.C. Grivel, F. Kubel, 1. Flukiger, DTAffG study of the formation of the (Bi,Pb)2Sr2Ca2Cu301ll+x
superconductor, J. Therm.Analys., 48 : 665 (1997)
7. G.L. Messing, SoC. Zhang, G.V. Jayanthi, Ceramic powder synthesisby spray pyrolysis,
J.Am .Ceram.Soc., 76, 11 : 2707 (1993)
8. L. Mancic and O. Milosevic, The influenceof droplet coalescenceon particle morphology of powders
derived by aerosol reactions, J. Min.Metall., 34, 1-2B : 37 (1998)
158
Part III. MECHANICAL ACTIVATION
INTERACTION OF THE POWDER PARTICLES WITH THE
PLASMA OF THE IMPULSE DISCHARGES AND THE USE OF THIS
PROCESS FOR CREATION OF PROTECTIVE COVERAGES
V .V. Mikhailov, A .E. Gitlevich

Institute of Applied Physics, Academy of Sciences of Moldova
2028 Kishinev
Plenum Press
New York, NY 10013
INTRODUCTION
At present the processes, based on interaction of low-temperature plasma stationary flows
with powder materials, are studied thoroughly in science and engineering and widely used in
production [1-3]. For example, plasma spraying of powders on detail working surfaces found an
application in industry for creation on them of wear-, heat- and corrosion-resistant coatings.
Stationary plasma flows are used to treat dispersed materials, to obtain spherical and fine- dispersed
powders, to synthesize refractory compounds, etc.
As for the processes, based on interaction of low-temperature plasma non-stationary
(impulsive) flows with powder particles, they are less investigated and their application is limited.
Such plasma flows (PF) are the most often formed at impulsing discharges in gases (gas-discharge
impulsive plasma originates) and have higher parameters according to the temperature, pressure,
rates, than stationary ones, e.g. obtained in industrial plasmatrons [1-8]. Moreover, at impulsive PF
the safety of composition and structure of coating particles and substrate is ensured owing to the
small time of particles-plasma interaction.
We've studied two variants of powder material particles - spark type impulsing discharge
plasma (condensed discharge) interaction under various conditions of powder particles entering into
the discharge channel. In the first variant the particles - low-voltage discharge plasma interaction
has been studied under the conditions of the fixed and varied with time interelectrode gap (IEG) at
voltage on the electrodes U 50.. .400 V, discharge energy W 5..50 J and particle entering into IEG
under gravitation action [6-8]. In the second variant powder particles - powerful (W 500 J) spark
discharge plasma interaction has been examined in the electrode coaxial system, ensuring formation
of impulsive high-rate flows (V 0,3+1,5 km/s) of plasma-powder particles two-phase system [4,5,7].
EXPERIMENTAL
Research technique. The first variant is a variety of the known process of electrospark
alloying (ESA) of metal surfaces by compact electrodes [6], carried out at low-voltage impulsing
discharges on account of electric erosion and the anode (instrument) material transfer to the cathode
(detail). ESA by compact electrodes side by side with merits has a number of demerits - a small
Advanced Science and Technology ofSintering , edited by Stojanovic et al.

Kluwer Acad emic/Plenum Publishers . New York. 1999 159
thickness offonned layers 0,1 mm, low productivity, as a rule 2.. .5 cm 2 /min, impossibility of non-
conducting material application, etc., which prevent from a wide utilization of this method in
production . If during such process the surface layer formation is realized not on the account of the
electrode-anode material, but on the account of powders, introduced into the gap between the
cathode-detail and the anode, it is possible to remove to a considerable extent the above mentioned
ESA demerits [6,8]. ESA process realization the powder materials being used in the first variant is
schematically presented in Fig. I.
Up=O,5 5kY R2
0
+
RI
+~_
.~; _A (()lK Fig 1. (a) Key diagram of electrospark
_U
C applying of powder material coating
coating a stationary electric field being
-1>-0 _ superimposed to lEG: A - working
electrode-anode; K -detail cathode; E -
bunker; C - energy capacitive storage;
+ ~ ..
.1....r:i' DI RI - ballast resistor; R2 - current-
Up C limiting resistor; D - dividing value.
(b) Key diagram ofESA by powder
materials a pulsed field being
TI T2 superimposed to lEG; D - dividing
value; TI, T2 - synchronization circuit
tiristors; C - energy capacitive storage;
Co ntrol un it
IT - peak transformer.
In the first device (Fig. I.a.b) coating formation is carried out without any contact between
anode and cathode-detail, in the second one the powder is supplied into lEG with a periodical
contact of anode with cathode-detail (Fig. 2).
As in the first device the lEG size is 0,3. .. 1,5 mm, and the process is conducted at working
pulse voltage Up - 50...400 V (at undervoltage regime), in order to initiate working discharges a
static field , voltage at the electrode being U - 3... 5 kV (Fig. l.a), or a weak-current high-voltage
impulse with U - 10.. . 15 kV (Fig.l ,b) is used.
RESULTS AND ANALYSES
Results and discussion. The field being static a particle, entering the lEG, becomes electrified
and moves to the cathode, where a microdischarge among the particle and the cathode takes place,
which plasma initiates the charge, playing the main role in melting and evaporation of particles [6].
Fig. 2 Scheme of a contact-powder variant of

coating applying: A - working electrode-anode; K -
G cathode-detail; B - vibrator; E - bunker with
powder; C - energy capacitive storage; G - supply
unit.
160
At high-voltage impulse a thin plasma column appears between the electrodes, and then a low-
voltage discharge originates. Plasma channel-particles interaction nature depends on its size,
uniformity and expansion rate, determined by the lEG size and the discharge parameters [8].
Powder particles (even of refractory materials) entering the discharge channel sphere, where energy
and temperature high densities (T~ 103 o C) are realized during very short time intervals (r - 5.10-5 -
3.10-3 s), may be heated till fusing and evaporation temperature. Polar transport and interaction of
the melted and evaporated material with the cathode-detail surface , on which partial discharge
energy release also takes place and melting and evaporation cells appear, lead to the interaction of
liquid and vapour phases of powder and substrate materials , causing phase, structure and other
transformations in the cathode surface layer. As a result of these phenomena a white layer with the
complex of corresponding properties is formed as a rule on the cathode surface and a high adhesion
of coatings with substrate is ensured .
As the investigation has shown the initiation of low-voltage high-current discharges by high-
voltage low-current impulses permits maximum realization of energetic potentialities of the
working pulse source at every discharge and the most useful utilization of the material of powder
particles entering the discharge channel [9].
Electrospark formation of powder coatings has a number of advantages in comparison with
ESA by compact electrodes. In the first place , coating material range is widened, as this process
allows to use semiconductors, dielectrics, including various oxides . Powder process permits to
obtain higher treatment productivity (2-3 times) and possesses a possibility of structure and phase
compos ition control owing to variation of powder mixture composition and the process parameters ;
powders make it easier to form coatings with thickness 0, I - 0,2 mm.
At the electrospark applying of powder coatings it is observed a complex of physicochemical
transformations in the forming layers, analog ous to the case of the ESA process taking place owing
to anode erosion [6]. Taking as an example the applying of variou s groups of materials (AI, Ni, Mo,
W, WC, B4C, CAn-3 , nrlJ.H80CP-4, ferroboral alloy powders, etc.) it was shown the coatings ,
formed by the considered method , usually consi st of several zones - white zone , applied material-
substrate interaction zone and zone of substrate material , subjected to the thermal influence of pulse
discharge. A typical structure of coatings is presented in Fig. 3.
It must be noted that non-etched upper layers of coatings are characterized by high values of
residual voltages analogous to the case of ESA by compact electrodes [6].
Roentgen phase and roentgen spectrum analyses show that the composition of the formed
layers is determined mainly by the nature of the used dispersed material.
Consider on some examples potentialities of ESA powder process. Electrospark applying of
powders at the non-contact variant (Fig . la) is promising in order to decre ase deformation of detail
working surface under the effect of cyclic loads [6]. At hardening of aluminum alloys AH-4, AH-9,
used at the production of radial bearings of crankshaft, powders Mo, Ni, nrX80CP-2, 80CP-4 and
I1n<1>-1 were employed to form coatings. Metallographic analysis showed that the thickness of the
obtained coatings is 100-150 urn, and their microhardness - 1145-1450 kg/mm". Relative
deformation tests of samples at cyclic loads approaching real ones appearing in the working engine
(load 6,5-13,5 tons changed with frequency 600 cycle s per minute amplitude being 0,3-0,5 mm)
showed that Ni and I1n<1>-1 coatings decreased AJI-9 and AK-4 alloys deformation 10 times, as for
rXP80CP-2 - 4 times.
Fig 3. Steel 45 microstructure, coated by Ni x200
161
I, Jldh I, Jlc/ h
12 12
8 8
1
:
/ 6
4 4
Q
I
0 2 4 6 8 10 t,h 0 8 t.h
Fig 4. Coating wearability rate kinetics, obtained for aluminum alloy from powder mixtures ;
copper-aluminum (2), nickel-aluminum (3), aluminum-graphite (4), copper-graphite (5),
titanium-graphite (6), nickel-graphite (7).
ESA compact-powder variant (Fig. 2) is effective enough to create wear-resistant coatings on

aluminum alloys . So when coatings ofCu, Ni, Ti, AI, graphite and their mixtures are applied on the
aluminum alloy AI-lOB [13], the layers, possessing wear-resistance 5-7 times more and coefficient
of friction 2-3 times less in comparison with the same properties of non-hardened surfaces, are
formed (Figs . 4-5).
The above-mentioned data show the powder electrospark applying method permits to create
formation technologies for the surfaces having a wide spectrum of operating characteristics.
The second variant of powder particles interaction is connected with high-speed flows,
created by a powerful discharge (PO) . Formation of pulse plasma flows, created by PO, and their
effect on powder materials may be realized in the systems analogous to shock electromagnetic
tunnels or pulse plasma accelerators [12,13]. For practical application the second ones are
preferable, as with their help it is possible to obtain plasma flows with a wide range of rates (from
several dozens till several thousands mls), that in its turn permits to control the rate and the
temperature of the applied materials, reaching (1...2).10 3 mls and evaporation temperature
correspondingly. Such parameters of the applied material flow ensure formation of coatings with a
high cohesion and adhesion strength, small porosity (:s; 1.. .2%), high values of density and
uniformity.
Formation of coatings with the help of PO is realized as a rule on the base of coaxial
accelerators (CA) of pulse plasma flows both on the expense of the central electrode erosion and the
powder material, introduced into the discharge zone or other parts of the accelerator. The powder
process is of the most interest thanks to a number of its advantages .
For powder material applying various construction schemes of CA and powder supply into the
plasma flow zone can be used [5,7,14] .
6
/
0,3
4
10
-------,-
0,5 1,5 2,5 0,5 1,5 2,5 P,MPa
Fig. 5. Coefficient of friction versus pressure in the contact zone at AJI -10 alloy coating test -
non-hardened (1) and with powder coatings (2-10). One-component powders of copper (2),
titanium (3), nickel (4), graphite (5), powder mixtures copper-aluminum (6), titanium-
aluminum (7), copper-graphite (8), titanium-graphite (9), nickel-graphite (10).
162
.z:z>.
2
5
3
Fig. 6. Schematic diagram of the installation for applying coating of powder materials by a
powerful discharge.
In order to heat and transport powder materials with the aim of forming coatings for various
functional purposes we investigated CA with the butt-end electrode system where plasma
acceleration occurs mainly because of the gradient, pressure and "electron wind" [13]. The
construction presented in Fig. 6 was used to realize this process. Powder (5) is poured into hollow
cylinder (2), being one of the electrodes, steel rod (4) - the second one, situated in the center of a
dielectric washer (3). When current pulse passes from condenser C through the discharge chamber
the powder is immediately heated to a high temperature, accelerated by plasma flow and applied to
the substrate (1). The discharge system was mounted directly on the conducting terminals of pulse
condenser battery the capacity being 70-280 ItF, terminal voltage being controlled in the range 103_
8.103 V.
Metallographic tests showed that at the interaction of metallized flows of copper, TiC+Ni
mixture with the substrate of steels 45, Y8 a transition zone, which microhardness may reach 700-
llOO kg/mnr', appeared in the surface layers, situated under the coating layer. Increase of the
discharge energy and reduction of the spraying distance lead to the growth of the reinforced zone
thickness that correlates with the change of plasma flow rate. Evidently, the momentary heating of
surface layers in the zone of plasma-powder flow effect till evaporation temperatures and the
following sharp hardening and the action of high pressures are the reasons of structure
transformations and microhardness increase. Such a reinforcement could be also observed at the
influence of plasma flow without powder particles.
With the help of PSD it is possible to obtain effective heat- and corrosion-resistant coatings
from aluminum and its alloys, compounds of aluminum with nickel, etc.
In conclusion it must be noted that the discussed method as one of the most universal gives
an opportunity to model nearly all forming methods of coats obtained from powder materials,
beginning with gas-flame ones till explosive, without any transporting gases, as the material
acceleration and displacement is realized owing to electrodynamic and gas dynamic forces, and
their heating by pulse plasma ensures a wide range of particle temperatures from fusing till boiling.
Pulse plasma flows with powder particles permit to form coats of any metal and ceramic materials,
if they could be obtained as powder of a certain fineness (~l 0.. . 1000 11m)
REFERENCES
1. Plasma processes in metallurgy and inorganic material technology. Paper collection dedicated
to N-N. Rykalin 70 - years jubilee Nauka, Moscow, 1973, p.243 [In Russian]
163
2. Kudinov V.V. Plasma coatings. M. Nauka, 1977, p.184 [In Russian]
3. Hasui A., Morigaki O. Surfacing and spraying. Trans. Japan. Machinostroenye, 1985, p.239
4. B.R. Lazarenco, AE. Ghitlevich, V.N. Tkacenko, S.P. Fursov Influence of spark discharge on
powders. Electron treatment of materials. 1997, No.4, p. 20-21 [In Russian]
5. B.R. Lazarenco, A.E. Ghitlevich, V.N. Tkacenko, S.P. Fursov Powder particles acceleration by
gas discharge plasma and their interaction with solid. Electronnaya obrabotka materialov,
1973, no. 5, p.31-33. [In Russian]
6. AE. Gitlevich, V.V.Mikhailov, N.Ya. Parkanskii, V.M. Revutskii, Electrospark Alloying of
Metal Surfaces, Kishinev, 1985, 196 c. [In Russian]
7. D. A Gasin, B.A. Urukov Movement and heating of particles in coaxial accelerator. Sibirian
dep. AS. USSR Mems, tech. sciences. ser, 1985, No. 16, p.92-99 [In Russian]
8. A.E. Ghitlevich, P.A. Topala, V.M. Revutskii, L.N. Shistik Powder particles - pulse discharge
channel interaction under the conditions of electrospark coat alloying. Electron treatment of
materials, 1998, No.6, p. 20-25 [In Russian]
9. AE. Ghitlevich, N.Ya. Parkanskii, V.M. Revutskii, V.V. Mikhailov, Method of electrospark
applying of coatings. Inventor's certificate No. 837716, Byul. No.15, 1985.
10. V.v. Mikhailov, A.E. Gitlevich, V.M. Revutskii and A.P. Abramchuk, USSR Inventor's
Certificate No. 1151403 "Method of applying coatings and clevice for cloing it", Byul.
No.15,1995
11. A.P. Abramchuk, G.A. Bovkun, V.V. Mikhailov, Iu.G. Tkacenko Antifriction coatings on
aluminum and its alloys, formed by electrospark allaying from powder materials. Powder
metallurgy, 1989, p.23-26 [In Russian]
12. P.M. Kolesnikov Plasma electrodynamic accelerators. M. Atomizdat, 1971, p. 389 [In Russian]
13. Morozov LA. Plasma accelerators. A.S. USSR Bulletin, 1974, no.1, p.15-23
14. V.M. Golubets, V.V. Shvets, G.N. Lukina Forming heterogeneous flows at impulsplasma
spraying. Physico - chemical mechanics of materials, 1991, No.7, p.60-66 [In Russian]
164
MECHANICAL ACTIVATION OF BaC03-Ah03-SiOz
S. Boskovic', B. Kosanovic', B .Bahloul-Houriier3, P.Thomas 3, S.Kis l
lInstitute of Nuclear Sciences-Vinca, Mat.Sci .Lab.POB 522, 11001,

Belgrade
zRefractory Institute Magnohrom-Kraljevo
3Laboratory for Ceramic Materials and Surface Treatment of the
Limoges University, France
ABSTRACT
A BaC03-Alz03-SiOz mixture was mechanically activated for 2 and 4 hours.

Chemical composition of the mixture corresponded to BaAlzSizOs. Reaction course was
followed in the temperature range 750 o-1200C as a function of activation time. Reaction
of celsian formation was followed using thermogravimetry as well as conventional and
high-temperature X-ray diffractions. The obtained data show that reaction rate increases
with prolonged activation time, under the same conditions of thermal treatment. Formation
of hexacelsian was favoured with increasing activation time . Formation of monoclinic
celsian was retarded, with longer activation .
INTRODUCTION
Ba-aluminiumsilicate has attracted much attention lately because of properties which

make it suitable for numerous applications It is, expected that BAS will be applied for high
temperature ceramic matrix composites. The properties which make it suitable for use in
ceramic matrix composites are its high melting temperature, low density, thermodynamic
stability and low CTE. BAS is therefore used as a matrix for alumina, SiC and C fibers,
and Si3N4
Reaction paths to celsian from BaC03-Alz03-SiO z mixture were studied by several
authors 1,2. Formation of BaAlzSiOzOs was observed at 900-1150C via Ba-silicate - path
(1)
(1)
or via Ba-aluminate, - path (2)

K1uwer Academic/Plenu m Publishe rs, New York , 1999 167
BaAh04 + 2SiOz= BaAhSizOs (2)
Independent of the preparation procedure, whether by glass crystallization or solid

state reaction, hexacelsian although metastable at these temperature, is the first to form.
Published data),4 point to the increased rate of solid state reactions and phase
transformations due to introduced mechanical energy in the system during activation. This
method is applied in our work with the aim to enhance the reaction of BAS formation from
BaCO), a-AhO) and SiOz (quarz). On the other hand the changes of the physical
conditions of the reactants including steric factors caused by mechanical activation, are
expected to affect the reaction path to celsian .
EXPERIMENTAL WORK
Mixture of BaCO) ("Zorka"-Sabac), s.o, (u-quarz "Merck"), and a-AhO) ("Alcoa",

A-16), the composition of which corresponded to BaAhSizOs, was mechanically activated
in vibratory mill made of WC (Fritsch-Pulverisset-9). Twenty grams of mixture was
activated for 2 and 4 hours. The non-activated mixture was, however, milled for only 2
min. The changes developed during milling were followed by X-ray diffraction, specific
surface area measurements and thermogravimetry. Reaction course was also followed by
high-temperature X-ray diffraction in the temperature range of 800-1200C. Heating rate
was 40 Imin .
Formation of celsian is a complex process involving a series of intermediate reaction

steps. Mtlhler-Hesse et all showed that starting from BaCO), y-AhO) and SiOz
(amorphous or quarz), BaSiO) and Ba zSi04 formed first at 650C. The reaction thereafter,
proceeds via several reaction steps', to give sunbornite, which finally reacts to form BAS
via reaction path (1).
Our results show the effect of mechanical activation time on the structure of BaCO)-
AhO)-SiOz mixture. X-ray patterns of non-activated - A, as well as activated mixtures B
and C show that with increasing activation time, the intensities of BaCO), SiOz and AhO)
diffraction lines decrease, and the broadening of the diffraction lines takes place. New
compounds were not detected. Besides micronization, amorphization and the distortion of
the crystal lattice is brought about during mechanical activation. Thermogravimetric
analysis of the three mixtures, revealed that with prolonged activation time the onset of
weight loss was shifted towards lower temperatures. Moreover, the reaction course of
weight loss appeared to be different for different activation time. While in non-activated
mixture decomposition starts at 1000C, and proceeds in a single step, with prolonged
activation time, two-step process gradually becomes evident (at 750C and 1160C). At the
same time the onset of weight loss was shifted below 500C. To show how far the reaction
advanced in the range of the first and second steps samples were heat treated at 750C and
1l60C for 30 min. X-ray analysis of samples heated at 750C (Fig.l), shows that the
relative intensities of the diffraction lines of all the reactants decrease with increasing
activation time. The advanced reaction in activated mixtures in comparison with non-
activated one, is easily recognized on the basis of the type of Ba-silicate formed under the
same conditions. Namely, in early stages of the celsian formation BazSi04 is formed in
non-activated sample, while sanbornite is formed in both activated samples which means
168
600
BaC03

750C
o AI 2
500 lIE SiO
3
2
S Ba
400 2Si04
~
.;n
-
300
c: A
Q)
E
200 0
100
20 40 60 80
20
400
750C BaC03
300

AI2 3
SiO
2
S BaS i
20S
0
200
~
.;n 0
c:
2c: B
100
20 40 60 80
20
Fig.l . X-ray patterns of samples A, Band C heated at 750C -30 min.
that the conditions in these samples are convenient for immediate development of the
reaction (1).
In samples heated at I I 60C, for 30 min (Fig.2) reaction advanced in comparison
with data for 750C. In non-activated sample - A, beside celsian , Ba2Si04, Ba 2ShOg and
BaAh04 are detected. After 2 hours of activation, sample B contained hexacelsian (Fig.2
middle), which is the dominant phase. Besides, celsian, alumina and Ba-silicates are
detected . Hexacelsian is also dominant phase in 4 hour activated sample - C (Fig.2
169
III
350
750C BaC0 3
300 o AI
203
)l( SiO
2
250 S BaSi
20S

~ 200
en
c:
Q) c
c: 150
100
50
0
20 40 60 80
20
Fig. 1. Continued
bottom), while celsian content is very low. In addition, alumina and Ba-silicates were
detected. These data (Fig.l and 2) show not only that the reaction to celsian is enhanced by
mechanical activation, but also that different polymorphs of BaAhShOg are formed
depending on activation time.
By comparing the results in Figs.l and 2, it can be concluded that in the case of non-
activated sample - A, BAS is formed mostly via intermediate reaction products - Ba-
silicates, starting with orthosilicate - reaction path (I), Orthosilicate is mainly formed by
reaction of BaC03 and Si02, since BaO was not detected in our samples. The presence of
400,...---------------------------,
1160 C lI( Ba Si0

2 4
300
o BaAI 0
2 4
)l(
Ba2SiP e
c celsian
~ 200 lie
enc:
- A
)l(
0
Q) )l( c C
.E lie
100
20 40 60 80
28
Fig. 2. X-ray patterns of samples A, B, and C, heated at I 160C - 30 min.
170
BazShOg shows, that reaction of other silicates and SiOz must have taken place. Great
variety of Ba-silicates (Fig.2) were found in activated samples (B and C) contrary to
sample A. The existence of these silicates - BaSi03, BazShOg and BasSigOzl confirms that
the reaction proceeds via reaction path (1). The fact that these silicates are detected in the
samples is due to better homogenization of constituents particles, achieved during
mechanical activation . This means that steric factors, changed during mechanical
activation, enabled more reaction sequences' to be detected.
Experimental data obtained under isothermal conditions after 1 hour of annealing in
high-temperature X-ray device (Tab.l), indicate that some amounts of BaAh04 may be
formed from BaC03 and alumina in sample AS. However, the fact that the amount of
300
h
1160 C h hexacelsian
250

C celsian
o AI2 3
200 h BaSi0
3
Ba
~ C h h
0
sSie0 2 1
iii 150
c:
2c: c c B
100
50
20 40 60 80
28
h
800 1160C h hexacelsian
c cels ian
Ba i
sS e0 2 1
600 h
Ba
2Si 3Oe
A IP3
~ h
iii 400 C
-
c:
Q)
E
200
20 40 60 80
281
Fig. 2. Continued
171
BaAh04 increases, while the content of Ba zSi04 decreases simultaneously, at higher
temperatures at which BaC03 had already been consumed points to the development of the
reaction", i.e.
(3)
Table 1. Detected phases depending on activation time and temperature
Sample Non-activated 2 hour activated 4 hour activated

BAS m,Ba zSi04 BAS m, BazSi04 tr.
Ah03, SiOz BaAh04, tr, Ah03,SiOz
900C Ah03, Ba zSi04 BAS m, BazSi04, BAS m,h, BaAh04
BaAh04 tr, BAS m,tr. Ah03
1000C BAS m, BaAh04 BAS , m,h, BaAh04, BAS h, BaAh04
Ba zSi04 Ah03
1100C BAS m, BaAh04 BAS h.m, BaAh04
Ba zSi04
1150C BAS m, BaAh04 BAS h,m, BaAh04
Ba zSi04
1200C BAS m, BazSi04, BAS h.m, BaAh04 BAS h, BaAh04 tr.
BaAh04, Ah03 tr.
The presence of BaAh04 which appears also in activated samples only at longer
heating times, indicates the development of reaction path (2), at higher temperatures
(Tab. 1, Fig.2) in all the investigated samples. According to these results the contribution of
reaction path (2) to overall reaction of celsian formation decreases with increasing
activation time . Results in Tab . 1 also prove that at 1200C, 1 hour, also BaAh04 content
decreases with increasing activation time , which means that the reaction is very close to an
end at longer activation times and is almost complete for sample C.
CONCLUSION
Mechanical activation enhances reaction of BaAhSizOg formation. Reaction path to

celsian is dominantly developing via series of intermediate reaction products - Ba-sil icates .
At higher temperatures or longer heating times, the reaction of BaAh04 formation takes
place . Reaction path via BaAh04 plays more considerable role in non-activated mixture, in
comparison with activated samples. Thus, mechanical activation affects the mechanism of
BAS formation.
With prolonged time of mechanical activation the content of monoclinic celsian
decreases, while the amount of hexacelsian increases at the same time . The conditions for
hexacelsian nucleation in activated samples may be connected with increased particles
surface which favours the nucleation of hex acelsian.
REFERENCES
1. J.E.Planz, H.Mtiller-Hesse, Ber .Detsch.Keram.Ges., 40 (1963), H 3, 191-200

Untersuchungen tiber Festkorperreaktionen im System BaO-Ah03-SiOz Teil II:
Uber die Celsianbildung durch Festkorperreaktionen.
2. S.W.Quander, A.Bandyopadhyay, P.B.Aswath, Synthesis and Properties of in situ
Si-Na-reinforced BaO .Ah03-SiOz Ceramic Matrix Composites, J.Mat.Sci. 32
(1997) 2021-2029.
172
3. E.Kostic, S.Kiss, SBoskovic, S.Zec, Mechanical Activation of the gamma to alpha
transit ion on Ah03, Powder Technology, 91 (1997) 49-54.
4. E.Kosti}, S.Kiss, S.Boskovic, Decrease of MgAh04 formation temperature, Powder
Technology, 92 (1997) 271-274 .
5. S.M.Allameh, K.H.Sandhage, Synthesis of Celsian (BaAhSi 20 g-from Solid Ba-Al-
Ah03-Si02 Precursors: I, X-ray and SEMIEDX Analyses of Phase Evolution,
J.Am.Ceram .Soc., 80/12/3109-26 (1997) .
173
MECHANOCHEMICAL SYNTHESIS OF NANOPHASED
CARBIDE TiC
LUvarova, M.Savyak, LTimofeeva, L.Isayeva
Institute for Probleme of Materials Science NAS Ukraine
INTRODUCTION
At topochemical reaction of interaction between two or more solid phases , the new
nucleus is formed in most defective places on the surface of initial phases. Later the nucleus
growth is taken place along with nucleation. The particle size of new phase will be
depended on the correlation between rates of nucleation and nucleus growth. Nucleation
velocity as well as nucleus growth rate increase with temperature. It is known , that the
correlation between rates of nucleation and nucleus growth is higher the dispersivity of
reaction products must is bigger. If the nucleus confluence (coalescence) is absent the
degree of dispersivity can be so large that X-ray line will be not resolved . There is initial
temperature of heterogeneous reaction, the more number of small new phase nucleus and in
low initial temperatures the small number of more large particles are formed .
Thus, the processes of coalescence decrease at lowering the initial temperature of
topochemical reactions . However, in normal conditions an every reaction is taken place
only at the definite temperature, which is depend from thermodynamic and kinetic
parameters. Therefore it can not be avoided the coalescence of new phase particle at
heterogeneous topochemical reactions, which is taken place with heating.
Let us examine the nucleation under topochemical solid reactions, which is taken
place at mechanochemical interaction . In this case the processes of chemical interaction
take place in low temperatures at the expense of superfluous tension which is arose in
"sock" of crack during intensive milling . Changing the range of particle dimension, the
density of dislocation system, the size of mosaic block we can be change the reaction ability
of reaction components. For formation of the product at chemical reactions it is need the
energy on generation the interfaces. Such value is directly proportional to square of these
surface [I].
0- free surface energy, r - characteristic size of the new phase nucleus, b - constant, which
Advanced Science and Technolo gy of Sintering , edited by Stojanov ic ct al.

depend from nucleus form. For example b = 41t for spherical nucleus.
It is known that the state of defective and neighboring atoms is distinguished form
the state in ideal crystal grate. The crystal defects play the definite role in topochemical
solid reactions. The defects can be facilitate the nucleation and be the center of nucleation.
The defects influence on the velocity of diffusion in solid. The defects can be taken part in
chemical stages. The study of defect's role can be explained why the some reactions are
passing in different way at the same conditions . Sometimes the reason of this difference is
the new surfaces. The defective structure of solid reagent in chemical reactions, taking
place under intensive milling is definite. In different from heterogeneous and solid reactions
which are passing at high temperatures, mechanochemical reactions is taking place in low
temperatures. To increase the reaction rate and to decrease the reaction temperature can be
by means of increase the number of potential nucleus. The potential nucleus can be the
defects, which is produced under intensive milling. The rate of nucleus growth is changed
more difficult, since it depend from defects not enough. The chemical processes under
intensive milling is taking place in the points of concentration of stresses at contact of
milling solid phases in consequence of the local liberation of heat and simultaneous rise of
very high pressure and shearing stress in this region of crystal. The top of moving crack
under failure of milling material is a second place of chemical processes. Here shearing
stress and the local liberation of heat are concentrated the same. In these cases the methods
of atoms excitation are distinguished from heat treatment. It was shown in the works of
novosibirsk scientist [I] the surfaces of prick is keeping the active center a long time after
crack was moving.
Thus, the main reasons of change of chemical activity during intensive milling are:
the formation of the new surfaces and dispersivity;
the formation of crystal defects;
a local liberation of heat.
It's known [2-6] that nanophased powders of refractory metals and carbides on their
base can be prepared by low temperatures reduction and carbonization in different gas
medium. It is a question - can be avoided the coalescence at topochemical heterogeneous
and solid reactions with use of heating.
The previous study was established that the coalescence at topochemical
heterogeneous and solid reactions with use of heating could not be avoided. For decrease of
a coalescence and nanophased powder production it is necessary to decrease of initial
temperatures of chemical reactions. This can be achieved at the expense of activation either
the chemical reaction (the use of catalyst) or the solid reaction reagents. Since in normal
chemical reactions we can not be avoid the heating of reagent it may not be avoid the
coalescence.
EXPERIMENTAL
Let us consider the reactions of mechanochemical synthesis, which can be passed

without heating. To compare how can be change the activity of reaction component at dry
milling on example of system Ti-C.
2/g)
Elemental powders of titanium (S=O,12 m , sponge titanium (S=O,05 m2/g),
2/g)
rolling titanium and carbon black (S=1O,5 m were mixed to the required proportion in
planetary ball mill at room temperature with stainless steel balls (6 mm in diameter) in air
and in nitrogen. The weight ratio of powder to ball was 1:3. The ball milling process was
periodically interrupted to remove powder portions for X-ray analysis and study the specific
surfaces.
176
Changes in X-ray diffraction patterns of 50 Ti (sponge)-50 at %C after different

milling times in air are shown in Fig 1 (a-d) for (the first sample portion was took after 15
min of milling ) and (e) (the first sample portion was took after 45 min of milling). It can be
seen from Fig.l that after 15 min milling the lines of reflection from carbon black
disappeared and the lines of reflection from titanium direct to side of small angles. This
characterized the increase of its intersurface distances and is a ground of the formation of
solid solution of carbon in titanium. The increase of intensity of line reflection from surface
(002) Ti after 15 min of milling in air can be indicated that the localization of dissolved
carbon atoms occurs mainly in this crystal plane thus the conditions of disintegration
powder texture. Let us notice that the X-ray line Ti0 2 oxide is also present at milling in air.
It is very interest that the periodically interruption of the proces s for removing of powder
portions for X-ray analysis and study the specific surfaces increase the content of oxygen
and impair the condition of interaction between titanium and carbon (compare Fig. 1 d and
e)(Table 1,2).
Table 1. The characteristic of milling products in air and nitrog en

I
I
No Milling X-ray analysis S, Milling X-ray ana lysis S,
time, min
On air
2
m /g time, min I On nitrogen
I m
2/g
1 15 aTi 48 15 aTi 42
2 20 a Ti, trace Ti0 2 38 20 aTi 44
3 25 a Ti, trace Ti0 2 48 25 TiC , trace Ti 13
4 30 a Ti, trace Ti0 2 24 30 TiC , trace Ti 13
5 35 TiC, trace Ti 13
6 40 TiC , trace Ti 13
7 45 a Ti, TiC (w.) 21 45 TiC, trace Ti 13
Table 2. The characteristic of milling products in air (the first sample portion was took after
30 min of milling)
I I
I
No Milling time, X-ra y analy sis
min
1 30 a Ti, trace TiC 34
2 45 TiC, trace Ti 12,4
3 60 TiC , trace Ti, trace Ti0 2 27
4 75 TiC 23
In order to avoid the influence of oxygen the milling was be realize d in atmosphere
of nitrogen. The medium was supp lied by liquid nitrogen, which was filled in mill before
the milling . Changes of X-ray diffrac tion patterns after different period of milling in
nitrogen are shown in Fig 2.
The change of specific surfaces at milling in air was shown in Tab le 1-2. Let us
attention that the specific surface is increased in the first moment of milling whe n the
formation of TiC is not observed. When we can assume the formation of nucleus of TiC the
specific surfaces decrease. In the case of milling in nitrogen this fact is more marked. It can
be seen that the compound of TiC is formed after 25 min of milling in nitrogen . It is very
interest that after 20 min of milling X-ray line TiC is not shown and after additional 5 min.
of milling it is shown.
177
Let us attention on the influence of nature of titanium. Early we consider the sponge
titanium , now we consider the rolling titanium. Changes in X-ray diffraction patterns of the
mixed rolling titanium and carbon powders after different milling times in nitrogen are
shown in Fig 3. It can be shown the rolling titanium did not interact with carbon even after
1 hour of milling in nitrogen and a very weak interaction begin after 1,5 hour of milling in
nitrogen.
b)
c)
tl~i
I~~i
44 42 40 38 36 34 32
'bL A
44 42
I
40
i
38 36
20 (0)
34 32
Figure 1. X-ray diffraction patterns of Ti-C powder Figure 2. X-ray diffraction patterns of Ti-C powder
milling for various times in air millied for various times in nitrogen
The first sample portion was took after 15 min The first sample portion was took after 15 min.
The line ofTi:a-15; b-20; c-30; d-45 min The line ofTi:a-15; b-20min ;
The first sample portion was took after 45 min. The line ofTiC c-25; d-30; e-45 min
The line ofTiC (e)
178
a)
I~
Figure 3. X-ray diffraction patterns of rolling titanium and
44 42 40 38 36 34 32 carbon powder milled for various times in nitrogen:
a-I hour the line ofTi
20 (0) b - 1.5 hours the line afTiC and Ti
CONCLUSIONS
The following assumption and conclusion can be made from this data.
The dispersive and defective structure were formed under milling in gas. Besides the
strong increase of specific surfaces during the intensive desperation in gas the activation the
dispersed products favors the solid interaction during milling. The presence of nitrogen in
planetary ball mill favors the acceleration of the interaction between titanium and carbon.
The X-ray lines of titanium carbide were founded after 45 min of milling in air and after 25
min of milling in nitrogen. The main phase solid solution of carbon in titanium is after 20
min of milling. Apparently the presence of nitrogen medium, protected the new formed
surfaces of titanium during milling from oxidation favors the development of the
pseudocircuit reactions, which was began in the top of moving crack. The temperature of
planetary ball mill is very increased in the moment of TiC phase formation. The sharp
transformation from solid solution of carbon in titanium to titanium carbide and added
heating of planetary ball mill in this period allow to assume the possibility of
mechanochemical explosion.
REFERENCE
I. V.V.Boldurev, N.Z.Lyachov, A.P.Tchuchachin The chemistry of solid, S.Chemistry, "Znanie", M. 1982

(in Russian)
2. V.V.Skorochod, Yu.M.Solonin, I.V.Uvarova Khimicheskie, diffuzionnye i reologicheskie processy v
technologii poroshkovyh materialov, Naukova dumka, Kiev, 1990 (in Russian)
3. l.V.Uvarova, Mechanism processa dispergirovaniya i relaksacii poverhnosti na nachalnyh etapah
prohozhdeniya geterogennoi reakcii, in "Fizikohimiya ultradispersnyh sistem", Nauka, Moskava, 1987,
pp. 230-237 (in Russian)
4. l.V.Uvarova , Fenomenologicheeskie aspecty dispergirovaniya productov pri topohimicheskih reakciyah
vosstanovleniya metallov iz oksidov, Poroshkovaya metallurgia, 1990, N 2, S. 55-65.
5. l.Uvarova , Processes of Surface Energy Relaxation in Topochemical Reactions, Sci. Sintering 1994,
26(3), P.245-250
6. l.Uvarova, T.Babutina, I.Timofeeva, A.Bukov, I.Slus, Nanostructured Compositio of Diamond -WC-Co,
Proceed. of the 14 Intern. Plansee Seminar, 1997, v.2, P. 730-734.
7. K.B.Chelimov, P.Yu.Butyagin, 0 vzruvnom mechanizme synteza tugoplavky soedineny .-DAN AN
SSSR.-1991 -316.-P.1439-1445
8. A.G.Merchanov Ucpechy ximii-Xl, V, -1976, 828-848
179
MATHEMATICAL MODELING OF COMBUSTION-TYPE INTERACTION
DURING MECHANICAL ALLOYING
B.B.Khina l and Yu.S.Sholpan2
'Physicotechnical Institute, National Academy of Sciences, Minsk, Belarus

2Polytechnic Institute, Chishinau, Moldova
INTRODUCTION
Mechanical alloying (MA) has received considerable attention from materials scientists
not only as a versatile method for producing materials with unique properties
(nanocrystalline alloys, supersaturated solid solutions, amorphous phases, etc.) but also due
to the unusual phase and structure formation mechanisms involved."? In a number of
systems with large negative enthalpy of mixing, combustion-type interaction has been
observed during MA.6-17 This phenomena was named "combustion synthesis by mechanical
alloying" (CSMA) :6 after an incipient period (plastic deformation/welding of particles, grain
size refinement and increase of the contact area), the conversion of reactants into a final
product occurs in a short time as a self-sustaining exothermic reaction . The instant of
"ignition" is marked by a sharp temperature increase registered by a thermocouple attached
to the outer surface of the vial. In most of the systems where CSMA was observed (CuO-M
(M=Ca, AI, Ti, Fe, Mg),6-10 Ni_AI,ll,12 Mo-Si,13 Ti-Ni,14 Ti-C-Ni/s Fe304-Al,16 Sn-Zn-S,17
and others) there was no noticeable product formation before the temperature peak, and
almost complete conversion to the final product in a short time after it. Characterization of
the particles immediately after the exothermic peak suggested that the interaction mechanism
involved melting of one or both of the reactants and solidification of the product from the
melt.6-8,12-16
According to Ref. 4, a combustion-type reaction in MA is not an "exotic" phenomena: it
can take place on a grain-by-grain basis in many systems having large negative heat of
mixing and hence remains unnoticed in a bulk-averaged investigation. The occurrence of
combustion during MA in strongly exothermic systems is usually prescribed to the
accumulation of defects due to plastic deformation and reduced grain/lamellar size, which
increase the diffusion rate of the interacting species. At a certain stage of the process, an
occasional collision can trigger an exothermic reaction in particles.4-6,ll,18
The effect of an interface kinetic barrier on the self-ignition of multilayer Ni-AI thin
films has been examined in Ref. 19 Here we intend to stress the role of contact surface area of
reactants .
Ad vanced Science and Technology 01 Sintering , edited by Stoja novic et al.

Certain aspects of CSMA resemble the phenomena observed in the combustion
synthesis, or the so-called self-propagating high-temperature synthesis (SHS):20-23 high
temperature and high heat release rate due to exothermic reaction, fast accomplishment of
interaction, occurrence of a transient liquid phase, and relatively fast cooling. However,
structure formation processes in the SHS wave and those during CSMA proceed on a
different spatial scale: in CSMA the reaction-diffusion of interacting species occurs in a
lamellar particle formed during the incipient period of milling (particle size 50-100 urn,
typical lamellae thickness 0.5-1 urn) while in SHS the interaction occurs in a zone containing
several unlike particles (particle diameter 1 to 100 urn with a relative porosity of the charge
mixture 0.3 to 0.7). Hence, a large contact area is an important factor .
The purpose of this research is to develop a simple model of the CSMA mechanism
using an analogy between CSMA and SHS. For numerical estimates, the Ni-AI system,
where CSMA has been observed ll ,12 and the reaction-diffusion parameters are available,19,24-
26 has been chosen as an example.
MODEL AND ANALYSIS
In SHS processes, structure formation mechanisms are complex and include several
stages.20-23 During heating in the preheat zone of the SHS wave, a thin film of an
intermediate product forms at the contact of unlike particles (e.g. intermetallic compound in
M 1-M2 systems'" or carbide in M-C systems.21,27 The major conversion of reactants into the
product is associated with melt formation.21-23,27,28 Melting and spreading ofa lower-melting-
point reactant and/or the formation of a eutectic melt bring a larger portion of reactants into
contact, the intermediate products and higher-melting-point reactant dissolve, and the final
product solidifies from melt. The characteristic spreading distance in the SHS wave is
comparable with the particle size. Typical example of such mechanism are Ti_C,21,27 Ti-C-M
(M=Ni,Co,Cr)28 and many MI-M2 systems." The final structure formation occurs in the so-
called post-reaction zone where sintering and other processes take place.20-23,27
Unlike SHS, in MA there is no heating from an external source, but if one of the
reactants is melted in a composite particle formed due to fracturing/cold welding, no
spreading is required to bring the components into contact. The heat necessary for melting
can be released due to the formation of an intermediate compound on the interfaces, which is
later dissolved in the melt. Thus, the following mechanism of CSMA is proposed .
After a certain critical state of the lamellar particles is reached, conversion into the final
product occurs within a short time as a combustion-type reaction triggered by an incidental
collision. The characteristic collision time, to, can be estimated within the mechanistic
approach" based on the Herzian collision concept. For a SPEX-800 shaker mixer/rnill" to=
3.IO-s s. The characteristic time of particle cooling is orders of magnitude larger", 10-4_10-3
s. Besides, in the mechanistic model" it is assumed that all the powder has stuck to the balls
and the vial wall while the elastic constants used in the formulas are those for the balls, i.e.
damping by the less-elastic powder layer is not taken into account. So, for the model
estimates, we assume the characteristic time to be tc10-4 s.
The temperature rise of a particle due to impact (implying that all the plastic
E
deformation energy dissipates as heat) is small:" ~T=[l/(dCp)] ~E ::::IS-10C for AI, 30

o
C for Fe, where E is strain, o is stress, Cp is specific heat per unit mass and d is the density.
However, this short-term temperature rise combined with plastic shear along the interfaces
in the lamellar particle can bring about the nucleation of an intermediate compound. As
shown in thin-film studies," the first phase to form at the interface is not necessarily the final
182
phase (e.g., NiAh in thin-film Ni-AI diffusion couples"); its nucleation is determined by
kinetic factors and not by thermodynamics. The heat released due to the intermediate phase
formation is expended in heating the particle. The heat sources are located on the lamellae
interfaces whose typical thickness is about 0.2 to 0.5 J.Ull.31 The characteristic distance of
conductive heat transfer L T - (atc)1 12 ~ 90 um for AI, 50 um for Fe and Ni, 20 urn for Mo,
where a = A./(dep) is the thermal difusivity, A is thermal conductivity.f far exceeds the
lamellae thickness. Hence the particle can be treated as thermally thin .
Assuming adiabatic conditions for a particle, the heat balance equation is written as
dj<>S[L1H~98 (i) + Tyc p (i)dT] + (x ~ - x~) d j<>S)[L1H m(A) + Tycp (A)dT]

298 To
(1)
+ [(1- x~) - (1- XT)dj<>S)]TYcp(i)dT= 0

To
where d is density, subscript "i" denotes the intermediate compound, Mr'298 is the standard
enthalpy, MI",(A) is the fusion enthalpy of the lower-melting-point reactant A, <> is the
intermediate phase thickness, To is the temperature in the mill (according to our
measurements, To = 40-50 "C), XOA and x<\ are the mass concentrations of A in the initial
charge and the intermediate compound, correspondingly, S is the NB contact surface area in
the lamellar particle per unit mass, Tad is the adiabatic temperature. Here Tad = Tm(A).
To define S, assume that a particle has a cubic shape of a size F with a lamellar spacing
A=AA+AB (Fig . 1). The NB contact surface area in an individual particle is SI=F 2(2F/A-
1)~2F3/A, the particle mass is rno=F3/[xO~dA+(1-xOA)/dB)]. The specific contact surface area
(2)
where kg is the geometrical factor allowing for the fact that the lamellae are convoluted and
the contact surfaces and non-planar (see Reel), its reasonable value is 2 to 10. Numerical
calculat ions for CSMA in the Ni-AI system (the first phase to form is NiAl3) with the charge
composition Ni 50Aho are presented in Fig. 2. At S=5 m2/g, which corresponds to A=0.5 urn
and kg=6.5, the NiAl3 thickness necessary to provide enough heat to attain Tm(AI) and to
melt aluminum is about 20 nm.
The heat release rate is determined by the compound layer growth rate, which is
controlled by the interface reaction kinetics or by solid-state interdiffusion.P'" As the
diffusion rate in intermetallics is usually orders of magnitude lower than in terminal solid
solutions, the diffusion transport of atoms through the compound layer is the rate-limiting
stage . The formation of a new phase in solid/solid systems is actually a lattice
transformation, " and thus it is difficult to imagine how a newly formed phase can "inherit"
the lattice defects (vacancies and dislocations) accumulated during plastic deformation in the
parent phases . Thus, within this model, we assume that the newly formed phase is defect-
free, and use the diffusion parameters reported in the literature for intermetallic compound
growth in thin-film and bulk diffusion couples. In the Ni-AI system, the parabolic growth
26
rate constant for NiAl3 is: Kp=0 .387exp[-(1.4 eV)/(kBT)] crnvs. Implying that the
temperature corresponds to Tm(AI), we obtain the NiAl3 thickness grown during the
characteristic time <> ~ (Kpt c)1 12 ~ 10 nm. Thus, the thermodynamic and kinetic estimates are
within the same order of magnitude.
As melt spreading is not required to bring the reactants into contact, the diffusion in the
melt is the rate-limiting stage. For most of the metallic melts, the diffusion coefficient in near
183
the melting point is Dm~10-S cm2/s (e.g ./ 4 for AI at Tm=933 K D m=1.35xl0-s cm%). The
characteristic diffusion length LD - (Dmtc)112 "" 0.3-0.4 J.11n, which is close to the lamellae
thickness . Thus, diffusion in the melt is fast enough to provide dissolution of solid phases
(intermediate phase and metal B) during the time teo
Figure 1. Geometry of a lamellar particle
12 rr---------,
10
E 8
..
::1.
N
o6
.04
2
o '--------'-------'---.1----'
o 4 8 12 16
2
S. specific conta::l surface <rea, m /g
Figure 2. Calculated thickness of the first phase, NiAI 3 , necessary to
attain the Al melting temperature in NisoAlso particles vs. the NilAI
specific contact surface area.
CONCLUSION
The estimates presented above support the validity of the proposed model for CSMA .
The stored energy of plastic deformation can also contribute to the heat release in the
lamellar particle. For heavily deformed metals, the dislocation density attains the value" p -
1016 m-2 . Then the energy of dislocations per unit volume, Ed ~ aGb2 p, where a = 0.5-1, G
IO
is the shear modulus and b is the Burger's vector (for AI: G=25.4 GPa, b=2.861O- m, for
36 1O
Ni: G=78.9GPa, b=2.4910- m) is rather small, 7.7 Jig for AI and 5.5 Jig for Ni, which in
the terms of thermal energy gives AT = Ed/Cp = 8.5 C for AI, 5.5 C for Ni. The energy
stored in the form of vacancies is AHv = evNAUrwhere cv is the vacancy concentration, NAis
the Avogadro number and Ur - 1 eV is the vacancy formation energy. For the upper-level
estimate we'll take ev=O.077 which corresponds to solid-state amorphization for pure
metals." Then, the enthalpy stored in the form of non-equilibrium vacancies can be
substantial: AHv = 180 Jig for AI and 175 Jig for Ni (the corresponding temperature rise is
AT"" 200C for AI, 400C for Ni).
184
ACKNOWLEDGMENTS
The work was partly supported by the Belarussian Fundamental Research Foundation
(grant # T97-249).
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interdiffusion in a binarysystem, Phys. Rev. B 44:10778(1991).
34. G.I.Barinov, Difusion Data, 5:615 (1971).
35. D.Hull and DJ.Bacon, Introduction to Dislocations, PergamonPress, Oxford (1984).
36. H.J.Frost and M.F.Ashby, Deformation-Mechanism Maps, PergamonPress, Oxford
(1982).
37. H.J.Fecht, Defect-induced melting and solid-state amorphization, Nature, 356:133
(1992).
186
EVOLUTION OF THE MICROSTRUCTURE OF
DISPERSE ZoO DURING MECHANICAL ACTIVATION
AND ITS INFLUENCE ON SINTERABILITY
T. V. Sreckovic,' M. G. Kakazey.' V. A. Melnikova,"

T. V. Tomila,2 M. M. Ristic 1
IJoint Laboratory for Advanced Materials of the

Serbian Academy of Sciences and Arts, Belgrade, Yugoslavia
2Institute for the Problems of Material Science of the National
Academy of Sciences of the Ukraine, Kiev, Ukraine
INTRODUCTION
For obtaining optimal properties of both materials and products, a very careful
control of changes of primarily morphological, microstructural and other
characteristics is necessary. This is the reason why the investigation of the process of
mechanical activation, which is very often used in powder technology, is of both
scientifically and practically interest1.2.
An investigation using methods which enable an insight into deeper levels of
the microstructure, like, for example, transmission electron microscopy (TEM) ,
electron diffraction (ED), X-ray powder diffractometry (XRPD) and infrar ed
spectroscopy (IRS), is necessary to be able to obtain a more complex and detailed
picture of the evolution of the microstructure of ZnO powders during mechanical
activatiorr'", In the case of the analysis of morphological changes of ZnO powders,
special attention should be paid to the possibilities of IRS, which follow from the
purely phonon theory, known as the theory of average dielectric constants (ADC).
This theory was generalized by Hayashi et. a1. 5 for the case of randomly oriented
ellipsoid particles, which have anisotropic dielectric properties. Changes of particle
shape, in this theory, are considered from the viewpoint of changes of ellipsoid
parameters and are characterized by depolarization factors L u and L1.' Their values
for cylindrical particles are 0 and 0.5, for spherical 0.33 and 0.33, and for plate-like 1
and 05,6. The ADC theory also enables the investigation of agglomerated powder
states 9,lo. A whole series of papers'" use these methods for investigating sintering
ZnO powders.
In the context of ceramic materials, sintering is refereed to as the densification
of a green compact into a physically and chemically homogeneous microstructure
manifested by a high sintered density, small grain size and narrow grain size
Advanced Science and Technol ogy ofSintering, edited by Stojanovic et al.

distribution 11. The desired densification of solid state sintering is, likewise, defined
as approaching the theoretical density Pth , and acquiring a relatively uniform
microstructure with the least porosity possible.
The mechanism of the sintering process has many complex aspects which cannot
at present be explained on the basis of one over-all theory. It is possible, however, to
separate various factors which must all play an important part in the general
phenomenon. The morphology, dispersivity of particles and agglomerates have a
major effect on various properties in polycrystalline materials and their full
characterization should be the first step in the study of materials.
EXPERIMENTAL
Reagent grade ZnO powder (ZnO-OOO) with a specific surface S, ~ 3.6 m2/g was
used . The ZnO powder was mechanically activated by grinding in a vibro-mill with
steel rings (CUP Mill Type MN 954/3 KHD HUMBOLDT WEDAG AG) in
continual regime in air (steel vassel volume was 500 ern", and quantity of grinding
powders was 200 g), and grinding time (r) was 3, 30 and 300 minutes (ZnO-003,
ZnO-030 and ZnO-300 respectively labeled appropriate powders).
The method of infrared spectroscopy (Specord-M80) was used in these
investigations. The preparation of samples for IRS consisted of carefully mixing
ZnO and KBr powders in the ratio 1:300 and the obtained mixture was pressed into
transparent rectangular plates.
Powders were additionally pressed into cylindrical compacts using no binder
under various pressures (25 - 200 MPa). Compacts with green density about 57 % of
theoretical were sintered in air for 0 - 120 min at 1050 C. A heating rate from room
temperature to 1050 C was 10 C/min. The density of specimens was calculated
from diameter, thickness and weight measurements of each specimens.
The morphology of particles and agglomerates and dispersivity of ZnO powders

in different stages of mechanical activation were previous investigated by TEM and
ED 3. Based on these results, one can conclude that the starting, non-activated ZnO
powder consists of microcrystal particles, with dimensions from 0.1 to 1 urn and a
high level of shape anisotropy. Electron diffraction patterns of individual particles
present a regular network of monocrystal reflections.
A three minute activation leads to the breaking-up first of all primarily
needlelike particles and large joined ones . With a further activation (up to 30
minutes) the trend of the increase of the number of small particles in the powder and
their tendency to agglomerate continues. The loss of sharp particle boundaries and
the increase of the dislocation density is noticed. The electron diffraction patterns
correspond to the set of reflections which originate from several monocrystals.
After activation for 300 minutes a powder, which can be considered a highly
disperse mixture of small particles, is obtained. Most of these particles are in the
form of aggregates, with dimensions of 0.3 - 0.1 urn, The ring-like ED patterns
indicate that these aggregates have a polycrystal structure. It was conclude that
mechanical activation by grinding leads to the breaking-up of starting particles into
fragments, which are very disordered and present domain of coherent scattering
which size is DlOo~ 0.0561lm and D oo2 ~ 0.048Ilm. Particles formed in this way, due to
mechanical activation join into aggregates of various sizes and forms .
188
(l)
u
t::
o::l
500
of:o 450
</l
.D 480
<e:
E 460
o ~
.
~
E
>
440
420
300 400 SOO soo 0.0 0.2 0.4 0.6 0.8
v (em ' ) f
Figure 1. IR-speetra for various Figure 2. The dependence of the position of the IR-
activated ZnO powders (0; 3; 30 and -absorption peak for spherical particles on the filling
300 minutes) and sintered samples. factor f; * denote the points calculated using".
The obtained spectra of ZnO powders using IRS are given in figure 1. In
accordance with ADC theory the contribution of the influence of the shapes of small
particles and agglomerates on two perpendicular optical modes (v TII - 377 cm'
and vn - 406 cm' determined from reflection IRS 12 or vTII - 380 cm' and Yr; - 413 cm'
from combination scattering spectra':') is considered through depolarization effects,
in which form factors L II and L.L (L II is connected with the crystallographic axis c and
L II + 2L.L = 1) appear and also the filling factor f, which presents part of the total
sample volume (its values are from 0 to 1). It is considered that an individual particle
has the shape of a rotation ellipsoid around axis c. A graph which illustrates the
positions of absorption peaks and also the form of some typical spectra in
dependence of particles shapes for the case when f ~ 0.003 is given inS and
corresponds to a system of non-interacting particles. This graph is used in this paper
to identify extremes of registered spectra for samples whose grinding time was
or :::; 30 min which given in table 1.
The influence of the filling factor f enables the investigation of interactions
between particles in the sample, i.e. to separate the case of a system with non-
interacting individual particles when f ~ 0 and aggregates when f ~ 19 10 The results
of calculations of the forms of IR-absorption spectra of spherical particles for several
values of f are given in", This enables the graphical presentation of vmax = F(f) (figure
2). The obtained dependence of vmax and the number of maximums of values Land f,
only emphasizes the complexity and difficulties that exist when working with real
systems . These systems are most often characterized by a set of different states. The
superposition of absorption zones of different origins in a narrow frequency range in
which the spectra are registered, makes their unique identification based only on IR
spectral analysis difficult.
189
Table 1. The position and identification of Vmax in IRS of mechanically activated
ZnO,values of depolarization factors Lj i LI and particle shape parameter LJ./ LI'
SAMPLE VI V2 V3 V4
(Vn) (VTI) (VTI) (VTI) L1 LJ. Lj ) L 1
ZnO-OOO 537 0.22 0.39 1.7
510 0.32 0.34 1
488 0.20 0.40 2
435 0.10 0.45 4.5
ZnO-003 540 0.20 0.40 2
515 0.33 0.33 1
490 0.20 0.40 2
440 0.11 0.45 4
ZnO-030 537 0.22 0.39 1.7
513 0.32 0.34 1
485 0.20 0.40 2
442 0.14 0.43 3
The results of electron microscope investigations given earlier3,4 enable a

classification of samples according to the character of particle interactions. Samples
of ZnO powder with 't ::;; 30 min are systems of non-interacting, individual particles,
while in samples with 't > 30 min, both individual particles and their agglomerates
appear.
This analysis enables the identification of registered absorption modes for
samples with grinding times from 0 to 30 minutes (figure 1) and also an estimation of
parameters L I and LJ.' which reflect the particles geometry (LJ./LII "'" 2 - elongated
particles, LJ./LII "'" 1 particles with an almost equal axis and L)LI "'" 3.5 - 4.5 for
particles with a needlelike shape). The appearance of modes VI' v2' V3 and V4
corresponds to the presence of a corresponding particle shape in samples of ZnO
powder. An insignificant reduction of modes VI' v3 and V 4 and enlargement of mode
V 2 with the continuation of the grinding time up to 30 minutes (figure 1) indicates a
decrease of the number of elongated and increase of the number of particles with
equal axis. The narrowing of the particle size distribution with the increase of t is
also indicated by the decrease of the values of full width at a half maximum of mode
L1V3min"", 170 cm' and L1V30min "'" 150 cm-'.
A further activation modifies the IR spectra, thus, that maximums which are
characteristic for a system of non-interacting particles disappear, intensities
generally reduce and two fairly wide modes with V =535 cm-' and V = 450 cnr! (figure
1, curve labeled with 300) appear. These spectral changes are the consequence of
collective processes which occur after long mechanical activation - the agglomeration
process. One can conclude that the mode with V = 450 cm-' originates from
agglomerates of particles with almost equal axis. The filling coefficient of these
agglomerates can be estimates from figure 2 to be f"'" 0.64. The existence of a mode
with V = 535 cm', in accordance with", points to the presence of platelike
agglomerates with the thickness/length ratio from 0.3 to 0.5. A similar character of
the modification of IR spectra is noticed but in sintered ZnO samples with 't ::;; 30
min (figure 1, curve labeled with sintered).
The process of densification during pressing of various activated powders was
investigated too. For a given consolidation pressure the non-activated ZnO powder,
with soft agglomerates, packs with a lower bulk density relative to the activated,
especially long activated ZnO powder (ZnO-300) with hard agglomerates - partially
sintered groups of fine particles (figure 3). Such behavior is expected if we have in
190
mind previous microstructural analysis and formation of aggregates, even smalerr
than particles in non-activated powder, during prolongation of activation time. All
above mention are permited a better particle-aggregate arrangement in the compact
and thus making a powder better for pressing reaching higher densities under same
pressure.
0.70
ZrO-300
------------.
0.65 . -y_. -- _ ..
ZrD030
..
..
. --.
A - " -"-
-
..-.. ..-
... ...... . ...

ZrOOO3
..
0.60 ,
.... .
or
.J::
.....
o.
.
,
0.55
'
0.50
1 1
Pressure (MPa)
Figure 3. Change of compact relative density with the pressure.
Densification during sintering process was investigated through the relative

sintered density and obtained time dependence is shown in figure 4. It can be seen
that the initial increase in density during heating from room temperature to 1050 C
is different for various activated ZnO, and that the densities after 30 minut es at
given temperature remain more or less constant (final stage of sintering -
discontinuous pore phase) over the time intervals of the experiments. As we can
expect a finer powders (activated for 3 - 30 min) are characterized by faster sintering
than a coarse one (non -activated), and the presence of aggregates in powders
(activated for 300 min) has a significant influence on the density of sintered pieces.
0.95
ZrD030
l)I-" _':~::: :'~::::'.s-:::':c::::c::::.e:-::::c::: ': c::::c::::;::::::::::8 ZrOOO3
r
'"
f
0 oZJi)(XX)
0.90
f".v---------
,
v- -------
_v-- ------------------v ZrO-300
cP
-.
0.85
.
. ,;
,-
c.,U'l J" :
:t,~(,-.- -,-. . . .- -.- ~.- .- - .- .- ,. .- ,- - .- -.-

100
Time of sintering (min)
150 '
Figure 4. Change of sintered specimens relative density with the sintering time at 1050 "C.
191
CONCLUSION
The non-activated powder presents a set of individual particles and has a wide
grain size and shape distribution, though one can say that most particles have an
almost mono crystal structure. In the starting activation stage (t s 30 min) the
existing agglomerates break down into parts and longer particles crumble . The
crumbling-deformation process is followed by the appearance and development of a
dislocation structure. For "C > 30 min both processes of further breaking down into
parts and deformation and also processes due to the influence of autocohesion
forces, which enable a qualitatively different consolidation of newly-formed particles
occur in parallel. The crumbling, breaking down into parts process continues until
the formation of particles with dimensions which correspond to the size of a domain
coherent scattering, but also due to autocohesion particle interaction, these particles
consolidate into polycrystal agglomerates whose hardness and shape depend on the
mechanical activation conditions.
The best densification is observed on the sintered specimens obtained from
ZnO powder activated for 30 minutes and the least for activated for 300 minute s.
Having in mind the influence of green density on sintered density, and knowing that
with ZnO activated for 3 and 30 minutes we can achieve more compacting specimens
than ones used in this investigations, it can be possible to obtain the sintered
specimen s with higher density and better properties even at lower sintering
temperature.
REFERENCES
1. YE .G. Avvakumov,Mechanical Methods olthe Activation olChemical Processes,

Nauka, Novo sibirsk :305, in Russian (1986).
2. G. Heinike, Tribochemistry, Mir, Moskva, :582, in Russian (1987).
3. T. Sreckovic, N.G . Kakazey, 'r.a Novakovic, SciSintering27, N 3:183 (1995).
4. N.G. Kakazey, T.V .Sreckovic and M.M. Ristic , J. Meter.Sci. 32:4619 (1997).
5. S. Hayashi, N. Nakarnori, H. Kanamori, J.Phys.Soc.Jap. 46, N 1:176 (1979).
6. C.J .Serna, J.E .Iglesias, J.Phys. C20:472 (1987).
7. M. Andres-Verges, c.r. Serna, J.Mat.SciLet. 20, N 9:970 (1988).
8. M. Andres-Verges, A .Misfud, c.r. Serna, J.Mat.SciLet. 8, N 3,4:115 (1989).
9. M. Andres-Verges, M. Martinez-Gallego, J.Mat.Sci. 27, N 14:1756 (1992).
10. P. Cipe, R .Ervard, Phys.Rev. B14, N 4:1715 (1971).
11. A. Rosen and H . Kent Bowen, J.Am.Ceram.Soc., 71(11):970 (1988.
12. E .C. Heltemes, H .L .Swinney, J.Appl.Phys. 38:2387 (1967).
13. c.A. Arguello, D .L. Rousseau, S.R.S.Porto, Phys.Rev. 181, N 3:1351 (1969).
14. A.D . Zimon, E.!. Andrianov, Autogeziya sipuchih materialov, Metallurgia, Moskwa:288 (1978).
192
PHYSICAL PROPERTIES OF MECHANICALLY
ACTIVATED GRAINS
Milan Petrov, Sinisa Milosevic
Institute for Technology of Nuclear and

Other Mineral Raw Materials
Franche d Epere 86,
INTRODUCTION
Mechanical activation process and mechanochemical activation of the solid matter

resulting from this process are represented by a new scientific discipline, developed within
the physics of a solid body. This multidisciplinary scientific discipline is currently dealt
mainly by the research scientists investigating the new materials technologies.
Technologies of mechanoactivation are based on the activity of mechanical energy applied
on certain material. A thorough study in this area impo ses a need to define
thermodynamically, mechanical physical and physicochemical processes occurring within
the material, comminuting to Micronics dimensions under influence of mechanical energy.
The main principles lying behind mechanoactivating technologies rely on changed energy
properties of processed solid materials, i.e. on gravitational and electromagnetic properties.
These properties are changed due to a changed energy condition of the solid matter,
induced by the activity of mechanical energy. Mechanical activation of material is the
process accompanied by the energy changes within the processed grains . Mechanical
activation proces s is the system, which comprises the fields of the active forces , devices
and mineral grains, in which the centrifugal acceleration may exceed gravitational
acceleration by 100 times . In the centrifugal field, mineral grains are brought together by a
strong force, whereby the gravitational force acting within a narrow space around particles
exceeds weight of the grains by several tenths times . Such a loading of material results in
elastic and plastic modifications, changing the shape, volume and surface density of the
grains. The energy properties induced by mechanical force are best expressed in the change
of the grain inertia. In this paper, the possibility of the grain inertia measurement by means
of automatic grain counter is presented.
THE BASIC OPERATING ASSUMPTION OF AUTOMATIC

GRAIN COUNTER
Automatic grain counter presented in Figs . I and 2, operating on the assumption

proposed by the authors , as shown by Allen,' provides response in the form of the voltage
Advanced Science and Techno logy ofSintering , edited by Stojanovi c et ai.

Kluwer Academic/Plenum Publishers. New York , 1999 193
pulse, generated as the grain passes through the opening, its value directly proportional to
the grain volume.
To vacuum
Thresho ld
circuit
---+
l1~~c~o~re~d I~ Digital
registe
Figure 1. Schematic representation of automatic grain counter
Mathematical relation between the counter response and grain coarseness can be
determined in the following way: resistance of electrolyte including the grain is equal to
resistance of two parallels connected resistors:
1
IR=-A---a--a- (1)
- - +-
Pf'4 ,44
Where P. and Pr denote resistances of grain and fluid, respectively, A is cross section of the
opening, is a cross section of the grain, 61 is thickness of the element or the segment.
Response of the electrolyte segment without grain is:
(2)
81 81
Cross sectional
area of orifice
2
fr . D
A =--
4
Cross sectional area of

parciale = a
L
Figure 2. General scheme of automatic grain counter
194
So, the change of the element resistance caused by the grain presence, o(L\R), will be:
o(LlR) = ORo - oR (3)
(4)
External resistance in the circle is high enough to annualize small change of the opening
resistance caused by the grain presence, L\R, i.e. its influence on the current density, I.
Generated voltage pulse will be I L\R. It was experimentally determined that response is
independent on the grain resistance, otherwise, the technique would be incorrect. Berg'
[2] holds that this response is independent on the grain resistance due to oxide films present
on the surface and ionic inertia of the Helmholtz double electric layer and solvent
molecules adhered on the gleans surface, whereby their electric resistance becomes infinite.
Therefore, the members involving pips can be neglected. So, equation (4) becomes:
(5)
For this reason, the response is not in proportion with the grain volume, but it is modified
because of the alA member. In this work, another assumption about the grain counter
response is proposed which differs from the basic operating assumption of the automatic
grain counter.
THE HYPOTHESIS ABOUT THE ON AUTOMATIC

GRAIN COUNTER RESPONSE
The measuring method described in the previous text is based on determination of

grain coarseness using the data obtained for counted grains and the assumption that
generated voltage is proportional to the grain volume. It is quite ordinary practice in
techniques that one physical value is representing the change of another. Automatic grain
counter operating on the basic assumption holds that generated voltage is representing the
change of the grain inertia. It can be noticed that dimension of electric voltage,
electromotive force or electric potentiality (frns' AI) is in fact the instrument response, also
that the part of it having dimension (12m) has defined physical meaning which is
momentum of inertia, recorded by a solid matter. In other words, the value recorded by a
solid matter and read by the automatic grain counter, has no influence on the instrument
response. As it comes out, voltage is the measure of the grain inertia, not its volume. Inertia
of spherical grain in its gravity center can be calculated according to the following
equation:
(6)
Where m is mass of the grain, in kg, and r is the grain radius.

Radius of the sphere r can be written as d.j2, so
2
2 d
r = -av- (7)
4
195
Since the volume sphere is:
N.d 3
V=-_ov- (8)
6
it follows that:
3 6V
d
ov =N- (9)
Specific surface area for the sphere, SSA, is:
d 2 ' N
SSA =_ov- (10)
m
I.e.
d 2 ' N
m= - ov-- (11)
SSA
Our hypothesis that automatic grain counter actually measures change of inertia, i.e. change
of the mechanical energy state, can be represented by the following equation:
3V d
J = 2.SS; .kgm' (12)
Materials an d Methods
Phosphate ore was exposed to mechanical activation process. Mechanical activation

was performed in a vibro mill; activation times were 1, 30, 60, 120, 180 and 240 minutes .
The samples of activated minerals were analyzed by the automatic grain counter and a great
number of data was collected. The experiments in which dso was constant were selected and
inertia calculated according to equation (12). Obtained data are presented in Fig.3 and
Tab. I.
0\
0
~
.... v:
!~
5
5 0\
<,
~
0
...
....
~
~
.5
..
0 ,
.;c
<.
_..... ...,............
~
e V"l
o 10 20 30 40 50 60 70
Mechanical activatio n ti m e I min
Figure 3. Change of grain inertia momentum depend ing on mechanical activation time
196
As seen from Fig.3, the values of inertia were lower if the activation times were
longer. It can be explained by the fact that extension of mechanical activation time
increases tribomechanical interaction between the grains, i.e. it supports the loss of
electrons . In that way, the grain mass is reduced. The grain mass is measured indirectly, by
measuring grain inertia at automatic grain counter . In Tab.1, the data read from the
automatic grain counter graphs (Fig.2) are presented.
In this work, rationalization of the data obtained from the automatic grain counter was
attempted . Variations of mean statistical diameter, specific surface area, total volume and
number of grains obtained by automatic grain counter are presented in Fig.4 . All these
variables , appearing in equation (12), represent one physical parameter, i.e. the grain inertia
momentum. This momentum reflects expected regularity in variation of mechanical
properties regrains after their mechanical activation . All this fits well into the model of the
grain, which lost its electrons due to tribomechanical effect and remained positively,
charged, with smaller mass. Phosphate ore contains three groups of mineral oxides. The
first group includes the minerals whose crystal lattice contains element belonging to metals.
These minerals are: A1 203 , CaO, MgO, N~O and KP, their participation in the ore
amounting to about 30%. The second group of minerals is represented by Si02, with Si
representing metalloids. Participation of Si oxides is maximal, amounting to about 50%.
Table 1. The survey of the analysis data for activated phosphate ore obtained
by automatic grain counter
Mechanica Sample Sample Mean Number Volume to Grain

1 specific volume, statisti cal of grains specific inertia, J
activation surface VOL gram in the surface area, (gmnr')
time (min) area, SSA (mrrr') diameter, sample VOLISSA
(mmvg) d50 (urn) (glmm)
1 2,31 11 7998000 2,635 96738 3,46-5 1,4]"9
30 3,96 11 2908000 2,635 121544 7,34-6 2,39.10
60 4,47 11 2545000 2,635 136966 5,69-6 1,64-10
The third group of minerals includes nonmetallic oxides . The prevailing mineral in this
group is P20 5 containing phosphorous as representative of nonmetal1ic elements.
Participation of mineral phosphate is about 20%. From what has been said, it can be
assumed that the grain which lost its electrons due to tribomechanical effect either remains
positively charged , with reduced mass, or its electrons remain built in the structure of the
crystal lattice composed of nonmetal1ic crystal1ites, so its mass increases. Having in mind
the composition of the phosphate ore, its mechanochemical activation is interesting for the
analysis using model which assumes that metals remain positively charged due to electron
losses, while nonmetals remain negatively charged due to acceptance of electrons.
Mechanochemically activated phosphate ore was analyzed using automatic grain counter in
order to prove that mass of the grains is more often reduced (inertia decrease) then
increased (inertia increase) , relative to participation of minerals "divided" in the phosphate
ore. The criterion for this conditional division, as already mentioned, is the element group
involving the element contained in the mineral crystal structure. This conditional division
involves three groups of minerals : those containing metals, metalloids and nonmetals. Their
participation in the phosphate ore was 30%, 50% and 20%, respectively.
In Tab.2, the tendency of the grain inertia decrease , accompanied by mass reduction is
presented depending on mechanical activation time. In one case only, representing 14.2% of
the total presented, we can see that the grain inertia (i.e. the grain mass) increased.
According to model presented, this grain was charged negatively, while its mass increased .
197
Table 2. The swvey of the analysis data for activated phosphate ore obtained by automatic
grain counter for three constant grain sizes
Mechan Statistic Grain Mecha Statistic Grain Mecha Statisti Grain

ical al grain inertia, nical al grain inertia, nical cal inertia,
activati size, (gmnr') activati size, (gmm') activati grain (gmm')
on (mm) on (mm) on size,
time, time, time, (mm)
(mins) (mins) (mins)
1 2,635 1,4r9 1 2,474 1,97"10 120 2,313 9,29-10
30 2,635 2,39- 10 60 2,474 1,38-10 180 2,313 9,75-10
As can be seen from the data contained in Tab.2, the grain inertia and grain size decrease
with increase of mechanical activation time.
CONCLUSION
The starting assumption in this work was that automatic grain counter measures the
grain inertia, not its volume. This assumption was supported by certain theoretical analyses
and the model was developed for the grain of higher energy level, viewed from the aspect
of mechanical parameters. By analyzing the data obtained by experimental investigations, it
was found that they fit well with developed model. This work describes the role of grain
inertia showing mechanical changes induced in grain by its mechanical activation.
REFERENCES
1. T. Allen, Particle size measurement, Soc. Analyst. Chern. London , 1981, p.392-413.
2. M.Petrov, S. Milosevic, Mechanical activation enthalpy of different minerals,
A.A.BalkemaIRotterdam/Brookfield/1996, p.3-7 .
3. K'Tkacova, Mechanical activation of minerals, Elsevier, Oxford-New York-Tokyo, 1989.
4. V vl. Molcanov, O.G.Slezneva, E.N.Zimov , Aktivacija mineralov pri izmelj cenii, Nedra, Moskva, 1988.
5. M.Petrov, S. Milosevic, Ionic crystals mechanical activation enthalpy, Journal of Mining &
Metallurgy, Bor , 1996 p.47 -56.
198
CHANGE OF THE PHYSICAL - CHEMICAL CHARACTERISTICS
OF THE MATERIALS BY MECHANICAL ACTNATION
Ljubisa Andric, Deana Zivanovic, Sinisa Milosevic
Institutefor Technology ofNuclear and

Other Mineral Raw Materials,
Franche d 'Epere 86,
Yugoslavia Belgrade
ABSTRACT
Mechanical activation-milling of a material changes the size and structure of its

particles, leading to an increase ofthe system potential energy, and also material chemical
activity as a consequence of increased free surface and concentration ofthe lattice defects.
These changes show that new change the properties of treated materials. Control of the
mechanical activation process and properties ofactivated materials are utilized in several
technologies (sintering; chemical synthesis, hido metallurgy etc.). In this paper
experimentally obtained results on changes of physico-chemical properties of alumina
during its mechanical activation in high energy vibro mill are presented.
Key words: mechanical activation, alumina, properties
INTRODUCTION
Rapid development of new generation industrial materials requires application of

fundamental laws in technology of advanced materials with predefined characteristics.
Having this in mind, the methods of mechanical activation, aimed to improvement of their
characteristics, are very attractive.
During mechanical activation of solid inorganic crystalline materials,the elements of
their crystal structure become thermodynamically unbalanced which is accompanied by an
increase of free enthalpy and chemical reactivity, in comparision with ideal or only slightly
damaged crystal structure.
Activation of inorganic material is the consequence of increased specific surface area,
concentration of dislocations, and increased number of atomic defects in activated material.
Advanced Scien ce and Technology ofSintering , edited by Stojanovic et al.

This activation, is not a simple change of the particles dimensions, but a complex
physicochemical process, during which potential energy, chemical activity and surface
reactivity of the system are increasing. Large amount of energy transferred onto the system
produces internal tension in certain points of processed material, whose relaxation causes
deformations inside the material structure (deterioration of lattice development, of defects
and dislocations).
Mechanical activation of the material can be viewed as a multi-stage process where
each stage is characterized by change of the energy parameters and the content of stored
energy.
The first stage of mechanical activation precedes to material destruction. Under
influence of the forces bellow the level characteristic for a given solid body, the zones of
the remaining strains, are developed by shifting atoms from their ordinary positions; crystal
lattice is damaged, interatomic, interionic and intermolecular distances, as well as the
angles of the structural orientations are changed. If the material is partly or completely
amorphous, the structural change is reflected also in change of the crystal lattice
parameters.
The second stage of mechanical activation is characterized by formation of new
surfaces. Destruction of material and crack development are interesting because of changed
energy condition and numerous physical and chemical changes in processed material.
The third stage of mechanical activation is fine micronizing grinding, accompanied by
further developmend of new surfaces and increased level of energy in the surface layer,
along the phase boundary. During fine micronization, thermodynamic characteristics of
processed material are changed. Along with increase of the free surface and decrease of the
particles dimensions, both, total and free surface energy are changed.
The fourth stage of mechanical activation is ultra-fine micronizing grinding, when the
starting material is, transformed into material with different structural characteristics. If
change of specific surface versus time is graphically represented, obtained curve would
show the maximum for many materials. This change is associated with two processes:
micronization and agglomeration, affecting the size of the specific surface in oppisite ways.
During mechanical activation, the ratio of the finer particles and concentration of the lattice
defects, increase with appearance of the free valences. This all favours agglomeration, thus
lowering the specific surface. Decrease of the specific surface beyond the maximum would
depend on the material characteristics and intensity of mechanical activation. The
maximum is usually achieved for materials of low hardness. The tendency to
agglomeration would increase if intensity of impacts during mechanical activation (in high-
energy vibrational mechanoactivator) is higher.
In this discussion on change of the specific surface and size of particles during
mechanical activation is correct, the grinding boundary is acheved in the moment when
specific surface reaches its maximum and starts to decrease due to agglomeration. The
boundarying specific surface, Sbd' acheved in boundaryng time, ~, represents optimal
duration of mechanical activation. It should also be pointed out that the comminutional
boundary would depend on the properties of activated material, particulary hardness and
cleavage.
In order to provide clearer picture of physico-chemical changes in processed material,
theoretical principles of operation of high-energy mechanoactivators should be well
understood.
EXPERIMENTAL
For investigation of mechanical activation and induced changes of the material

characteristics, two types of mechanoactivators were used: planetary mechanoactivator
"Retsch PM 4" and vibrational mechanoactivator with rings, "Siebetechnik TS 250".
Characterization of products was based on instrumental techniques, using the following
devices:Coulter Electronics-Coulter Multisizer (physical characterization), Riedhammer
200
Gradient furnace G 100/9 (heat treatment), Philips PW 1710 (X-ray examinations),
Bomem-Hartman and Braun Michelson MB-toO, FT IC spectrometer for IC spectra and
leol lSM T20 electron microscope for determination of the shape factor, average particle
diameter and specific surface area.
In the experiments of mechanical activation aimed to improvement of investigated

material characteristics (alumina), the parameters of the mechanoactivator operation (time,
number of revolutions and vibrations, specific energy, gravity force) were observed,
together with parameters for obtained products (specific surface area, granulometric
composition, the shape factor, average diameter, calcination temperature, X-ray, and IC
analyses).
The starting material used in these investigations was y-alumina, collected from the
"Aluminium Combine - Podgorica". As a reference material, Alcoa alumina was used (5).
Results of granulometric and chemical compositions of the starting and reference alumina
are presented in Tab.I. In Tab.2, the results for mechanochemically and thermically treated
aluminas from the Aluminium Combine - Podgorica are presented (6).
Table 1. Granulometric and chemical composition of the starting and reference

alumina samples
Alumina Starting sample Reference sample Chemical composition
Size Starting samp. Referenc samp.

class, in M% R% D% M% R% D% Components and contents
!=tm
-63+20 74.23 74.23 100.0 0.70 0.70 100.0 Si02 2.09 Si02 0.08
-20+15 10.50 84.73 25.77 0.80 1.50 99.30 Alp) 94.79 AI20) 99.57
-15+10 6.00 90.73 15.27 1.70 3.20 98.50 Fe 2O) 0.30 Fe20 ) 0.044
- 10+5 5.66 96.39 9.27 3.80 7.00 96.80 Ti02 < 0.10 Ti02
-5+3 2.69 99.08 3.61 2.70 9.70 93.00 CaO 0.15 CaO
-3+2 0.36 99.44 0.92 l.l 0 10.80 90.30 MgO < 0.05 MgO
-2+ 1 0.30 99.74 0.56 7.7018.50 89.20 N~O 0.40 N~O 0.03
N~O 0.28 N~O 0.062
-1+0 0.26 100.00 0.26 81.50100.081.00 soluble in H,D soluble in H2O
Total 100.00 100.00 LOI 2.09 LOI 0.28
Table 2. Granulometric and chemical composition of mechanical and thermically

processed alumina from the Aluminium Combine Podgorica, a. - AIlO)
Size class, in um M% R% D% Component Content

- 63 + 20 5.88 5.88 100.00 Si02 0.12
- 20 + 15 3.52 9.40 94.12 AI20 ] 99.61
- 15 + 10 5.06 14.46 90.60 Fe20] 0.025
- 10 + 5 5.08 19.54 85.54 Ti02
- 5 + 3 5.32 24.86 80.46 CaO
- 3 + 2 4.08 28.94 75.14 MgO
Na.Osoluble in
- 2 + 1 7.10 36.04 71.06 H20 0.106
- 1 + 0 63.93 100.00 63.96 L.O .I. 0.14
Total 100.00
201
Examination of the shape factor (Table 3) slowes that sphericity of investigated
samples was in the range of 0.55-1 .00. For most of them, this factor was 0.95; for only a
few of them, this factor was 0.55, mostly for agglomerates of irregular shape. Also, as can
be seen from Table 3, the size of particles in investigated samples was in the range of 6 to
30 mm, while the values of the specific surface were in the range of 0.074 to 0.158 m 2/g.
Specific surface area, calculated on the basis of the approximating shape factor , showed
that development of th specific surface area was greater from that for regular elipsoid of the
corresponding shape factor; therefore, obtained results can be regarded as conservative, i.e,
minimal for investigated samples.
Table 3. Basic physical characteristics of ex. - Al 20 3 following to mechanochemical

and heat treatment
Sample Number of Shape factor , f, Specific surface Average grain diameter

notation investigated rom. max. avg. area, dav , J.UD
particles S, m2/g
Starting 203 0.55 1 0.847 0.074 30.00
2/1000 430 0.55 1 0.850 0.087 16.28
2/1050 475 0.55 1 0.890 0.092 10.97
2/1100 484 0.55 1 0.935 0.134 10.44
2/1150 493 0.55 1 0.945 0.150 9.17
4/1200 686 0.55 1 0.967 0.156 7.87
ALCOA 653 0.55 1 0.993 0.158-0.349 6.18
Alumina samples were investigated by a method of X-ray diffraction, prior and

following to mechanical and heat treatment (7). In the starting sample, sharp, well
expressed diffractional maximums correspond to ex. - A12 0 3, while a great number of weak
and diffuse, partly overlapping maximums correspond to y-A120 3 (Fig.1).
Flgure.I. Diffractional maximums and intensities of the starting sample
Experimental investigations of physical-chemical characteristics of the alumina

samples, mechanically activated in vibrational mechanoactivator for 2-4h and subsequently
thermically treated at the temperatures of 1000-1200C produced diffractional images
similar to the starting sample characterized by significant participation of the ex. - A120 3
Diffractional maximums and intensities of investigated alumina samples are shown in Figs .
2 and 3 (5-8) .
202
~ .... I
- l
Figure 2. XRD intensities of the sample Figure 3. XRD intensities of the

mechanically activated for 4h/1200C reference Alcoa alumina
Quantitative participation of the best crystallized, Ct.-AI20 3 phase in investigated

samples, was examined by the X-ray diffractional analysis (8). As a measuring standard,
also used for calculation of 1100 data, intensities of selected pure Ct. - A1203 component of
Alcoa sample were used. In Tab. 4, the data about quantitative participation of Ct. - phase in
investigated samples are presented.
Table 4. Participation of Ct. - Al203 phase in investigated samples
Sample d= 3.48 d= 2.55 d= 2.09 Participation of Lattice parameters for

notation Ct.-AI203 Ct.-Al203
I w I w I w aA cA vN
Starting 102 .35 154 .29 154 .32 32 4.769 J 13.001 1 256.066
211000 154 .52 234 .44 243 .50 49 4.759 1 12.9962 254.885
2/1050 169 .57 234 .44 262 .54 54
2/1100 253 .86 376 .70 357 .73 76
2/1150 266 .90 433 .81 445 .91 87 4.757 1 12.9932 254.636
4/1200 282 .96 449 .84 433 .89 90 4.743] 12.9864 252.97 J4
ALCOA 295 1.00 535 1.00 4881.00 100 4.758 J 12.9874 254.64 11
In Figs. 4 and 5, results of IC spectrophotometric investigations of the reference

sample and the sample mechanochemically activated for 4h, are presented.
Figure 4. Absorption spectra of the Figure 5. Absorption spectra of the sample

reference Alcoa sample mechanically activated for 4h
203
CONCLUSION
In this paper, a possible improvement of the alumina physical-chemical properties by

mechanical activation in mechanoactivators of specific desing was considered. Based on
performed experiments and achieved results, it became obvious that investigation of the
physical-chemical properties of material exposed to mechanical activation is a complex
task. On the other hand, new materials are expected to satisfy strictly defined physical-
chemical, structural, mineralogical and mechanical requirements.
Performed experimental investigation of alumina mechanical activation enabled
determination of:
- basic characteristics of mechanical activation products (granulometric composition, grain
shape, specific surface etc) depending on the optimal values of relevant technical and
technological parameters,
- kinetic parameters of mechanical activation whose change during the process cause
structural defects and change of the materials reactivity,
- thermodinarnically instable states, caused by redistribution and prolonged activation,
- structural and reological changes (grain size and grain shape) of materials processed by
combination of mechanical activation and heat treatment.
REFERENCES
1. K. Torka , "Reactivity of Solids", Elsevier, Amsterdam, (1961).

2. M. Senna, "Finest Grinding and Mechanical Act ivation for Advanced Materials ", 7th European
Symposium on Comminution, Ljubljana, p. 21-37, (1990).
3. M.M. Ristic.t'Kinetics and Mechanism of Mechanochemical Processes" , Chem. Rev., p. 32, 75,
(1991).
4. G. Heinicke, "Tribochemistry", Academie - Verlag , Berlin, (1984).
5. K. Wefers, C. Micra , "Alcoa Technucal paper N 19 Revised", Alcoa Laboratories, Pittsburg, P.A.
USA, (1987) .
6. S. Milosevic, M. Tomasevic-Canovic, R. Dimitrijevic, Lj.Andric.j.l'ostupak za dobijanje a -
aluminijum oksida (a-AIP3, korunda) iz metalurske glinice primenom mehanohemijsko-termickog
procesa" Patent P-294/93, Patent-komerc, Sumatova~ka 108, Beograd, maj (1993).
7. H.P. Klug, L.E. Alexander, "X-ray Diffraction Procedures" , New York,(1974) .
8. R.G.Garvey, "LSUCRIPC Least Squares Unit-Cell Refinement with Indexing in the
PersonalComputer" Powd. Diff., 1(1), 114, (1986).
9. Lj. Andric , "Investigation of the kinetics of dry micronization of mica in ultra-centrifugal mill of a
pherifipheral comminution path"(M.Sc.Thesis, in Serbian) Faculty of Mining and Geology,
Belgrade, Yugoslavia, (1993).
10. Lj. Andric , M. Petrov, S. Milosevic, M. Tomasevic-Canovier'Ultra-fine Micron ization of Mica in
Ultra -Centrifugal Mill of Peripheral Comminution Path", 8th European Sympos ium on Comminution,
Stockholm, Sweden VoI.II,p .501,(1994)
11. D.Zivanovic, Investigation of the mica mechanochemical process,(MSc.Thesis in Serbian),
Universityof Belgrade , (1995).
12. S .Pa~alic,"Reaktivnost mehanicki aktiviranog apatita",(M .Sc.Thesis,inSerbian) University of
Belgrade, (1995) .
13. S.Milo~evic, M'Tomasevic, M.Petrov, M.Duri~ic, R.Dimitr ijevic, B.Zivanovic"Amortphization of
alumino silicate minerals during micronizationprocess" American Ceramic Bulletin, 71(5), 771,
(1992).
14. M. Tomasevic-Canovic, S. Milosevic, M. Duricic, R. Dimitrijevic, M. Dumic.t'Physico-chemical
aspects of kaolin fine grinding" I: The X-rey and thermographic study", J. Serb. Chem. Soc. 57(1), 35,
(1992) .
15. M. Tomasevic-Canovic, S. Milosevic, M. Durieic, R. Dimitrijevic, M. Dumic ,L. Mihovilovic,
"Physico-chemical aspects of kaolin fine grinding" II : Change in reactivity and structure, J. Serb.
Chem . Soc. 57(9), 605, (1992).
204
MECHANICALLY ACTIVATED BaCOrAhOrSi(h MIXTURE AS AN ADDITIVE
FOR LIQUID PHASE SINTERING OF ShN4
Dj. Kosanovic', S. Boskovic', S. 'Lec2,
1. Institute of Refractory Materials, Magnohrom Kraljevo, Yugoslavia

2. Institute of Nuclear Sciences Vinca, Mat-Sci.Lab.POB 52211000
Belgrade Yugoslavia
ABSTRACT
Densification as well as a ~ B phase transformation in ShN4 were followed as a

function of activation time of the additive mixture BaC03-Ah03-Si02. The composition of
the ternary mixture corresponds to celsian (BaAhSi20s - BAS). Previously mechanically
activated powder mixtures for various lengths of time, were added to Si3N4 in the amount of
10 - 30 %. Sintering was performed at l650-1700C in nitrogen atmosphere up to 8 hours.
The changes in densification degree as well as phase composition were followed as a function
of heating time and the time of mechan ical activation of the additive mixture . The results
obtained, showed that mechanical activation retarded densification in samples heated for up
to 4 hours up to l700C. On the other hand, for the constant sintering time, a ~ B
transformation of Si3N4 was enhanced with increasing activation time, and the amount of
additives.
1. INTRODUCTION
Compo site materials on the basis of ShN4 have been intensively studied for a long
time, although some of these materials have already found the way to successful application
in different branches of industry. One of the materials which attracts much attention lately, is
the composite Si3N4 celsian (1,2,3) . This materials can be easily produced by applying
pressureless sintering, it has good mechanical properties, good resistance to oxidation and
corrosion and is economically justified, Celsian as an additive to Si3N4 can be obtained, in
different ways, Beside from the mixtures of BAS forming oxides (BaO\, Ah03, Si0 2), it
could be obtained from Ba-carbonate or Ba-sulphate in reaction with kaoline, as well as from
amorphous precursors like Ba-zeolites .r"
In this paper the mixture of BaC03, Ah03 and Si02 was used to produce celsian in
the sintered body. The mixture of the above given reactants was mechanically activated for 2
and 4 hours. The influence of activation time of the additives mixture on phase changes and
densification degree of ShN 4 was followed .
Mechanical activation of additives was used because more homogeneous mixture of
additive can be obtained, as well as because during activation micronization of particles takes
place(6) which can cause more beneficial conditions for particles packing in the green body.
Advanced Science and Technology ofSintering , edited by Stoja novic et al.

Kluwer Academic/Plenum Publ ishers, New York, 1999 205
Higher green densities produce higher sintered densities of the material. Besides, bearing in
mind that during sintering of ShN4 both densification and phase transformation of a into B -
ShN4 take place, it is expected that the change of physical condition in the additives caused
by application of mechanical activation, will affect densification as well as phase
transformation.
2. EXPERIMENTAL WORK
Powders used in the experimental work were Si3N4 - UBEI0, BaC03 - "Zorka",
Sabac,Yugoslavia, Ah03-Alcoa A-16, and SiOz -quartz, Merck. Mechanical activation of the
mixture 40,85 % BaO (from BaC03), 27.34 % Ah03 and 32.01 % SiOz, the composition of
which corresponds to BaAhShOg (celsian) was performed in vibratory mill. Twenty g of the
mixture were activated for 2 and 4 hours . Three additives were prepared, A- non-activated
mixture, B- 2 hour activated, and C- 4 hour activated mixture . The amount of additives to
ShN4 ranged from 10-30 %. After homogenisation in isopropanol, the powders were
prepressed, in hydraulic press, and thereafter isostatically pressed under 300 MPa . Green
densities of the studied compositions are given in Tab. 1 Sintering was performed in an
Astro furnace in nitrogen atmosphere at 1650C to 1750C up to 8 hours. At 1150C the
samples were heated 3 hours to allow for carbonate decomposition according to TG analysis.
Heating rate was 43 DC/min. Cooling from sintering temperature was natural (cooling down
of the furnace) . Sintered densities were measured using Archimedes method , while phase
changes were followed using Siemens X-ray equipment.
Tab 1: Green densities vs. additive amount and activation time
additive amount greendensity (g/cm')

A B C
10 1.75 1.76 1.88
20 1.81 1.82 1.91
30 1.88 1.91 1.91
3. RESULTS AND DISCUSSION
It is well known that the increasing of additive concentration enhances densification

during liquid phase sintering at constant temperature, up to optimum concentration. This was
proved in our case, as well (Fig. 1). Namely, with increasing concentration of BAS forming
mixture (both activated and non-activated) at constant sintering temperature and time,
densification degree increases with increasing additive concentration from 10 to 30 %, i.e.
with increasing liquid phase amount. Besides, at 1700C, maximum density was achieved
with 20 % of non-activated additive-A. This means that for 1700C, optimum content of
additive A is 20 %. The data from Fig. 1 further show that with prolonged activation time of
the additive, densities differ, the difference being most expressed at lowest additive
concentration (10 %). At higher additive concentrations the difference in sintered densities
are getting smaller (Figs. 2 and 3) and almost disappears at 30 % of additive. It is also evident
from Fig. 1., that the most efficient additive for the densification of ShN4 appears to be non-
206
activated mixture of additive - A. The same result was obtained at different sintering
temperatures, as shown in Figs. 2 and 3.
-=r
104 ...
100.--------------,----,
100
0-96
25 92
-c
Q
C
1
94
-c
88 - -B 92 --B
-A
84+-........~-;:...~..,......~..-..--,~-r-~ -A
90 +---r-.......,-...,......-r--.-,c-...,..........,..-.-,~
o 5 10 15 20 25 30 35 02345 6 7 8 9
add. (%) or (h)
Fig. 1. Densification degree as a function Fig. 2. Densification degree vs. sintering

of additive concentration time, 20% add. 1700C
100....--------------,
98
~-96
94
-c
92 --B
9O+-.....,..-~.....,..-~___.--__r~
-A
4
2 or (h) 3
Fig.3. Densification degree vs. sintering time , 30% add . 1650 -c
During sintering of Si3N4 in the presence of BaC03-Ah03-Si02 mixture, reaction

of BaAhShOg formation takes place. The results on the studying of this reaction as a
function of time of the mechanical activation'f showed that the reaction rate increased with
prolonged activation time. Bearing in mind that BAS is being formed among the additive
constituents, which also form liquid phase the enhancement of BAS formation has as a
consequence , the decreased amount of unreacted starting materials which at liquidus
temperature form liquid phase needed for SiJN4 densification . It was mentioned that the
differences in densification degree got smaller with increasing additive amount. This is a
consequence of the increased amount of the liquid phase in the system being sintered, which
masked the effect of mechanical activation on the densification of SiJN4.
During sintering of the system under study, beside densification, phase transformation of a
into 13 - ShN4 takes place, for which the presence of the liquid phase in needed also. Phase
transformation of a ~ 13 ShN4 is reconstructive and defined by several parameters like
sintering time, temperature , amount and the properties of the liquid phase. Results in Fig. 4
show that with increased amount of additive, the content of a phase decreased ( Figs. 4 a and
b). The amount of a phase decreases also with increasing sintering temperature as is obvious
from Figs. 4a, 4c and 5. In another words, with increasing additive amount and temperature,
the content of the liquid phase increases and its viscosity decreases, which beneficially affects
207
a
b c
20 25 30 35 40 20 25 30 35 40 20 25 30 35 40
Fig.4. X-ray patterns of samples sintered with a. 20% A,1750C- 4h,b. 30% A,1700C-4h,c.20%
A,1700C-8h
a b
1 1 11
JJUU~l)
11
20 25 30 35 40 20 25 30 35 40
Fig.5X-ray patterns of Si3N4 +30%B,at different sintering temperatures;a.1650C,b.1700C (8 h)
100 - - -- ---- ~ ~ - --- -
z... 90
MQ)
%~80 Co I
I
'0 oE 70
II'
i
p
~~ '-60
~ -.---A
". - - 8
50 :I
f----r----r-~,---~--l
-c
o 100 200 300 400 500

t (minutes)
Fig.6. Contentof Pphase(%)as a fimction of sinteringtime
208
both densification and phase transformation. It should be added that with increasing
additive amount relative fraction of Si02 introduced via starting Si3N4 , decreases which
brings about the decrease of the liquid phase viscosity .
By comparing the curves showing the dependence of the densification and the degree
of a to B conversion of Si 3N4 on time, at 1700C (Figs. 2 and 6), the same time dependence
can be observed. The explanation can be found in the fact that both processes are controlled
by the liquid phase properties. However, these results show Figs . 2 and 6 as well, that the
amount of the liquid phase is not the only parameter affecting phase transformation. Namely,
the samples with non-activated additive-A, achieve full densification at 1700C, 8 hours
(Figs . 1,2 and 3) while phase transformation is legging, inspite the largest amount of the
liquid phase in this system.
The comparison of the results obtained at constant concentration of the activated with
non-activated additives can be done only in respect to the reaction rate of the celsian
formation, or on the basis of the contents of reactants and intermediate products which at the
liquidus temperature will form the liquid phase . At the same additive concentration however
the amount ofSi02 introduced via SbN4 keeps constant independent of mechanical activation
time .
Phase transformation of a into B SbN 4 takes place via nucleation and growth of B
phase, through processes like solution-diffusion-precipitation. Nucleation of the new phase
can be homogeneous or heterogeneous, as is well known. The activation energy for
homogeneous nucleation is much higher, which means that heterogeneous nucleation is
developing more easily . As the seeds for crystallisation of the new phase, different aids can
be used , which is widely applied in the practice for systems with low rate of nuclei formation.
Structurally similar compounds which may be present in the system can also be helpful as
nucleation seeds. In our case, hexacelsian is structurally very close to SbN4 (hexagonal
structure). It is unambiguously proved that with increasing time of mechanical activation of
the additives, the amount of hexacelsian increases. This could explain the presence of larger
number of crystallisation seeds on which the nucleation of the new phase , B - Si3N4, starts in
the case of mechanically activated additives .
CONCLUSION
The increasing amount of additives (BaC03-Ah03-Si02) from 10-30 % brings about

increasing densification degree of Si3NJ celsian composites. With increasing additive
amount, maximum temperature at which full densification is attained, decreases.
Prolonged time of mechanical activation of the additives retards densification.
Transformation of a~B SbN4 is enhanced with increasing additive content, time and
temperature of isothermal sintering.
Phase transformation a~B Si 3N4 is enhanced in samples containing mechanically
activated additives, in which the amount of submicronsized hexacelsian is higher in
comparison with sample containing non-activated additive
REFERENCES
I. K.K.Richardson, D.W.Treitag, D.L.Hunn, Barium Alumino-silicate Reinforced in Situ Silicon Nitride,

J.Am .Ceram .So c. 78(1995)2662
2. N.P.Bansal, M.Hyatt, Crystallisat ion Kinetics of BaO-AI203-Si02, J. Matter. Res. 4( 1989)1257
3. C.Drummond, N.Bansal, Crystallisation Behaviour and Properties of BaO.AI203.Si02, Glass Matrices,
Ceram. Engn.Sci. Proc .II (1990) I 072
4. H.W.Hennicke, S.Kowsiridse , Celsian Ceramics with Barite as a Raw Material, Keram .Z. 33( 1981)389
5. V.Dondur, et. all. Structural Characterisat ion of Hexagonal Bal-xAI2-2xSi2+2XO Phases Synthetized
from Zeolite Precursors, in Advances in Science and Tehnology, Ed P.Vincenzini, Techna , Faenza,
3(1995)687
209
6. C.J.Hwang, R.A.Newman, Silicon nitride ceramics with celsian as an additive, J.Mat.Sci. 31(1996)150
7. S.Boskovic, Dj.Kosanovic, Dj.Bahloul-Hourlier, P.Thoma,S. Kis, Formation of Celsian From
Mechanically Activated BaC03-AI203-Si02 Mixtures, IX SINTERING98, Bgd.I998
8. A.Bandyopadhyay et all, Kinetics of In-Situ a to b Si3N4 Transformation in a Barium Aluminosilicate
Matrix, Scripta Metallurgica et Materialia 32(1995)1417.
210
MECHANICAL ACTIVATION OF MICA
Deana Zivanovic, Ljubisa Andric, Zivko Sekulic, Sinisa Milosevic
Institute for Technology ofNuclearand

OtherMineralRaw Materials,
Franse d'Epere 86,
ABSTRACT
In thispaper, the investigation results on the changes occurring during mechanochemical

activation ofmicaperformedin planetaryand vibrational mills, arepresented. The modelofthe
particle size distribution and specific surface change developed, by Bet method is propose.
Mechanochemically activated mica can be usedasfiller in industry ofpigments.
Key words: mechanochemical activation, specific surface, particlesize
INTRODUCTION
Mechanochemical activation of the material caused by the activity of mechanical forces

can be viewed as change of its free energy and its entropy. By activated material, we understand
the material whose crystal lattice is thermodynamically and structurally unstable, differing from
ideal or only partly damaged structure by increased enthalpy content. Such solid materials
(mica, quartz, felspar etc.), characterized by disordered state instead of ordered tridimensional
structure, can be described as amorphous materials',
Active state, or activity, is thermodynamically determined by difference of free enthalpies,
i.e, free energies. This active state of solid materials is a consequence of enlarged specific
surface, raised amount of the point defects and deformation ofthe crystal lattice.
If mechanochemical activated material is not considered as a total change of its free energy
and Its entropy, mechanochemical activation can be viewed as multi-stage process, whereby the
character of the energy parameters and amount of accumulated energy would change from stage
to stage. Irrespective ofthe fact that specific surface ofprocessed material can vary, from is very
large, to very small, the final result is the surface of some average size which differs from
material to material. For the majority of investigated materials, the surface change with
micronization time reaches its maximum . This maximum is associated with two processes
micronization and agglomeration, having the opposite effects on size of the specific surface.
Micronization dominates in the early stages of the fine grinding process. Decrease of specific
surface after the maximum will depend on nature of the processed material and intensity of the
grinding process. The maximum usually appears in the materials of lower hardness. The
tendency to agglomeration registered in vibrational mill increases with increase of the impact
intensity.
Advanced Science and Technology ofSime ring, edited by Stojan ovi c et al.
Kluwcr Academi c/Plenum Publishers, New York , 1999 211
If this analysis on change of the specific swface and particles size occurring during
grinding is correct, it would mean that the comminution limit would coincide with attaining of
the maximal specific surface, further decreasing as a result of agglomeration and functionally
depending on grinding time. This would also be the yield specific swface, SLT> reached in yield
grinding time, tLT> equal to optimal grinding time. It should be pointed out that yield
comminution depends on characteristics of activated material, particulary its hardness and
cleavage.
EXPERIMENTAL
Device for mechanochemic al activation was selected with regard to the type of mechanical
energy transmitted onto processed material. High-energy vibrational mill with rings, (TUR MN
9547/3 KHD HUMBOLDT WEDAG AG) and planetary mill (pULVERSITTE 0) were
selected. Grinding times were 30, 60, 120 and 360 minutes. Change of the particles size and
change of the specific surface were followed by BET method on "Gilas-Alcatel" granulometer
HR850.
Basic characteristics of investigated powders are presented in Tables 1 and 2.
Table 1. Characteristics of mica powder ground in vibrational mill with rings
Sample t (min) d.v(mm) Sp(cm2/g)

A-OO 0 109.7 1208
A-Ol 30 6.44 14854
A-02 60 4.08 21746
A-03 120 1.32 40697
A-04 360 1.27 106295
14
12
10
~a
.t
e
4
2
.....
0
0 15 10 115 20 215 30
D (f.UTI)
Figure 1. Gaussian particle size distribution for the mica samples activated
in vibrational mill with rings for 30 mins
212
12

10
~6
4
2
0
0 .0 0.5 1.0 1.5 2.0 2.5 3.0
D(J.ttn)
Figure 2. Gaussian particle size distribution for the mica samples
activated in vibrational mill with rings for 360 mins
16
14
12
10
20 40 60 80 100 120 140 160 180 200 220

D (urn)
Figure 3. Gaussian particle size distribution for the mica samples
activated in planetary mill for 30 mins
213
Table 2. Characteristics of mica powderground in planetarymill
Sample t (min) d.v(mm) Sp(cm2/g)

B-Ol 30 67.19 2009
B-02 60 89.60 1289
B-03 120 79.81 1664
B-04 360 32.59 4740
DISCUSSION
Mechanochemical activation of materials, particulary dispersed ones, is accompaned by

formation of new swfaces, structuraldefects and change their reactivity. At the same time, the
size of particles decreases. Size distribution of powdersparticlesmicronizedin vibrational mill
with rings or planetarymill micratesfrom the Gaussian distribution (with severalmaximums) to
one-maximum distribution, i.e. distribution with yield particle size, characteristic for defined
processing conditions. By the analysis of obtained results, particle size distributions shown in
Figures 1-4,were determined.
The analysis of experimentally obtained results indicates that particle size distribution is
significantly changeddepending on mill type and activation time. In vibrational mill with rings,
particlesize distribution with three maximumstransforms into one-maximum distribution (time:
360 mins),with majorityof particlesin the range of 1-2 um (Figs 1. and 2.). These changescan
be describedby the following equation:
d",-d -kt
--=e (1)
d.s-d;
were dw is maximal averageparticlesize achieved by grinding, do is initial averageparticle size,

d- is medium particle size after t mins of micronization and k is the constantof micronization.
14
12
10
20 40 60 80 100 120 140 180 180 200 220

o (11m)
Figure 4. Gaussian particlesize distribution for the mica samples
activated in planetarymill for 360 mins
214
Equation(1) can be transformedas follows:
(2)
or
(3)
In vibrationalmill with rings, changeof the parameterD is regular, which is not the case in
planetary mill. This is the consequence of agglomeration proceeding throughout 360 min
grinding.
Comparative analysis of kinetic parametersshows that mill type is more influentialon the
comminution process then grinding time due to the way of the energy transfer onto powder
particles(Fig.5).
If can be assumedthat activityof the system A, is reciprocal to the averageparticlesize (d),
so:
(4)
where k, is the constantof proportionality.

In that case,
(5)
where subscripts v and p denote vibrational and planetarymill, respectively and k' = k/kp.
The influence of mill type on the mechanical activation during grinding process can be
followed by changeof the specificsurfaceareaversus millingtime (Figs. 6 and 7).
60
50
40
>
-0
~30
10.....
o
----T"'""----T"'""----......---_
100 100 300 400
t (min)
Figure 5. Changeof dJ<\, ratio dependingon processingtime
215
120000 r - - - - - - - - - - - . ,
100 200 300 400

t(min)
Figure6. Change of S, depending on micronization time in

vibrational mill with rings
500D
4000
.S1}
N
3000
E
,.
c, ZOOO
oo
D
0 100 JOO 300 400
t(min)
Figure 7. Change of S, depending on micronization time in planetary mill
As can be seen from Fig.7., comminutionallimit in planetary mill is attained after 60 mins,
when agglomeration starts, without accompanying amorphization. In vibrational mill with rings,
(Fig.6.), comminutionallimit is attained after 360 mins, accompanied by amorphization (3).
CONCLUSION
Based on obtained results, the following conclusions are derived:

the type of mechanical energy transfer on to ground material produces stronger effects on
micronization then micronization time,
during micronization of mica in planetary mill, agglomeration starts after only 60 mins,
while in the planetary mill it was not registered till the end of investigating period (360
mins),
during micronization of mica in vibrational mill, partial or even complete amorphization
occurs, which is not the case with in planetary mill,
the conception of critical particle size was implemented, understood as a measure of
micronizational efficiency in various mill types.
216
REFERENCES
1. S.Milosevic, Mechanochemical Processes in Technology of materials (in Serbian), Center

for Multidisciplinary Studies, University of Belgrade, Belgrade 1992.
2. G. Heinickie, Tribochemistry, Academic-Verlag, Berlin, 1987.
3. D. Zivanovic et all., Science of sintering, 28(2), 117-122 (1996)
4. D. B. Zivanovic, Change of the mica reactivity by mechanochemical treatment (in
Serbian), M.Sc thesis, University of Belgrade, 1995.
217
THE INFLUENCE OF MECHANICAL TREATMENT ON
ACTIVATION OF THE ZoO-SoO! SYSTEM
A.Tucic,' N.Nikolic,' B.Marinkovic2
'Institute of Technical Sciences of SASA, Belgrade, Yugoslavia

2Center for Multidisciplinary Studies, University of Belgrade, Belgrade,
Yugoslavia
INTRODUCTION
Solid state reaction between zinc oxide and tin oxide at elevated temperature can result
in formation of zinc stannate, Zn 2Sn04 ' . The materials based on this compound have
various applications with the emphasize on production of different types of sensors for
humidity and gas' detection . One of the widely used process for obtaining ultradispersed
powders of inorganic materials with defined physico-chemical properties is mechanical
activation".
The aim of this work was to determine the changes that occurred in the starting
mixture of ZnO-Sn0 2 system during mechanical activation using the planetary mill. X-ray
powder diffraction analysis was performed to study the microstructural changes that take
place in oxides during mechanical activation. Therefore, the evolution of the average
crystallite sizes and dislocation densities for both oxides in the ZnO-Sn0 2 system was
studied. Determination of the specific surface area was performed using BET method.
EXPERIMENTAL
Mixtures of 2ZnO : ISn0 2 (tetragonal) powders were treated in the planetary mill
(model FRITSCH) from 5 to 160 min. Each milling was performed under the following
conditions : dry grinding of 50g of each powder mixture sample; 19 aghate balls of 11 mm
diameter; aghate pots; rotational speed of planet carrier 300 mm' .
The phase composition and microstructural analysis of activated powders were
obtained by X-ray powder diffractometer with CuKall2 radiation and graphite
monochromator with step scanning conditions 0.02/1s (PHILIPS PW-1820).
The specific surface area SBET of mixtures was obtained by adsorbing nitrogen at 17K,
by using the Flowsorb 2300 equipment manufactured by Micromeritics .
Advanced Science and Technology ofSintering, edited by Stoj anovic et al.

Kluwer Academi c/Plenum Publishers. New York, 1999 219
X-ray diffraction patterns of samples activated for various times ranging from 5 to 160
min showed that activation is accompanied only by an increase of the diffraction line
widths and the slight decrease of their intensities (Fig 1.). Also, there was no evidence of
zinc stannate formation.
I x;
a) x: x ZoO
300 0 5002
x
250
200
x
150
x
100
0
50
A~ Vi ~
0
r-. 0
"'"
10 20 30 40 50 2&
x
b) x ZoO
o 5002
x
140 x
100
60 x x
o
10 20 30
Figure 1. X-ra y diffraction patterns of 2ZnO -Sn02 mixtures mechanically activated for (a) 5 min and
(b) 160 min
The average crystallite size and dislocation density calculated from diffraction data
were performed. The analysis revealed that for the [II 0] direction, the average size of ZnO
crystallites is nearly ten times higher than ones of 8n02 (Tab. 1). However, the increase of
activation time in the range from 5 to 160 min decrease the crystallite size in the case of
ZnO as well as 8n02 crystallites approximately in the same manner. The reduction amount
of average crystallite sizes of both oxides is about 50% .
220
Table 1. The influence of activation time on crystallite size (D) and dislocation density (p)
calculated from XRD patterns
ZnO [110] Sn02 [110]

t [min] D [A] p [em"] D[A] p [ern"]
5 2010 7.43 -10 274 4.00-10 11
160 1000 3.00 .10 10 137 1.60 -10 12
The dislocation densities were calculated using Williamson-Smallman approach and

pointed out on significant increase of dislocation densities (up to l O" em") with the
increase of activation time. Thus, it can be inferred that significant deformation of initial
crystal lattices took place during the activation, particularly for SnO z.
The values of specific surface area of Zn O-SnO z system during the activation
calculated using BET method are shown on Fig. 2. The decrease of specific surface areas
with the increase of activation time is probably the consequence of the agglomeration of
particles during the activation.
i
40
of!! 35 System 2ZnO -S n~

E
.;
~ 30
::l
v:
U
<;::
'u
OJ
25
0.
til
20
0 50 100 150
Activation time, min
Figure 2. Change s of the spec ific surface area s during mechanical activation
CONCLUSION
Mechanical activation of the ZnO-SnO z system in the planetary mill was investigated
in order to determine the influence of activation time on physico-chemical properties of the
system . It was established that, up to 160 min of activation , there was no evidence of
mechanochemical synthesis of zinc stannate. The significant changes on the microstructural
level as well as the decrease of the specific surface area were observed.
ACKNOWLEDGMENT
This work was performed as part of the project "Prognosis of materials properties from
the viewpoint of the synthesis-structure-properties relationship" financed by the Ministry
for Science and Technology of the Republic of Serbia.
221
REFERENCES
1. T.Hashemi, H.M.AI-AIIal<, J.Illingsworth, A.W.Brinkman, J.Woods , Sintering Behavior of Zinc stannate,

J.Mat .Sci. Lett.,9 (1990) 776-778
2 . I.Stambolova, K. Konstantinov, D.Kovacheva, P.Peshev, T.Donchev , Spray Pyrolysis Preparation and
Humidity Sensing Characteristics of Spinel Zinc stannate Thin Films, J. Solid State Chern., 128 (1997)
305-309
3. N.Hiratsuka, A.Hosoi , H.Kobayashi, K.Kakizaki, J. Cer. Soc. Japan , 104 (1996) 1173-1175
4. E.G.Avakumov, Mekhanicheskie Metody Aktivatsii Hirnicheskikh Protsessov, Nauka, Novosibirsk, 1986
(in Russian)
222
Part IV. SINTERING OF OXIDE SYSTEMS
VACUUM SINTERING OF ZIRCONIA BASED CERAMICS
S.Kulkov, T.Sablina, N .Savchenko
Institite of Str ength Physics and Mat erial Sciences, RAS

2/1 , pr .Academicheskii , 634021 , Tomsk , Ru ssia
Il\TTRODUCTION
Plasma spray pyrolysis method for fabricating ceramics is growing in attention

from scientific and technological points of view [1,2]. This method seems to be a suitable
one for the preparation of ultrafine powders of the multicomponent oxide systems in
which each component is uniformly distributed . Although these unique spray pyrolysis
zirconia-base powders have been synthesized, only few investigators have been reported
dealing with the fabrication of specimens from the dense, high-strength ceramics. It may
be due to the major disadvantage of the spray pyrolysis powders. As a rule , they consist
from the hollow spheres and irregularly-shaped particles [1 ,3]. To improve the
sinterability of highly agglomerated ceramic powders , various approaches such as
mechanical milling of powders [4] as well as adding of various dopant, [5] have been
reported in the literature. However, these methods often reveal themselves to be too
tedious processes. The increase of the sintering temperature with the purpose to
intensify diffusion processes is technically easier to do, however this may used not for all
materials. For example, optimum sintering temperatures for conventionally fabricated
Y-TZP at which the densification will be reasonably rapid , but where the abnormal grain
growth will not occur are less 1600 0C [6]. At temperatures above 1600C the increasing
grain size exceeds the critical grain size for spontaneous tetragonal-to-monoclinic
transformation in the sample and leads to the cracking which accompany the
transformation reduces the overall density.
In this work it have been studied the microstructure, phase content and mechanical
properties of Y-TZP ceramics obtained from plasma spray pyrolysis powders after
vacuum sintering at a broad range of temperatures and time schedules and compared
with results of microstructure and properties of the Y-TZP being sintered in air from the
same initial powders under the almost identical conditions.
EXPER~ENTALPROCEDURE
Powders of Zr02 - 3 mol% Y 203 were prepared by spraying Zr-Y nitrate solutions
in inductively coupled plasma of ultrahigh temperature. Bar-shaped samples were
formed by steel die pressing (200 MPa). The samples' density after the die pressing was
about 35% of the theoretical one. The samples were sintered in two different ways: in a
air furnace and in an electric vacuum furnace (vacuum Ix 10-5 Torr). Both sintering

Kluwer Academic/Plenum Publishers , New York, 1999 225
processes were performed at a constant heating rate of 3000C/h up to the desir ed
temperatures, held there from I to 50 h, and then cooled with the furnace .
It have been studied the phase content by X-ray diffractometry, carried out
transmission and scanning electron microscope investigations.
Three-point flexural strengths were determined from as-ground specimens (3 mm high , 3
mm wide, and 20 mm long) . The fracture toughness (Ki.) measurements were made by
the microindentation techn ique [9] with a 100 N Vickers load being applied to the bend
test piece after polishing it to an optical quality.
The transmission and scanning electron micrographs presented in Fig .1 show that
the powder consists of hollow spheres and a significant quantity of shell structures.
Although the hollow spheres has micrometer in size, the Zr02crystallites' size is 20 nm .
Figure 1. TEM micro-graphs ofY-TZP powders synthesis by plasma spray pyrolysis meth od .
X-ray diffraction data have shown that the powders consi st of metastable tetragonal
ZrOz. This powder is po ssible to be described as highly agglomerated nanocrystallin e
particles. The peculiarity of the powd er lies in fact that because of the high cooling rat e
in the process of fabrication and th eir small size they must show the high sinterability.
On the other hand, the presence of crystallites in the form of pol ycrystallin e hollow
particles (agglomerates) reduces their applicability from standpoints of being used as a
sta rting material for engineering ceramics.
The X-ray diffraction patterns of the polished surface of the samp les after sintering
indicated that the samples consisted of two or three phases: tetragonal or tetragonal and
small content of monoclinic phases and cubic phase. When the grain size exceeded the
critical grain size during its growth there occurred spontaneous t-m transformation and
the cracking which accompanied the tom transformation which reduced the density of the
sample.
The density data of the all sintered materials show that although each sample had
approximately the same green density , the samples sintered in vacuum at 1750 0C had
approximately the theoretical density , whereas at 1600 C had density approximatel y
95%. The samples sintered in air had more coarse grains than those samples sintered in
vacuum, despite of having a lower density. The effect of vacuum-sintered ceramics is
higher densities for a equal grain size in comparison with that in ceramics after same heat
treatment but sintered in air. The average grain size of the Y-TZP could reach Sum
without destabilizing effect on the tetragonal phase as generally, in case of yttria-doped
tetragonal samples sintered in the stability range of the tetragonal phase, the criti cal
grain size above which the spontaneous transformation to the monoclinic phase occurs is
about I to 2 urn [8,9] and in our case the critical grain size data for air-sintered cerami cs
are in agreement with this studies.
226
A possible reason why the results for vacuum -sintered materials do not agree with
the results of other works may be due to the enhanced stabilization of t-Zr02 caused by
a large number of anion vacancies which introduced during vacuum sintering at high
temperature. The fact that high amount of vacancies is present in vacuum sintered
ceramics is evidenced by the darkening of the samples after the vacuum sintering [10,II] .
There is one more slight distinction for Y-TZP after sintering in vacuum at high
temperature in comparison with other materials. There is a difference in the amount of
Zr02 particles which have been transformed to the monoclinic state. The amount of the
monoclinic Zr02 both on polished and fracture surfaces of the samples, that has a
spontaneous tetragonal-to-monoclinic transformation , does not exceed 65% for Y-TZP
after sintering in vacuum at I7500C while for other materials it reaches more than 80 %.
High-temperature X-ray data have shown , that increasing the sintering temperature
from 1600 to 1750 0C one may increase the amount of a cubic phase from 20 to 35-
40%. Such cubic -tetragonal phase rat io (35% cubic phase-65% tetragonal phase at 1750
C) is expected on the basis of the known phase diagram [12]. The fact that only 10 %
of the initial cubic phase are remained after cooling down to the room temperature is
due to the diffusion-controlled cubic-tetragonal transformation.
So , we could make the conclusion that all studied materials consist of large
transformable tetragonal phase grains (for the vacuum-sintered and air-sintered
ceramics - 65% and 80%, respectively) and cubic grains which can undergo the diffusion-
controlled cubic-to-tetragonal transformation during cooling from sint ering
temperatures.
For microstructure-mechanical property relations, only samples consisting of 95-
100% of the tetragonal phase were used . Fig .2 shows the variation of the fracture
toughness and fracture surface monoclinic phase content as a function of grain size of Y-
TZP. The KI C and the fracture surface monoclinic phase content for air-sintered Y-TZP
increased linearly with the increase in gra in size. Such behavior agrees with th e
previously reported data [13]. This is due to the stress-induced phase transformation of
tetragonal to monoclinic zirconia. Figure 2 shows that the fracture toughness of the
ceramics sintered in vacuum at high temperatures is almost unaffected when the grain
size is varied. It is quite interesting to note that the samples of Y-TZP after vacuum
sintering at I750C and containing a coarse structure exhibit a higher Ki, despite of a
decrease in volume fraction of the tetragonal zirconia in comparison to the air-sintered
samples. It is also worth to note that 70% of the available t-phase in vacuum -sintered at
17500C materials transform martenstically in the fracture . This is much greater as
compared to that of in air-sintered samples (about 40%).
14 .......- - - - - - - - - - --';
LO
~
E
12 -
~ 10 r-r-
~
~ 8 r-t-
c
.c 6 -
OJ
::J
.Q
2!
::J
U 2 - n
d:
I I
o 1 4
Figure 2. Variation of the fracture toughness and fractured surface monoclinic content as a function of grain
sizeofY-TZP. ,1750 C; , 1600C.
227
1200
(1)
(1) 13 2 crT=1 .9 GPa . (2)
ro
a..
1000
Ko=5 MPa*m"0.5
-,
-,
5 800 (2) 13 2 c T=1.4 GPa.

s:
en
c 600
Ko=3 MPa*m"0.5
~ o 0
iii 400
OJ
.s o
-c
c 200 ~ 1600 DC. air
Q)
rn 0 1 1750 DC. vacuum
0 2 4 6 8 10 12 14
Fracture toughness (MPa*m"0.5)
Figure 3. Relation between bend strength and fracture toughness of Y-TZP. The hyperbolic curves are
calculated from Swain's [14] equation (I) using the data induced for each line.
The relationship between bending strength fracture toughness obtained for Y-TZP
is shown in Fig .3. It can be seen, that the Ki, data and strength for ceramics can be
plotted as a curve with maximum and were characterized by a combination of high
strength and high fracture toughness.
To approximately evaluate the contribution of toughening to the mechani cal
properties, fracture toughness (Kn) of non-transformable part of materials was
calculated using the expression of Swain and Rose [14]. They proposed an expression to
evaluate the strength limitation for transformation-toughened materials and those with a
hyperbolic curve of toughness and strength being predicted:
crc=p crT Ko/(Kc - Ko) (I)
In this expression, crT is a function of volume of transformable tetragonal phase,

Poisson's ratio , volume dilation associated with transformation, and Young's modulus.
The value p is a proportionality constant (0.66 for Y-TZP) and Kc=~K +Ko. K o is the
fracture toughness of the matrix which does not undergo transformation.
This calculations of K , - the fracture toughness of non-transformable part of
ceramic, are shown on fig.3, line I and 2. Curve I in fig.3 is for Y-TZP with 80%
transformable tetragonal ph ase (P2crT = 1.4 GPa) and Ko=2.5 MPaxm 112. Most of the
data points for air-sintered Y-TZP fall within the bounds of the line. The second line in
Content of fracture , %
1 0 0 r - - - - -- - - -- - -- - ---,
'0.... ductile
80 '00-.. brittle
60
40
20
2 3 4
Grain Size (urn)
Figure 4. Data of the qu antitative fracture analysis ofY-TZP.
228
fig.3 is for 65% transformable tetragonal phase (P2a T =1.9 GPa), being related to
17500C vacuum sintering Y-TZP and a Ko=5.
The quantitative analysis carried out by TEM micrographs, fig.4, showed that
there is a decrease in fracture surface area corresponding to the brittle fracture and on
the contrary, the increase in ductile fracture part with the increase in the grain size. The
results of quantitative fractogra-phic analysis show that the high fracture toughness
(Ko) of vacuum-sintered cera-mics is provided by both the multi -phase structure of the
ceramics obtained in cooling from high temperatures and combi-nation of toughening
mechanisms existing in such materials.
So, in th is work we have obtained a material with multi-phase structure that is non-
usual for this chemical composition of ceramics. Under its fracture in transgranual
manner, the potential toughening mechanisms are more effectively involved by
comparison with traditional materials.
CONCLUSION
The vacuum sintering at moderate and high temperature has a marked effect on the
sinterability of the highly agglomerated plasma-sprayed Zr02 - 3 mol % Y203 powders.
Ceramics prepared by sintering in vacuum have higher densities and higher mechanical
properties in comparison with that after almost same heat treatment but conducted in
air. The most interesting results were obtained after high temperature sintering.
Ceramics sintered in vacuum at 17500 C demonstrate close to the theoretical density, have
uniform structure with the average grain size up to 5 urn without the destabilizing
tetragonal phase. These materials demonstrate a combination of both good strength (up
to 1000 MPa) and high fracture toughness (up to 15 MPa x m 1/2).
Its mechanical properties are due to multi-phase structure and combined action of
to ughening mechanisms existing in such materials. Toughening mechanism of this
materials may be described as resulting from both transformation-toughened
mechanisms and other toughening mechanisms caused multi -phase structure of the
ceramics obtained from cooling from high temperature.
References
1. L.Messing, SoC. Zhang, and G . V. Jayanthi, "Ceramic Powder Synthesis by Spray Pyrolysis," J. Am.
Ceram. Soc., 76 [II) 2707-26 (1993).
2. M .K agawa, M . K ikuch i, Y. Syono , and T. Nagae, "Stability of Ultrafine Tetr agonal Zr0 2 Co -
precipitated with Ab03 by the Spray-ICP Technique," J. Am Ceram. Soc., 66 [11] 751-754 (1983).
3. T.Yano, K . N onaka, N . Ot suka, K . Kawai , K. Ue ma tsu, and K . Saito, "Preparation and
Characterization of Fine Alumina-Zirconia Powders by Spray Pyrolysis of Nitrate Solutions"; pp. 165-
72 in Proceeding of MRS International Meeting on Advances Materials, Vol. 3, Edited by M . Doyama,
S. Somiy a, N. Yamamoto, and R . P. H . Chang. Mat erials Research Society , Pittsburgh , PA, 1989.
4. F.Lange. H. Shubert , N. Claussen , and Ruhle M , "Effects of Attrition Millin g and Post-Sintering Heat
Tre atm ent on Fabrication Microstructure and Properties of Transformation Toughened Zr02,"J.
Mater. Sci., 21,768-74 (1986) .
5. G .Theunissen, A . M . Winnubst , and A. J . Burggraaf, "Effect of Dopants on Sintering Behavior and
Stability of Tetragonal Zirconia Ceramics," J. Europ. Ceram. Sci., 9 [4]251-63 (1992).
6. I.Nettleship and R . Stevens, "Tetrago nal Zirconia Polycrystal (TZP) - A Review ," Int. J. High
Technology Ceramics, 3, 1-32 (1987) .
7. K .Niihara, R . Moren a , and D . P. H . H asselman, "Evalu ation of Ki, of Britt le Solids , by Indentation
Method with Low Crack-to-Indent Rat io," J. Mater. Sci. Lett., 1,13-16 (1982) .
8. A.Heuer, R . Chaim , and V. Lanteri "Review: Ph ase Transformations and Microstructural
Characterization of Allo ys in the System Y203 -Zr02" ; pp . 3-20 in Advances in Cer amics , Vol. 24,
Science and Technology of Zir conia Ill. Edited by S. Somiya, N . Yam amoto, and H . Yan agida.
American Ceramic Society , Westerville, OH , 1988.
9. A.Heuer, N . Claussen, W. M . Kriven , and M. Ruhle, "Stability of Tetragonal Zr02Particles in Ceramic
Matrices," J. Am . Ceram. Soc., 65 [12]642-50 (1982) .
10. R.Rice, "Comment o n "Black Color in Partially Stabilized Zirconia" ," J. Am . Ceram. Soc .,. 74 [7]1745-
46 (1991).
229
11 . V.Verneker and D . Nagle , "Effect of Reduction on Vickers Hardness of Stabilized Zirconia," J. Mal er.
Sci . u. 9, 192-94 (1990).
12. H.Scott , "Phase Relationships in the Zirconia-Ittria System," J. Maler. Sci ., 10, 1527-35 (1975).
13. M.Swain, "Grain-Size Dependence of Toughness and Transformability of 2 Mol% Y-TZP Ceramics ,"
J. Maler. Sci. Lett. , 5, 1159-62 (1986).
14. M .Swain and L. R . F. Rose , "Strength Limitations of Transformation-Toughened Zirconia Alloys," 1.
Am. Ceram. Soc ., 69 (7)511-18 (1986).
230
A STUDY OF REACTIVITY AND SINTERABILITY OF URANIUM DIOXIDE
POWDER THROUGH SURFACE ADSORPTION.
G.P.Tiwari, I A.G.C. Nair,2
IMaterials Science Division

2Radiochemistry Division
Bhabha Atomic Research Centre, Trombay
Mumbai - 400085
India
INTRODUCTION
The choice of a suitable parameter to characterise the sintering behaviour of

different powders is important from scientific as well as technological considerations.
Scientifically, it will be very interesting to understand the physical basis for the difference
in the reactivity of the different powders of the same material which governs their sintering
characteristics. Despite nearly identical or only marginal differences in particle size and
surface area, reactivity variation among the powders of the same material can bring about
significant differences in their sintering behaviour. Technologically, the assessment of the
sintering characteristics is of great importance in controlling the final density and the quality
of the sintered product. The U0 2 powders are usually prepared through the decomposition
of ammonium diuranate or carbonate . The powders prepared through decomposition at
lower temperatures sinter to higher densities at relatively lower temperatures and vice-
versa. In general, lower the temperature of decomposition, higher is the surface reactivity .
Uranium dioxide powders produced through decomposition of ADU at temperatures greater
than 1273 K are almost inactive and can be sintered only with great difficulty. It has been
shown '" earlier that the adsorption of metal ions on the surface of uranium dioxide powder
taking place in an aqueous medium can distinguish clearly the sintering characteristics of
various U0 2 powders with varying surface reactivities . In a survey of the adsorption
Advan ced Science and Technology ofSintering, edited by Stojanovi c et .1.

Kluwer Academic /Plenum Publishers , New York, 1999 231
characteristics of several elements', it was found that manganese, iron and niobium were
adsorbed strongly and provided satisfactory distinction between different grades of powder .
Detailed studies on manganese have already been reported'. In the present report,
adsorption characteristics of iron on uranium dioxide powders of varying activity are
presented . In the previous cases, the powders were prepared by decomposition of ADD
in the laboratory . The materials for the present series of experiment were obtained from
Nuclear Fuel Complex, Hyderabad and were prepared by the decomposition of ADD.
The adsorption experiments were carried out through the introduction of nearly one
gram of uranium dioxide powder in 30 C.c. of distilled water kept in a beaker . A mixture of
radioactive as well as inactive Fe2(S04h in a fixed ratio was added to the same beaker and
the whole system was stirred well for ten minutes to facilitate the adsorption of iron ions on
the surface of D02 powder. At this stage, it is essential to maintain proper pH control so
that the dissolution ofD0 2 is completely avoided and a fixed ionicity of the iron atoms in the
aqueous medium is maintained. Next D0 2 was filtered off in a gooch crucible and washed
with pure distilled water till no radioactiv ity was detected in the filtrate. To estimate amount
of iron adsorbed on the surface of D0 2, it was first dried, then dissolved in nitric acid
followed by gamma spectrometric assay in a HPGe detector attached to a 4K analyser.
The peak area under 1099 and 1292 keY gamma lines were used for estimation of 59Fe . The
59Fe radioactivity data was then converted into the total amount of iron adsorbed per gram
of D02 in standard manner. Surface area was measured by BET method and sintering
densities were measured after annealing at 1973 K in ammonia atmosphere. Sintering
densities represent the average of two values and the AlP values are accurate within two
percent.
In adsorption experiments, it is essential to determine whether the adsorption is single

layered or multi-layered. Only if the adsorption is monolayered, it can be affirmed with
certainty that the adsorption is controlled by the mutual interaction between the adsorbent
and the adsorbate. In the present case, the adsorption of iron atoms on the surface of D0 2
was found to exhibit Langmuir type of adsorption . Langmuir type of adsorption behaviour
characterises monolayered adsorption':'. Hence the adsorption behaviour reported here is
characterist ic of the nature of surface of the D0 2 powder and its interaction with ferric ions.
SURFACE ADSORPTION AND SINTERABILITY
The amount of adsorption per gram of uranium doxide is taken as an index of

adsorption and designated as Adsorption Index Parameter (AlP). The experimental results
are recorded in Table 1.
232
Table 1. Data on specific surface area,average particle size,sintered density and ferric ion
adsorption for uranium dioxide powder.
SSA Sintered Density AlP
( mz'/g) (glee) ( Ilg)
I 3.46 10.65 719
2 2.92 10.51 616
3 2.64 10.41 532
4 3.04 10.43 683
5 3.07 10.51 666
6 3.27 10.45 494
7 3.17 10.40 507
8 3.03 10.51 580
9 2.83 10.35 598
10 3.37 10.42 577
11 2.11 10.05 357
Figures land 2 show the results of the table in graphic form. Fig. I is a plot of
sintering density against AlP and shows an increasing trend with AlP. If AlP is taken as a
measure of the surface reactivity, then the fig. I shows the expected behaviour. A linear
regression analysis of the data yields a value of 0.83. Hence the linear representation of the
data is justified. The final sintered density is also influenced in an important way by other
sintering variables such as surface area, particle size, grain density etc. Despite this, a
satisfactory linear correlation, albeit empirical, between AlP and sintering density is
10.7

10.6
10.5

~
enz 10.4
w
0
0

W
0:: 10.3
W
I-
Z
en
10.2
10.1

10.0 -+----r---,-----r---,--.,.---r-----,----,----f
300 400 500 600 700
AlP
Figure 1. Plot of sintered density against the amount of iron adsorbed per gram of VO z powder (AlP) .
233
10.7

10.6
10.5

~
c;; 10.4
Z
W
Cl
Cl

w
ffi 10.3
I-
z
c;;
10.2
10.1

10.0 +-..-,--r-.--r-r--.----,-,-..,.-.-.,---;r--r----r-;
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
SURFACE AREA (SSA)
Figure 2. Plot between sintered density and specific surface area (SSA) .
obtained . It shows that if the variation of other parameters listed above is maintained
within the normal limits, AlP is indeed a reliable parameter to assess the sintering
behabviour of uranium dioxide powder.
SURFACE AREA AND SINTERABILITY
In Fig. 2, sintered density is plotted against surface area. With the increase of
surface area, surface reactivity is expected to decrease. This expectation is fulfilled. Linear
regression coefficient of the plot in fig. 2 is 0.82 and therefore the linear relationship
between these two parameters is validated . Although in the present case, the correlation
between surface area and sintered density is found to hold good, it is not universally true.
According to Pollanz 4, it is possible to prepare uranium dioxide powder having same
surface area and varying surface reactivities . Hence surface area cannot be considered as a
reliable measure of surface reactivity. In an interesting experiment , Marajofsky et al 5
separated the different size particles of uranium dioxide through centrifuge from the same
lot of powder. Though the different group of powder had varying surface areas and particle
sizes, sintered densities in all cases were the same. Hence neither the surface area nor the
particle size can provide a reliable indication of sinterability. In contrast, AlP depends only
on surface activity and also exhibits a correlation with the final sintered density .
234
CONCLUSION
Present experiments when considered together with previous results'" demonstrate

in an unequivocal manner that AlP does indeed provide a reliable measure of surface
reactivity and sinterability. It can be used to compare the surface activity of different
grades of the powders of same material. Because of the ease with which AlP can be
determined, it is very wel1 suited for use as a control parameter in commercial operations.
The net surface reactivity of the powder which provides the driving force for
sintering as wel1 as adsorption depends upon the defects (present within the particle and on
surface) and uncompensated bonds of the surface atoms . The basic issue is how do these
properties vary with the reactiv ity of the powder. Further experimental work is essential to
gain insignt into this phenomenon.
ACKNOWLEDGEMENT
The authors grateful1y acknowledge several interest ing discussions on the subject with
Drs. S.K.Kulshreshtha, R. Venkatramani of Chemistry Division and Shri. Ram Prasad of
Materials Processing Division, BARe.
REFERENCES
1. G.P.Tiwari, N.C. Soni and S.V.K. Rao, Characterisation ofV0 2 powders by

radioactive adsorption, J. Nucl. Mat. 61:110(1976)
2. G.P.Tiwari, N.C. Soni, A.G. e. Nair and Satya Prakash, Characterisation of
V0 2 powders by radioactive adsorption, 1. Nucl. Mat. 127:225(1985)
3. D.M. Young and A. D. Crowel1, Physical Adsorption of Gases, Butterworths,
London (1962) .
4. H. Pol1anz., Determination ofV0 2 powder activity by DTA,
J. Nucl. Mat. 46 : 210(1973).
5. A. Marajofsky, L Perez and J. Celora , On the dependence of characteristics
of powders on the ADV process parameters, 1. Nucl. Mat. 178:143(1991)
235
SINTERING AND CREATION OF POROUS STRUCTURE
OF BIOACTIVE CERAMICS
Emilija Fidancevska' , Jorg Bossert' and Milosav Milosevski '
'Faculty of Technology and Metallurgy,University "St Ciril and

Methodius" 91000 Skopje, Republic of Macedonia
zUniversitat "Friedrich Schiller" , Technisches Institut, 07743
Jena,Germany
INTRODUCTION
Biomaterials are used in nearly all areas of human medicine such as

pharmaceutical purposes, implant materials, and medical devices. Some biomaterials
are designed to remain in the human body for the lifetime of the patient, such as
total joint replacements, or for as long as the device is designed to function , such as
catheters.
The following definition for biomaterial was agreed on at Consensu s
Conference of the European Society for Biomaterials which was held in Chester ,
England, in 1986, 1:
A "biomaterial is a non-viable material used in a medical device intended to
interact with biological system ". A "medical device" was defined at the same
conference as "an instrument, apparatus, implement, machine, contrivance, in vitro
reagent, or other similar or related article , including any component, part or
accessory, which is intended for use in the diagnosis of disease or other conditions,
or in the cure, mitigation, treatment or prevention of disease in man ". Biomaterials
represent all group of materials, namely ceramics, metals, polymers and composit es.
Metals and ceramics are mainly used for hard tissue replacements: metals for parts
that are exposed to bending and tensile stresses and ceramics for parts that require
especially good wear and friction properties. Polymers are used for both hard and
soft tissue replacements due to their wide range of properties. Composite materials
are specially interesting for biomaterials applications due to the possibility of
tailoring their properties to match the properties of the surrounding tissue.
Hydroxylapatite Ca lO(P04MOH)z is a ceramic that closely resembles the chemical
composition of bone and is therefore one of only two materials (the other being
bioactive glass formulations) capable of forming a direct chemical bond with bone"
Because of the bonding ability of this material to bone, the dense and porous forms
Advanced Scien ce and Technology ofSintering , edited by Stojanov ie et aI.

of hydroxyapatite ceramics have been suggested for toot implantation, periodontal
treatment, alveolar ridge augmentation,etc. In order to introduce the newly formed
bone fully into the material and increase the bone mass, the hydroxyapatite must be
designed as high porous one , with interconnecting pore structure with large surfac e
area as much as possible.
The purpose of this pap er was the pr eparation of 2 types of hydrox yapatite
cer amics, with two types of microstructure: dense compacts and porous sponge. Both
types of hydrox yapatite are a potential candidate for use in medicine.
EXPERIMENTAL METHODS
Hydroxyapatite for bioceramics (Firm Merck ,Germany) has been used for
these investigations. The Ca/P ratio was analyzed by a standard EDTA titration for
Ca" and phosphomolybdate technique for P0 43 For the purpose of the increase of
the geometrical activity, the powd er was milled by attriting (1500 r/min, during 0.5h).
The powder was isostaticaly pressed at 50-600 MPa and than sintered at 1100
and 1200C for 0.5 - 3h in air atmosphere using heating rate of 5/min. The bulk
density of the compacts was measured by immersion method. Ceramographic
investigations of the dens e samples were mad e with a scanning electron microscope
(Leica S 4401) E-m odulus, shear modulus and Poisson 's rati o were det ermined by
ultra sonic method (Krautkramer USD 15).Thermal expansion properties were
determined by dilatometer (Netzsch 402E).
The porous structure of hydrox yapatite has been creat ed : by use of
polyurethane foam , C-fibres and hydrogen peroxide. Op en-celled macrostructure
was fabricated by coating the stru ts of a polyurethane foam with a ceramic slurry and
than firing the resultant structure to pyrolyse the substra te and sinter the ceramic
system. Polyurethane with density of 22 kg/rrr' was used as substrate which was
coat ed with powd ered slurry of hydr oxyapatite. Th e foam was squeezed and dipp ed
into the slurry, looking in that case like a spongy. During the expansion to the
original shape and size, the foam was impregnated by the menti oned slurry. TG
analysis has been used for determination of the fully mass lost of the polyurethane
foam . This analysis has been used for the determination of the temperature
schedule of the heating treatment of polyurethane coat ed substrate. After dr ying at
room temperature 24h and at 105C/6h, the coat ed substrates were heated up to
1200C in a schedule which minimized disruption during pyrolysis and allowed the
ceramic to fully density. Th e heating schedule consisted of a heating rate of OS/min
up to 800C, rapid heating of IOvmin from 800 to 1200C and allowed to cool in the
furnace .
C-fibres (Toko Rayon C.Ltd) as bundles with diameter of 500 mm have been
embedded in a very dense pulp of hydroxyapatite, water and deflocculant. After
drying of the system, it was sintered at 1200C/3h, using heating rate of l /min.
HzOz with concentration of 4% was used as a creator of porous structure. A slip
of hydroxyapatite powder, defloculant Dolapix CE 64 and unstabilised HzO z was
continuously mixed at room temperature. During the mixing an visible formation of
bubbles of free oxygen was not notic ed . The slip was poured into aluminum frames ,
forming cakes with dimensions lOx5x2 em. Aft er drying at room temperature 24h
and at 105C/5h, the porous material was sintered at 1200 C/3h in air atmosphere.
The relative density of the foam material was determined from the ratio of mass
to volume. SEM microscop y was used for investigation of the form , size and
orientation of the cells and struts of the foam mat erial. E-m odulus and bending
238
strength were determined by three point method (Netzsch 403), using crosshead
speed of 0,5 mm/min and span of 30 mm. Compressive strength tests were
performed on an Instron-model 1126 tester at crosshead speed of 0,5 mm/min.
The Ca/P ratio of the hydroxyapatite was 1.63 0.02. Average size of the
agglomerates of the powder was 1 0.5 mm . These agglomerates were composed of
primary particles of 100 - 200 nm. Specific surface area of the powder was 8.6 m 2/g.
During the sintering in the temperature interval RT-1100/1200C for 0.5-3h
compacts with density varying from 60 -95 % TD have been obtained. A maximal
density of 95 % TD has been achieved at a temperature of 1200C for 1h, where a
shrinkage of 15 % has been registrated. XRD of the sintered compacts showed an
absence of the secondary phase.
A SEM micrograph of the fractured surface of dense hydroxyapatite is shown in
Fig.1. The size of the closed pores was 0.2 0.1 mm.
Figure 1. SEM micrograph of fractured surface of den se hydroxyapatite (x2000)
The variation of E- and shear modulus of the compacts with porosity is shown
in Fig.2 and 3. These variations can be approximated by the equations (1) and (2)
E = 113 exp(-3 .90W-28) E[GPa] 8[%] (1)
G = 49 exp(-3.491O-28) G[GPa] 8[%] (2)
In the first approximation, for zero porosity E- and shear modulus for
hydroxylapatite have values E = 113 18 GPa and G = 41 8 GPa.
239
40
35
0
30
25 0
ro
0..20
~
ill 15
10
0
0 5 10 15 20 25 30 35 40 45
e (%)
Figure 2. Variation ofE-modulus with porosity
Thermal expansion characteristics of the investigated system in the interval RT-

1000-RT showed absence of hysteresis effect, that proves , that the system is in
thermal equilibrium. The technical coefficient of thermal expansion was 1O.51O-6/K.
In order to define the temperature region of the thermal treatment for slurry
coated substrates obtainment, the knowledge of the parameters of pyrolysis of
polyurethane foam is important. Fig.4 illustrates a weight loss of the polyurethane
foam as a function of temperature .The pyrolysis was carried out in air atmosphere .
The density of the foam ceramics obtained by using polyurethane foam vas 35
5%TD, Fig.5. The average sizes of the open cells was 200 - 500 mm. One part of the
struts contain partial cracks caused by disruptive of polyurethane substrate. The
struts have wall thickness between 30 and 80 mm. Bending strength of this porous
material was 1.6 0.3 MPa.
100r--------------------,
90
80 o
70
60 o
co
0.. 50
o

w40
30
20
10
OL_.o...~L_.o...~L_.o...~...........~...........~...........~...........~L._............._ ~
o 5
Figure 3. Variation of shear modulus with porosity
240
120 r -- - - - - - -- - -- - - - - - - ----,
100
80
Figure 4. Weight loss as a function of the tempera ture for pyroly sis of polyurethane foam (dT/dt=I /min)
Figure s. Typical porous structure of hydroxylapatite produced by polyurethan e foam (x20)
Figure 6. Typical porous structure of hydro xy-hydroxy-apatite produced by C fibers (x 20)
241
Figure 7. Typical porous structure of apatite produced by H202 (bar I mm)
Figure 8. Microstructure of the densified walls ( x 4000)
By use of C-fibres (oriented) and their sacrificing in air atmosphere (RT-

1200C) a structure presented in Fig.6 was obtained. The porosity of the system is
dependent on the quantity of the used C-fibres. Using C-fibres in the oriented
position, it doesn't exist a communication among the formed channels. The diameter
of these channels was 400 - 500 mm. Its variation is enabled by use of C-fibres
bundles with different diameter.
By use of hydrogen peroxide as a creator of porous structure, the structure
presented in Fig.7 was obtained. The integral porosity of the porous bodies was
685%.The pores are interconnected among each other and with a size of 100 -
1000mm.
In Fig.8 a microstructure of pores wall is presented. It is evident that the walls
are with density closed to the theoretical one. The grain size is in interval from 0.5-2
mm. In the boundaries of the grains a small amount of closed pores with size of 0.5
to 0.8 mm are located. Some mechanical properties of this porous system are given in
Table 1.
242
Table 1. E-modulus, bending and compressive strength of cellular hydroxyapatite
E-modulus, GPa bending strength,MPa compressive strength,MPa

1.6OA 20.3 72
The value of bending strength is close to that one presented in the literature.'.
Yokozeki et al 4 refers to the value of compressiv e strength of 12.5 MPa for
hydroxyapatite with porosity of 60 5 % . In Table 2, the values of E-modulus,
bending and compressive strength of cortical and cancellous bon e." are shown.
Table 2. Some mechanical characteristics of cortical and cancellous bone z.s
Propertie Cortical bone Cancellous bone

E-modulus,GPa 7-25 0.05-0.5
Bending strength,MPa 50-150
Compressive 130-180 2-12
strength,MPa
On the base of the data presented in Table 1 and 2 it could be concluded that
porous hydroxyapatite obtained by HzOz as a pores creator, considering mechanical
properties and porosity, could be ranged between cortical and cancellous bone .
Having in mind its biocompatibility it could be successfully applied in medicine .
REFERENCES
1. D.F.Williams (ed .), Proceedings of a Consensus Conference of the European

Society for Biomaterials,Chester,England , March 3-5,1986,Elsevier Science
Publischers,Amsterdam-Oxford-New York -Tokyo (1987).
2. L.L.Hench,Bioceramics:From concept to clinic, JAm.Ceram.Soc.,74(7)1487(1991)
3. A.S10sarczyk, Highly porous hydroxyapatite material,
Powder Metallurgy International, 21(4)24(1989)
4. K.Ioku ,H.Kuro sawa,K.Shibuy a,H.Yokozeki,T.Hayashi, In vivo reactions of the porous
hydroxyap atite,b-TCP and b-TCP coated hydroxyapatite,in Bioceramics, Voll,
O.H.Anderson and Yli-Urpo,ed.,Butterworthhh-Heinemann (1994).
5. A.Ravaglioli ,A.Krajewski, Bioceramics, Chapman & Hall,Lond on (1996).
243
ANALYSIS OF THE SINTERING PROCESS
OF ZoO AND CdO BY THE APPLICATION
OF SINTERING DIAGRAMS
V.M.Minic! Z.S.Nikolic,2 and M.M.Ristic 3
ICenter for Multidisciplinary Studies , University of Belgrade ,

2Faculty of Electronic Engineering , University of Nis,Yugoslavia
3Serbian Academy of Science and Arts, Belgrade, Yugoslav ia
INTRODUCTION
The complexibylity of sintering process, which is effect of simultaneous and

successive actions of elementary mechanisms, induced the develop and application of
theoretical method in the mean of problems of mathematical modelling and process
simulations 2 . In that view, the sintering diagrams developed by Ashby I, were showed as
effective and exact method for complex analysis of sintering process. In the most cases
sintering diagrams here application for identification of dominant transport mechanisms and
comparative analyse of theoretical and experimental data as well as in term of prognosis of
the process. The investigation in this paper present calculation and analysing of sintering
diagrams of zinc and cadmium oxides, which determined dominant transport mechanisms
and field of dominanc e in investigated oxide systems.
SELECTION OF DIFFUSION CONSTANTS FOR CONSTRUCTION

SINTERING DIAGRAMS
The construction of sintering diagrams are based on equations which defined the rates
of mass transport during sintering process, which can be shown in general form
i = f(a ,y p,J.1A.T; ,n.N,ogz 'op ' o.; Dov' Dop' p"g, Qz'Qgz.Qp, Qg) , (1)
where, a- particle radius, yp-surface energy , zz-shear modulus, dt-density, Tt-melting point,
n - molecular volume, N- dislocation density , ogz- effective grain boundary thickness, 0,-
effective surface thickness, D oz - pre-exp, grain boundary diffusion , D ov- pre-exp, lattice
diffusion, Dop - pre-exp, surface diffusion, Pog - pre-exp, vaporisation, Qz-activ. energy,
Advanced Science and Technology of Sintering, edited by Stoja novic et al.

lattice diffusion, Qgz-activ. energy, grain boundary diffusion, Qp-activ. energy, surface
diffusion, Qg-activ. energy, vaporisation.
The initial supposition for construction of sintering diagrams is identification of exact
values of all physical parameters which figured in equation (1) . The chose of physical
parameters of zinc and cadmium oxides is determined by experimental investigations 3-6.
The construction of sintering diagram of zinc oxide was made by constants listed in Tab.l .
Table 1. Values of physical parameters for zinc oxide.
Parameters I Values I References

n (m') 2.38IO-l " 7
T, (K) 2248 3
P (kg/rn") 5.642.10-3 3
2
Yp (11m ) 0.90 14
l! (MPa) 4.93.107 17
Temp. coif. for l! (K"I) 2.210-4 17
N (m") 1010
Ogz (m) 5.10-10 16
op(m) 1-10- 10 16
n, 2
(m /s) 4.9.10-10 9
Q.(kl/mol) 168.93 9
2
Dogz (m /s) 1.16.10-7 9
QgZ(kl{mol) 144.78 9
n, (m Is) 1.10-7 12
Qp(kl/mol) 83.74 12
Pv (MPa) 210-4 13
o., (klIm ol) 114.8 13
Table 2. Values of physical parameters for cadmium oxide.
Parameters I Values I References

n (m'') 1.31610- 4
TSUblimati"f, (K) 1770 4
P (kg/m) 8.2.10-3 4
2
t; (11m ) 1.2 II
l! (MPa) 12.6.107 18
Temp. coif. l! (K"I) 3.810-4 18
N (m") 1010
Ogz (m) 5.10-10 16
op(m) 2.5.10-10 16
Doz(m%) 4.2.10-8 14
Q.(kll mo!) 266.0 14
Dogz (m s)
2/
9.7.10-10 IS
Qgz(kl/mol) 133.43 IS
2
Dop (m /s) 2.2.10-9 IS
Qp(kl/mol) IIO.61 15
Pv (MPa) 3.424.10-3 4
Quo, (kl/mol) 243.7 8
246
Sintering diagram of cadmium oxide was construction by values of physical
parameters listed in Tab.2. The value of melting temperature of CdO dose not exist,
because on atmosphere pressure it sublime, so for construction of sintering diagram,
sublimating temperature will be used instead of melting temperature.
On the sintering diagram of ZnO, shown a Fig.l , during sintering process of systems
spherical particles (particle radius IOum ) of zinc oxide, the 0, 1,2 and 3 stage sintering can
by determined. In the initial stage of sintering, the dominant role during the transport matter
have surface diffusion, grain boundaries diffusion and on temperatures over 1500 K, the
volume diffusion from grain boundaries. The driving force at the beginning of sintering
process is surface free energy of the system'. According to tendentious of the system to
decrease the surface energy, the surface diffusion at the beginning of sintering process has a
dominant role.
With advancing of sintering process, the neck size increased and the rate diffusion
among the grain boundaries between spheres is also increace 10. When the neck size became
x=0.88a, the grain boundaries diffusion have a dominant role in mass transport is
providing highest diffusion migration among grain boundaries. On the temperatures over
1500 K, at the finish of the initial stage of sintering, a dominant role in transport matter has
the volume diffusion. That dominant role can be explain by dissociation zinc oxide lattice
19
on temperatures over 1273 K With increasing of temperature this process is intensified.
The increase concentration of oxygen vacancy create the field with predominant volume
diffusion. This diagram (Fig.l) distribution fields of surface diffusion, diffusion from grain
boundaries and volume diffusion was affmned by theoretical investigations': 17. 10. When
T IKJ
0
500 1000 1500 2000
0I
GRAIN BOUNDARJ ES
2{j VOLUME DIFRJSION
::T D1FRISJON
FROM GRAIN
0I BOUNDARIES
co
0I
CI.:
"x
LJ "l
0
-l - I
CD
0 :
~j ~
0.0 0.2 0. 4 0 .6 0 .8 1. 0
Tr M
Figure 1. Sintering diagram of zinc oxide spherical particles system (a = l 0l!m).
247
the neck size increase to x=0.45 a, the initial stage is finished and intermediate and final
stage beginning. The dominant role in the mass transport during the intermediate and final
stage sintering is played by grain boundaries diffusion and volume diffusion from grain
boundaries.
The sintering diagram of cadmium oxide spherical particles system (particle radius
l Oum) sowed on Fig.2.
During the sintering process of CdO, the initial, intermediate and final stage sintering can
be determined. In the initial stage of sintering, the dominant role during the transport
matter have surface diffusion, grain boundaries diffusion and the volume diffusion from
grain boundaries for temperatures over 1250 K. The rate of all three transport mechanism
are same, so the "triple" point is appeared it the temperature 1250 K.
T (K)
0
500 1000 1500
ci
I
VOLUME DIFFUSION
GRAIN BOUNDARIES FROMGRAIN
::r 2/3 DIffUSION \ BOUNDARIES
ci
I
GRAINBOUNDARIES
DIFFUSION
(X)
ciI
a:
<,
~
l:)(\J
0
-.J -
I
SURFACE DlFl-USION
-
lD
0
N ADHESIONS
I
0.0 0.2 0.1I 0 .6 0.8 1.0
TITM
Figure 2. Sintering diagram of cadmium oxide spherical particles system (a=lOJlm).
In order to decrease the system free energy, the surface diffusion has a dominant role at the
beginning of sintering process. When the neck size became x=O.Ia and when sintering
temperature is 1250 K, the grain boundaries diffusion have a dominant role in mass
transport . The as-formed grain boundary between cadmium oxide spherical particles
represents the sink for oxygen vacancies, providing the highest diffusion mobility in the
grain boundary area. The cadmium oxide begin evaporate at temperatures interval 1173-
6
1273 K The oxygen joins left cadmium oxide lattice, so increase concentration of oxygen
vacancies, providing highest diffusion mobility across volume lattice. That is affirmed by
on sintering diagram by appeared field of dominant volume diffusion. When the neck size
increase to x=0.45a, the initial stage is finished and intermediate and final stage beginning .
The dominant role in the mass transport during the intermediate and final stage sintering is
played by grain boundaries diffusion and volume diffusion from grain boundaries .
248
CONCLUSION
The sintering process of zinc oxide and cadmium oxide was examined by analysing
sintering diagrams. Based on the analysis of sintering diagrams of zinc oxide and cadmium
oxide , the 0, 1, 2 and 3 stage sintering were determined. In the initial stage of sintering the
mass transport is taking place by simultaneous effect of surface diffusion, by grain
boundaries diffusion and volume diffusion from grain boundaries. The dominant role in the
mass transport during the intermediate and final stage sintering is played by grain
boundaries diffusion and volume diffusion from grain boundaries.
REFERENCES
1. M.F.Ashby, Acta Metall., 22, 275 (1974)

2. M.M.Ristic, Z.S.Nikolic, The theory of sintering diagrams with elements of sintering physics, SASA,
Monographs, Department of technical sciences No 27, Belgrade, 1987 (in Serbia)
3. K.P.Kuzmina, V.A.Nikitenko, Zinc oxide to obtain and optical properties, Nauka, Moskva, 1984 (in
Russian)
4 . A.M.Chizhik ov, Cadmium , Nauka, Moskva, 1962 (in Russian)
5. A.N.Men , Y.P.Borobyev, G.I.Chufarov, Physic-Chemical properties nonstoichiometric oxides,
Chemical, Leningrad, 1973 (in Russian)
6. M.H.R.Lankhorst, HJ.M.Bouwmeester, H.Verweij, l.Am.Ceram.Soc., 80 (9), 2175 (1997)
7. G.D.Mahan , l.App'phys., 54, 53 (1983)
8. Physic-Chemical properties oxides (editorial work G.V.Samsonova), Moskva, 1978 (in Russian)
9. BJ.Wuench, H.L.Tuller, l.Phys.Chem. Solids, 55, 975 (1994)
10. R.M.German, Powder Metal1urgy Science, Metals Powder Industries Federation, 1984
11. C.Gandh i, M.F.Ashby, Acta Metall., 27,1565 (1979)
12. DUskokovic, Z.S.N ikolic, M.M.Ri stic, Sci. Sintering, II , spec . ISSUE, 59 (1979)
13. Ya.I.Gerasimov, A.H.Krestovnikov, A.S.Chahov, Chemical thermodynamics in non -ferrous metallurgy,
Moskva, 1960 (in Russian)
14. M.F.Ashby , S.Bahk, J. Bevk, D.Tumbull, Progress in Materials Science, 25, 1-34, Pergamon Press, Great
Britain, 1980
15. W.Gust, S.Mayer, A.Bogel, B.Predel , Journal de Physiqu e, 46 , C4-537 (1985)
16. J.P.Roberts, C.Wheeler, Trans.Faraday Soc., 56, 570 (1960)
17. K.Hauffe, Solids and surface reaction, Moskva, 1960
18. HJ.Frost, M.F.Ashby, Deformation-Mechanism maps, Great Britain, 1982
19. O'Milo sevic, Magi strate thesis., CMSBU, Belgrade, 1986
249
CERAMIC PROPERTIES OF THE SINTERED
MATERIALS IN THE Sn-Sb-Cu-O SYSTEM
Maria Zaharescu, Susana Mihaiu, Stefania Zuca
Romanian Academy, Institute of Physical-Chemistry,

202 Splaiul Independentei, 77208, Bucharest
INTRODUCTION
Sintered SnOrbased ceramics were considered to be prormsmg materials for

manufacturing the stable electrodes for the various technological applications, as aluminium
electrolysis 1 (inert anodes) or glass industry 2,3. For such applications, a high electrical
conductivity and high sintering ability ensuring a high density and, consequently low
porosity of the final product are necessary .
Addition of various metallic oxides has been suggested to increase the electrical
conductivity and raise the sintering capacity of Sn02. The best results were claimed for a
combined addition of Sb203 and CuO . The addition of antimony (III) oxide is claimed to
increase dramatically (by four to five orders of magnitude) the electrical conductivity of
Sn02, which is attributed to the increased charge carrier concentration. Copper (II) oxide is
added in order to improve the sintering ability and enhance the densification of Sn02 4,5.
Below 900C, the rate of densification can be explained in terms of viscous flow model,
while at higher temperature a copper oxide rich liquid is formed and a rearrangement is
occurring even for short sintering time.
In the manufacturing of stable electrodes Sn02 rich composition are required (Sn02
content above 90%) .
Complementary studies 6, 7 covering the whole concentration range of composition in
the Sn02-Sb203-CuO system pointed out the complexity of the process that occur during
the formation of the several phases in the system. The following reactions occur:
Sb203 + 1/ 202 = Sb204
"., 500C: (1)
>750C: Sb204 + CuO + 1/ 202 = CuO Sb20S (2)
>950C: CuO Sb20S + 7CuO = 4Cu20 . Sb20S + 202 (3)
>1OOOC: Sn02 + CuO . Sb20S + Sb20 4 ~ Sn02 ( ss) (4)
The reactions mentioned above strongly influence the sintering ability of the samples in
the considered system.
Ad vanced Science and Technol ogy ofSintering, ed ited by Stojan ovi c et aJ.
Kluw cr Acad em ic/Plenum Publishers, New York , 1999 251
In order to establish oxide compositions, which lead to dense ceramics a systematic
study of the sintering of a semnificative number of samples in the Sn02-Sb 20 3-CuO, were
performed .
EXPERIMENTAL
The samples were composed from Sn02, Sb20 3 , CuO all reagent grade . The oxide
mixtures were obtained by wet homogenisation of powders with particle size of less than
60llm . Then cylindrical samples of 10 mm diameter were pressed at 30 MPa and thermally
treated at temperatures between 600 and 1200C, with 1 hour plateau. The heating rate was
3-SoC/min.
After thermal treatment, the samples were analysed by X-ray diffraction using a TUR
M-63 apparatus equipped with HZG diffractometer operating with COka.
The porosity was determined by weighing samples before and after 24 hours immersion
in toluene.
The linear shrinkage was determined by measuring the diameter of the samples before
and after the thermal treatment with a Carl Zeiss micrometer.
The density was determined by the hydrostatic method .
RESULTS AND DISSCUSION
Phase composition
The initial oxide composition of studied samples is shown in Figurel. The hatchured
zone in the triangle represents studied mixtures in a previous paper 4 . The reactions
presented also show that whenever Sn02 and CuO coexist with Sb20 3, its tendency to react
CuO 10 20 30 40 50 60 70 80 90 Sb 20 3
Figure 1. The starting composition of the samples .
252
Sn
A=CuO.Sb20 S
B=4Cu 20 .Sb20 S
Cu o
Sb
Figure 2. The framing of the samples in the Sn-Sb-Cu-O quaternary system .
with CuO and yield CuOSb20 S is much higher than the forming solid solution based on
Sn02 . Owing to this finding all subsequent reactions are determined by CuO :Sb20 3 initial
ratio .
This ratio affords the classification of the samples in three categories:
-CuO:Sb20 3=1 ; samples lie on Sn02-equimolecular mixture
-CuO :Sb20 3> I; samples lie on CuO excess zone .
-CuO :Sb 20 3<1; samples lie on Sb20 3 excess zone .
Based on phase composition identified at various sintering temperatures, the mixtures
studied may be placed in the quaternary systems shown in Figure 2.
At 800C the samples belong to the quaternary section SnOrCUO-CuOSb 20 S-Sb20 4;
at 1000C they belong to the Sn02-Sb204-CUOSb20s-4Cu20Sb20S quaternary subsystem.
The phase composition of thermally treated samples at llOOC-one hour, is shown in
Table 1. Compared to the phase composition mentioned at 1000C one can note the
formation of rutile type Sn02(ss) and trirutile CuOSb 20S (ss) solid solutions 8.
Ceramic properties
The samples thermally treated at 600C are insufficiently sintered to allow the
determining of ceramic properties. The ceramic properties of thermally treated samples
above 800C are shown in Figures 3 and 4.
At 800C (Figure 3a) most of samples exhibit linear expansion rather than linear
shrinkage. At 1000C (Figure 3b) most samples also show linear expansion; a small
contraction of samples in the CuO-rich zone was also noted.
A sensitive linear shrinkage of most samples was noted at 1050C (Figure 3c) . It was
found out that the samples that still expand possess a CuO :Sb20 3 ratio lower than unit and
samples whose CuO Sb 20Sor 4Cu 20 Sb 20 S are majority phase components.
The linear shrinkage of samples becomes significant at IIOOC except those whose
CuO :Sb20 3 initial ratio is smaller than one or CuO :Sb20 3=1 and Sn02 content is lower than
40% .
253
Table I.The phase composition and the density of the samples thennally treated at 1100C.
Sample Oxide composition (mol. %) Phase composition Density
Sn02 Sb203 CuO
ratio CuO :Sb 20 3 =1
Al 80 10 10 Sn02 (ss) 5.816
A2 60 20 20 Sn02 (ss) 5.9237
A3 40 30 30 Sn02, CuO Sb 20S
At 33.3 33.3 33.3 CuO Sb20S
As 20 40 40 CuO Sb 20S(ss)
Ar, 10 45 45 CuO Sb 20 S
ratio CuO :Sb20 3 > 1
BI 70 10 20 Sn02 (ss)
B2 60 10 30 Sn02 (ss), 4CU20Sb20S
B4 50 10 40 Sn02 (ss), 4Cu 20 Sb 20S
B3 50 20 30 Sn02 (ss)
B6 40 10 50 Sn02 (ss), 4Cu 20 Sb 20S 6.3018
1
B5 40 20 40 Sn02 (ss), 4Cu 20 Sb 20S
n, 30 10 60 Sn02 (ss), 4Cu 20 Sb 20S
Bs 30 20 50 Sn02 (ss), 4Cu20Sb20S 5.9920
B7 30 30 40 Sn02 , CuOSb20 S
B 12 20 10 70 CuOS~Os (ss), 4CU20Sb 20 S 5.8785
Bu 20 20 60 CuO Sb20 S (ss), 4CU20S~OS 6.0248
B IO 20 30 50 CuO Sb 20S(ss), 4Cu20Sb20S 5.6297
BI6 10 10 80 4Cu20Sb20S, Sn02 (ss)
B is 10 20 70 CuOS~Os (ss), 4Cu 20 Sb 20 S 5.8088
B I4 10 30 60 CuO Sb 20S(ss), 4Cu20Sb20/ 5.7790
B13 10 40 50 CuOSb20S(ss)
ratio CuO:S~03<1
CI 70 20 10 Sn02 (ss)
C2 60 30 10 Sn02 (ss), CuOSb20 S
C3 20 50 30 CuOSb 20S, Sn02 (ss)
C4 10 50 40 CuOSb20S(ss)
254
SnOz SnOz
!
80 80
70 70
50 50
40 40
30
10 10
\
CuO
800C
SbA CuO
1000C
b)
a)
SnOz Sn~
/\
!
I
10 80
\ " eo" ' ( 12 +1 70
/ :J.II" ('-13-
!-- 4\J: /
-' 5 0 ..,
50 50
//;.?! :~
40 40
..;
/
/ ~
./ +2~ ~
0 -2 -,
+3
30
o -/ j,
1/(;7
-oU ;<;
+1
30
10
/
/ \
CuO 'S~0.J CuO
1050C
c) d)
Figure 3. Shrinka ge of the sample s thermall y treated at different temperatures ..
255
Sn~
7" 3 l ,ll
I
4,17 7-'2
1-
6,43 6,30 ~7
3~~0 . 40
3,63
--.- -
6,31 6,797 F- - - - - - - -
- -- -- \ 4.91 0,11 4;376.,77 - - - - - - -
s: . - - ..- t - - - -
~ 6;,67 7;.01 161 _ -3~? --3,~ 0- ~,~ _ 1_~6 '.:.
7,36

6-' 3
~
6,91 7"1
- e .. . -
~ - - - - - - - - - -
6,19
. - - .-- -
3,16
.
4,71
I
-- -- - - -
CuO I:1 SbPJ ceo I :1
1000 C 1050 C
a) b)
. -- - ~
- - - \ 50
0,43 3S- - 3: (; - - - ,,
-_ ... _-- ... - - ... 40
O,SS
. . -. r -;- - -- -- --'
0,33 0.'n. 6.2S
ir------ ,
,
0;.31 0.1 f - -~ - -
1,4S 0 0 S,29 r-~ - - " - ,
. - - - - - - - - - - - - - - 10
euo I:1
ll OO C
c)
Figure 4, Porosity of the samples thermally treated at different temperatures.
256
The values of porosity are shown in Figure 4 (a-c) and suggest an inadequate sintering
of the samples at temperatures lower than 1100C. At 11 OOC remain porous only samples
whose initial ratio is CuO:Sb203=I and the Sn02 and content < 40% and the sample with
the highest content ofCuO. The samples with CuO:Sb203 ratio <1 unit exhibit no sintering
properties .
The increase of sintering temperature over IIOOC does not improve the ceramic
properties of the studied samples. Thus at I200C all samples, except the sample with
80%Sn02, are deformed owing to the high content of liquid phase formed at the mentioned
temperature.
The density of samples (characterised by reduced porosity) is shown in Table 1.
Although the samples exhibit comparable porosities, the values of their densities are
different. This finding may be correlated with the phase composition of various samples.
The results presented show that only samples ofCuO :Sb203~I initial ratio offers better
properties adequate for sintering.
In our experimental conditions, the sintering takes place simultaneously with the phase
formation. That makes difficult to draw a sintering mechanism. Further investigation on
under way on samples in which the phases formation was previously realised.
CONCLUSIONS
A systematic study of the sintering over the whole concentration range of composition in
the Sn02-Sb 203-CuO system was performed
The sintering properties strongly depend on the starting compositions of the mixtures
and the phase composition obtained by thermal treatment
The oxide compositions that lead to dense ceramic were obtained starting with mixtures
with CuO :Sb203~I, and contain either Sn02(ss) or a mixture of phases.
Acknowledgements:
We gratefully acknowledge for the financial support by the Grant nr. 60/l998 from
Romanian Academy.
REFERENCES:
1. K. Billehaug and H. A 0ye, Aluminium 57 (1981) 146

2. W. Ziemba and B. Ziemba, .Szklo i Ceram 24 (1973) 12
3. T. Chvatal, .Sprechsaal Keram. Glass Baust. 8107 (1974) 1058
4. M. Zaharescu, S. Mihaiu, S. ZucaandK. Matiasovski, J . Mater . Sci. 26 (1991) 1666
5.1. A Varela, D. Gouvea, E. Longo , N. Dolet, M. Onillon, 1. P. Bonnet Diffuse. Defect. Data Pt. B (1992)
25 (Sintering 91) 259
6. M. Zaharescu, S. Mihaiu, D . Crisan and S. Zuca, Third Euro-Ceramics Ed. P. Duran and J. F.
Fernandez, Faenza Editrice Iberica vol. 2 (1993) 359
7. S. Mihaiu, M. Zaharescu, D. Crisan and S. Zuca Adv. Sci. Technol. , 83 (Ceramics Charting the Future)
(1995) 695
8. M. Stan, S. Mihaiu, D. Crisan, M. Zaharescu, Key Engineering Materials, Ed . Trans. Tech Publications,
Switzerland (1997) 790
257
GRAIN GROWTH IN SYSTEM CdO-Bi z0 3
' B ran k OVIC

( 1. . ,,I . , ,:) an dBJ
D . K rsmanovic . ord OVIC
")-
lCenter fo r Multidisciplinary Studies, University o f Belgrade,

~Teh n ical Faculty, Cacak, Yugoslavia
INTRODUCTION
Grain growth in metal oxide powders during isothermal sintering is described

by the phenomenological kinetic grain growth equation':
- -~
G JI - G0 JI . e RT ,
= k . t = k0 t (1)
where ar e (; - ave rage grain size at th e time t, Go- initial grain size , k o - constant, Q
- activation energy, R - gas constant, T - abs olute temperature, t - time and n -
kinetic grain growth expone nt.
According to literature data" , parameter n most frequently has the value 3 for
pure metal oxides (CdO , ZnO , Nb~0 3) ' H owev er , addition of small quantity of
another component to th e pure metal oxide powder results in increase in the
parameter n valu e. For exa mp le, in system ZnO-Bi~0 3 (Bi~03 ::;4 wt%) parameter
n = 1.7-8.1, depending on temperature and composition I . Authors estimated average
valu e of n to calculate activation energy of the grain growth. This average value was
n = 5. Similarly, th e experimental values of n in system ZnO-Sb~0 3 scattered from 4
to 12, and authors averaged them to 5 or 6, depending on composition".
In this work kin etics otgrsin growth in system C(JO-Bi20,1 (Bi2 0 ,s 2.97mol %)
during isothermal sintering was investigated using the same calculation procedure as
discussed above. The possible explanation ot great change in parameter n with smell
addition olIJi20,1 to Cdt) is presented.
Three compositions CBl - 99.30mol%CdO + O.70mol%Biz0 3, CB2 -

98.57mol%CdO + O.70mol%Bi~0 3 and CB3 - 97.03mol%CdO + 2 .97mol(YoBi~03
wer e systematically investigated. Th e samples were isothermal sinter ed in air at
Advanced Science and Technology ofSintering, edited by Stojanov ic et al.

MOC, 680C and noc for 0, 15, 60, and 240 min . Microstructural analysis was
performed using optical and scanning electron microscopy of polished and
chemically etched samples. Mean grain size (G ) was determined using intercept
method. The samples were also characterised by X-ray powder diffraction method
and parameters of CdO crystal lattice were calculated.
Mean grain size of CdO as the function of time and temperature of sintering is
shown in Fig. 1. Initial grain size is mean grain size of samples heated up to sintering
temperature and cooled (t =0). In these samples the grain growth also occurred, and
increased with increase in Bi z0 3 content. The most intensive grain growth was
observed for samples CBl (at all sintering temperatures) during isothermal sintering
of 240 min. Tendency of fast initial grain growth in period of 15 minutes, followed
by rapid decrease in growth rate was observed for sintering temperatures MOC and
680C. This tendency was more expressed for samples with greater content of BiZ0 3
At noc grain growth rate was more uniform in all samples.
Experimental values of mean grain size as a function of t, for different sintering
temperatures were fitted based on equation G" = k t - Gon (Fig . 1.).
7 n=7.06
6 6
_5 _5
E
~4 =1. 4
C) 3 C) 3
2
2
1 h~--,--...--,.~~:;=;::=:;::::::;:::::"'"
o 50 100 150 200 250 o 50 100 150 200 250
t (nin) t (min)
a) b)
p
6
E 5
=1. 4
C) 3
.:;::;9,:0.c
2 680C
1 720C
~....--........,----r---,---'-----,---':"'::"::"""::":"
o 50 100 150 200 250

t (min)
c)
Figure 1. The dependence of CdO mean grain size on time and temperature of sintering for different
composition: a) CBl, b) CB2 and c) CB3 .
260
It could be se en that parameter n was not constant for different temperatures and
compositions, possibly because of different amounts of Bi 3+ ions incorporated into
CdO lattice, as well as different phase compositions", However, n was not constant
for T=const., but different compositions, either. This could be explained by different
lengths of diffusion paths when samples contain different amounts of Bi z0 3, as well
as differ ent amounts of Bi 3 + in CdO lattice. SEM microphotographs of sample CB3
(Fig . 2.b) showed the presence of liquid phase (Bi z0 3 ) which covering CdO grains.
Samples CBl (Fig. 2.a) contains small quantity of liquid phase that can not be seen
from photographs. That means that diffusion paths in samples CB3 wer e
sign ificantly long er. Longer diffusion paths affects valu e of paramet er n and slows
down the grain growth . For calculations of kinetic paramet ers k oand Q paramet er n,
obtained for different sintering temperatures, had to be averaged' <. That enables us
to apply Arrhenius relation for rate constant k:
Q
k=ko .(R.T , (2)
where k o is rate constant at T= 0 and Q is activation energy (Tab. I) .
Figure 2. SEM microphotographs of samples CHI (a) and Cn 3 (b) sinte rcd at 720C during 240 min.
Table 1. Calculated values of activation energy(Q) and In k o.
composition n Q (KJ/mol) In k o
CBl 3.9 1317 17.8O.8
CB2 8 2747 42.6O.8
CB3 8 49020 692
261
Dissolving of Bi2 0 J in CdO lattice has a great influence on sintering kinetics .
During this process one Hi 3+ ion substitutes one Cd 2 + ion, oxygen vacancies
concentration decreases and transition Cd 2+ ~ Cd!+ takes place because of
electroneutrality principle (Fig. 3.f Values of CdO crystal lattice constants, for
different sintering conditions, are given in Table 2, 3 and 4. Bj3+ ions have greater
ionic radius (1.20 A) than Cd 2+ions (0.97 A) so it could be concluded that increase in
CdO lattice constant is consequence of Bj3+ incorporation into CdO crystal lattice .
Figure 3. Incorporation of Bi3+ ions into cadmium oxide crystal lattice .
Table 2. CdO lattice constansts and width of diffraction peak (422)

of samples CB3 sintered for 120 minutes at different temperatures.
sintering a (nm) b/2 of (422) peak

temperature (0C) (lO'3 ra d)
640 0.47040 2.488
680 0.47045 2.158
no 0.47055 2.067

of samples CB3 sintered at noc for different sintering times.
time of sintering (min) a (nm) b/2 of(422) peak (lO3rad)

15 0.47045 2.094
120 0.47055 2.067
240 0.47058 1.983

of samples of different compositions, sintered at noc for 120 minutes.
mol% Biz0 3 a (nm) b/2 of (422) peak (lO 3rad)

0 0.46996 2.466
0.70 0.47035 2.430
1.43 0.47053 2.337
2.97 0.47055 2.067
262
Amount of dissolved Bi3+ increased with increase in time and temperature of
sintering, as well as Bi z0 3 content. Substituted Cdz+ ions diffuse to grain boundaries
which results in increase in defect concentration at grain boundaries and
consequently accelerates diffusion processes. Incorporation rate is proportional to
chemical potential gradient at grain boundaries of CdO, which has the maximum
value at just the beginning of the sintering process . Further, that means that mass
transport is the most intensive during heating up to sintering temperature and just at
the grain boundaries. Increase in Bi z0 3 content resulted in more intensive CdO
grains growth (Fig.I.), as well as in increase in initial rate of grain growth during
isothermal sintering (Fig. 1.). Decrease in grain growth rate was the most intensive
for samples with maximum Bi z0 3 content and vice versa . Chemical potential
gradient decreased at grain boundaries, but increased in CdO grains interior with
prolongation of sintering. Dissolving of Bi z0 3 in CdO crystal lattice decreased
oxygen vacancies concentration and slowed down diffusion through the anion
sublattice. Besides, Bi3+and Cd!+ions in cation sublattice are potential barriers and
potential trough for interstitial Cd" ions diffusion , so diffusion was slowed down. All
these proce sses resulted in decrease in grain growth.
For samples sintered at 720C presence of liquid phase have to be included in
consideration together with all discussed processes. Liquid phase enables more
homogeneous distribution of chemical potential gradient across CdO grain
boundaries and promotes incorporation of Be+ ions in CdO crystal lattice.
CONCLUSION
Main results of investigation of CdO grain growth in system CdO- Bi z0 3 (Bi z0 3 ~

2.97mol%) in temperature interval 640-720C are:
-addition of 0.70 mol.% of Biz0 3 resulted in relatively the greatest grain growth .
Parameter n was 3.9 and activation energy Owas 131 Kllmol,
-when the content of Bi z0 3 was raised to 1.43 and 2.97 mol. % , the parameter n was 8
and activation energy was 274 Kllmol and 490 Kllmol.
Incorporation of Be+into CdO crystal lattice has important influence on CdO
grain growth and resulted in fast initial grain growth. Also , presence of Bi3 +in CdO
crystall lattice retards diffusion through cation and anion sublattices. Dissolving of
Bi z0 3 in CdO lattice decreases defect concentration in anion sublattice. Also ,
presence of Bi3+ and Cd!+ions in CdO lattice could be treated as potential barriers
and trough for diffusion along cation sublattice.
ACKNOWLEDGMENT
This work was performed as part of project "Prognosis of Materials Properties

from the Viewpoint of the Triad SSP (Synthesis-Structure- Properties)" financed by
the Ministry for Science and Technology of Serbia.
REFERENCES
1. T. Senda and R. C. Bradt, Grain growth in sintered ZnO and ZnO-Bi203 ceramics, J. Am. Ceram.
Soc. 73:106 (1990)
2. V. Petrovic and M.M. Ristic, Isohronaland isothermal grain growth during sintering of cadmium
oxide, Metallography 13:319 (1980)
263
3. T. K. Gupta and R. L. Coble, Sintering of ZnO: I , Densification and grain growth, 1. Am. Ceram.
Soc., 51:521 (1968)
4. V. Petrovic, S.M. Radic, D. Uskokovic and M.M. Ristic, A contribution to investigation of grain
growth during oxide sintering, Sci. Sint., 17:81 (1985)
5. T. Senda, R. C. Bradt, 1. Am. Ceram. Soc. 74:1296 (1991)
6. G. Brankovic, V. Divjakovic, S.Mitrovski, V'Pavlovic, B.Stojanovic, M.M.Ristic : "Reactive
Sintering in the System CdO- Bi203 (Bi 203 < 10 mol.%), Sci. Sinter., 30: 91 (1998)
7.1. Krstanovic, A . Radakovic, S.M. Radic, M.M. Ristic, Crystallographic state of the CdO lattice
during sintering with added Bi203, Journal ofMaterial Science, 21:4185 (1986)
264
THE INFLUENCE OF THE COMPOSITION AND
TIME OF ISOTHERMAL SINTERING ON THE
MICROSTRUCTURE OF THE CdO-Bi z0 3 SYSTEM
Dragana R. Krsmanovic,' Branka A. Jordovic,'

and Goran 0. Brankovic Z
1 Technical
Faculty, Cacak, Yugoslavia
Z Center
for Multidisciplinary Studies,
University of Belgrade, Belgrade, Yugoslavia
ABSTRACT
In this paper the influence of the composition and time of isothermal sintering on the
microstructure of CdO-Biz0 3 ceramics has been investigated. Powders with compositions
of 95 wt% CdO -5 wt% Biz0 3 and 90 wt% CdO -10 wt% Bi z0 3 were used in our
investigations. The powders were first homogenized and then pressed under the pressure of
200 MPa. Obtained compacts were isothermally sintered at the temperature of 680 "C for
15, 60 and 240 minutes. Methods of quantitative microstructure analysis were used to
define the microstructure as a function of the composition and time of isothermal sintering.
Based on obtained results, the trend of microstructure changes as a function of these
parameters was determined.
INTRODUCTION
In a last few decades, the development of various new materials is caused by electronic
industry expansion. A survey of literature leads to the conclusion that there is a great
interest for semiconducting materials. In spite of this, only a few authors have been
investigated CdO - Bi z0 3 binary ceramics I. Z. 3. The most of results for CdO - Biz0 3 binary
ceramics are related to phase diagram of this system. Phase diagram of this system was
investigated in details for concentrations of CdO up to 80 mol%, but for higher
concentrations it was only presumed", There are some disagreement among authors, but
most of them confirmed the presence of two phases: metastable 6Bi z0 3CdO and
5Biz0 33CdO which has two modifications - high and low temperature.
In this paper the influence of the composition and time of isothermal sintering on the
microstructure of CdO-Bi z0 3 ceramics has been investigated by methods of quantitative
microstructure analysis.
Advanced SCIen ce and Technol ogy ofSintering , edited by Stojanovi c et al .

Kluwer Academic/Plenum Publishers. New York, 1999 265
EXPERIMENTAL
Powders with compositions of 95wt%CdO-5wt%Bi20 3 and 90wt%CdO-lOwt%Bi 20 3

were homogenized in agate planetary ball mill for 3h. After homogenization, the obtained
powders were pressed into pellets under the pressure of 200MPa. The compacts were
isothermally sintered in air at 680C for 15, 60 and 240 min. Polished specimens were
etched in a dilute acetic acid solution. Quantitative microstructural analysis of sintered
samples were performed on an automatic image analyzer QUANTIMET 500MC-Leica. The
areal method was used for determining grain characteristic as well as second phase - formed
during sintering . The following parameters have been measured : planar area (A, ~m2),
perimeter (Lp , urn), Feret-X diameter (Fx, urn), perimeter form factor (fL ) and area form
factor (fA)' The volume fraction (Vv, %) and numerical density (NA, ~m-2) of a second
phase have been determined, too. At the same time, the grain size was determined using the
standard linear intercept method (L, urn).
The characteristic microstructures of sintered samples are shown on Fig. 1.
Fig. 1. Microstructures of samples sintered at 680 C for 15,60 and 240 min. (~)
266
Characteristic microstructures of sintered samples, Fig. I, show that the system is
multiphase. At all samples with 5 wt% Biz0 3 it is noticed the presence of grains as a basic
phase on the basis of CdO, pores and clearly defined light phase area which according tal
presents phase 5Biz0 3 3CdO. At samples with 10 wt% Biz0 3 the grains of the basic phase
are also noticed, pores, clearly defined light phase area, but also in the areas where there are
two phases according to colour. Quantitative characteristics of these phases were
determined in the same way, as a unique phase, Fig. 3.
Results of grain characteristics measurements as a function of sintering time and
content of Biz0 3 are given in Table 1. Minimal, maximal and mean values of geometric
parameters of grains have been given.
Table 1. Geometrical parameters of grains
5wt% Bi20 3 IOwt% Bi20 3

sintering time, min. sintering time, min.
15 60 240 15 60 240
min 0.164 0.164 0.164 0.111 0.065 0.065
A,~m2 max 17.22 30.31 58.78 15.06 16.51 23.04
mean 2.78 4.63 7.39 2.20 2.81 3.48
min 1.67 1.67 1.79 1.45 1.21 1.21
Lp.~m max 15.90 21.54 31.03 16.13 15.57 19.68
mean 6.32 8.11 9.97 5.40 6.15 6.69
min 0.256 0.385 0.385 0.403 0.242 0.081
Fx.~m max 5.64 6.67 9.10 5.48 4.76 6.13
mean 1.89 2.41 3.00 1.63 1.85 2.02
min 0.897 0.578 0.881 0.509 0.693 0.170
Lc um max 5.39 7.55 7.39 9.93 10.19 10.02
mean 2.53 2.91 3.10 2.42 2.62 2.96
min 0.326 0.386 0.183 0.474 0.258 0.222
fL max 0.896 0.899 0.888 0.909 0.906 0.894
mean 0.774 0.777 0.768 0.791 0.776 0.749
min 0.529 0.68 0.555 0.684 0.635 0.646
r, max 1.905 1.587 1.439 1.315 1.317 1.587
mean 0.966 0.960 0.942 0.960 0.947 0.936
Histograms of the grain size distribution are shown on Fig. 2.
Fig. 2. Histogram s of Ihe grain size distribution
267
Mean grain size values and other phases present in the function of content and
sintering time shown in Fig . 3.
8..---- - - -- - - ,
1.1:~
4 .~
,.
2 +---~-~-~ --.,...J
60' 120 180 240 o 60 120 180 240
time. min time. min
3,2..-- -- -- - - ---.
3'O ~ 3,0
~ ~':~: ~
e,x ' ..------ .
. 2,8
...J

1,5 . ::::J :::::::::::::::::::::::: .A 2,6
1,0
2,4 1--_~-~-~-___._'
o 60 . 120 . 180 240 o 60 120 180 240
tim e , 10m time. min
grain - . - 5wt % Bi 0 - e- lOwt %B i 0

2 3 2 3
phase --.oIl.-- 5wt % Bi 0 -- y--IOwl % Bi 0
2 3 2 3
Fig. 3. Mean size of grain and second phase vs. sintering time
Volume fraction and numerical density of other phases in the function of content and
sintering time shown in Fig. 4.
60
10
8
10wt % 1 50
:1-
IOw t%
e'<
,; 6
",' 40
i:>.
> ~ 30
4 <:
Z 20
2
~ 10
5wt%

0 60 120 180 240 0 60 120 180 240
time, min time, min
a) b)
Fig. 4. Volume fraction (a) and numerical density (b) of second phase vs. sintering time
50 , - -- - - - -- ---, 50, -- - - - - -----"

- . -15 min - -1 5min
40 -e- 60min 40 - e - 60min
E 30 -A- 240 min E 30 - A-240min ............
:1- ::1.
.1 20 ......
.1 20
10
10 20 30 40 10 20 30 40
A,J.Im2 A, J.Im2
a) 5 wt% Bi20 3 b) 10 wt% Bi20 3;
Fig. 5. Scalier diagrams
268
Measure results, Table I and Fig. 2, show that grain size as well as range of parameters
value A, Ls, F x and L increas proportionally with the sintering time for both compositions
tested (5 and 10 wt% Bi 203). It can also be seen that the measured values of all parameters
are within narrow range, so that all mean values can be considered as representative
indicator of kinetics of these isothermal sintering systems.
It is obvious, Fig. 3, that grain increases with the sintering time at a greater rate at the
content of 5 wt% Bi 203 related to 10 wt% Bi 203. At the same time, the same regularity of
parameters change can be noticed: A, L p and F x measured by areal method. However, trend
change of grain mean size, showed over intercept, L, obtained by linear method, Fig. 3,
does not show significant difference in the content function, which proves less sensitivity of
this parameter.
This trend is a consequence of presence and behaviour of other phases during
sintering.
Grain faster growth at samples with 5 wt% Bi 203 was the consequence of less ratio,
Fig. 4a and b, size, Fig. 3, and area distribution of the second phase which acts as an
inhibitor.
As for quantitative characteristics of other phases present, the same change trend can
be noticed as with the grain, Fig. 3. Their volume fraction increases with content Bi 20 3
growth, Fig. 4a, while numerical density for samples 10 wt% Bi 203 increases. Regarding
presence of these phases, the structure is more dispersive and smaller in comparison with
samples of 5 wt% Bi 203, so in this way such creation morphology of these phases has
greater inhibitor influence on grain growth which is shown by the results given in Table I
and Fig. 3.
Observing the grain shape during isothermal sintering over fL and fA parameters it is
concluded that they don't show significant changes in the composition functioning and
sintering time, Table 1. Scatter diagram gives better picture of these changes, Fig. 5. It
shows that in the course of sintering time, more regular grain shape is obtained. When the
second phase is present, more significant differences occur only at samples with 5 wt%
Bi 203
CONCLUSION
The following was established using methods of qualitative and quantitative

microstructural analyses:
- the structure of binary system investigated 95 wt% CdO -5 wt% Bii03 and 90 wt%
CdO -10 wt% Bi 203 is multiphase.
- with the isothermal sintering time increase, the grain and phase growth are present,
where the growth of samples with 5 wt% Bi 203 is faster as a consequence of stronger
inhibitor influence of other phases. At the same time the grain shape becomes more regular.
- in case of this structure, areal method of microstructural constituent size defining is
more sensitive regarding linear method.
ACKNOWLEDGMENT
This work is a part of research activity which was carried out through projects
"Prognosis of Material Properties from the Viewpoint of the Synthesis-Structure-Properties
Relationship". The authors would like to express their gratitude to the Ministry for Science
and Technology Republic of Serbia for fmancial support for these projects.
269
REFERENCES
1.V. A. Kutvicki, A. V. Kosov, V. M. Skorikov and T . 1. Koryagina, Sistema okisi bismuta-okisi kadmiya,
Neorganicheskie Malerialy, 11:2190 (1975) (In Russian)
2.A. Jager and D. Kolar , Phase relation in the system Bi203 - CdO, JoumalofSolid State Chemistry,53:35
(1984)
3. A. V. Shchenev, V. M. Skorikov and Yu. F. Kargin, Issledovanie metastabilnogo ravnovesiya v sisteme
Bi20 3 - CdO, Zhumal Neorganicheskoi Himii, 33:721 (1988) (In Russian)
4. S. D. Kirk, L. S. Curgan, T. 1. Koryagina, V.A.Kutvickii and G. G. Gulyaeva, Issledovanie fazovyh
prevrashchenii v 5Bi 20 3'3CdO metodom vysokotemperatumoi rentgenografii, Neorganicheskie
Msterialy, 26:1901 (1990), (In Russian)
270
CHARACTERIZATION OF THICK FILMS OF Fe20 ;j
OBTAINED BY CHEMICAL DEPOSITION
Verica Z. P ejovi c" , Biljan a D. Stoj anovi cf , Nad a B. Leko vic '
1 IRITEL Telecommunications a nd Elect ronics Co ., Belgrade,

Yugoslavi a
2 Cen ter for Mul tidiscipliny Studies Uni ver sit y of Belgr ade,
Belgr ad e, Yugoslavia
ABSTRACT
The Fe20;j powders wh er e prepar ed following t he che m ica l deposition methods

from chloride sal t s. Aft er deposition the obt ain ed powders wh ere thermally treated up
to temper ature wh ich allowed com plete form ation of oFe 20;j . This tem pe rat ure was
determined usin g DCS a nd X-ray a nalisis. The sur face area was determined usin g the
BET-method . Aft er cha racterization of ob t ained powders,the sus pe ns ion-paste was
prepa red . The thick films whe re pr ep ar ed usin g t he technique of screen-prin t ing wit h
t he suport of AI20;j. Aft er firing at t he temper ature of 800C the elect ric resistiviti es
wh er e determined.
keywords: deposition, thick film , Fe20;j, powder
INTRODUCTION
It is well known that well-p rocessed fine powder s yield soft , easily pr essed ag-
glom er ates that form and sinte r mu ch more effecti vely a nd enchancing the overall
sinte rability. The under st anding of t he production pr ocesses of powder s, espec ially
the influen ce of processing par amet er s an d powder characteris t ics on beh aviour of
ceramic m ateri als ar e pr esently of almost inter est (1). Vari ables like ini ti al com pact
den sity, p articles morephology a nd cristallinity and pr essen ce of ag glomerated par-
ticles are of gre at importance (2). Numerous st ud ies show t hat t he final res ult s are
very sens it ive t o a number of paramet er s. T he interd ipende nce of va ria bles , sa me-
times hardly, controled are subject of m an y liter ature d ata (3). During t he past two
decades t he invest igation of Fe20;j has been of great int erest , espec ially rela te d to
sen sor applications. As it is well known that the bulk elect rical prop er ti es of aFe20;j
are ver y usefull for many potential a pplications (2), the thick film of Fe20;j ob tained
by che mical deposition has be en investig ated.
Advanced Scien ce and Technology of Sintering , edited by Stoj anovic et al.

The previous powders of ferrous and ferric hydroxides from chloride solutions by
chemical deposition methods was synthesed. The chlorides solutions as FeCl 2 and
FeCl3 where deposited using solution of NH 40H . The pH of initial chlorides was 2.0
and after finaly deposition was approximately 6.0. After filtration , washing and dry-
ing the ferrous or ferric hydroxides were obtained. The obtained hydroxides were
heated at 500C and 750C for two hours of air atmosphere. The characterizations
of obtained powders using X-ray powder diffraction method (PHILIPS 1820 with
graphite monochromator and step-scanning mode of 0.02 and 1 s), differential scan-
ning calorimeter (SHIMADZU - DSC 50) and BET method for specific surface area
(MICROMERITICS flow-sorb II 2300) were used .
After characterization the paste was prepared using the previously prepared ox-
ide powders, organic vehicle and a glass based on lead-bor-silicate. The Fe203 powder
presents a functional ccomponent of paste, the glass is a connective component, be-
tween suport of Al 203 and paste.
The organic component was mixed with powders for preparing the paste. The
paste was screen-printed on alumina substrates and sintered at 800C in air for 10
minutes. The view of screen printed sample is present in fig. 1.

II III III
II II III
II II II
lr
Figure 1 The screen printed sample of Fe203 paste after firing
Many investigators have studied the influence of previous salts and thermal treat-
ment an sintering and microstructure of oxide ceramics. It was pointed out that an
optimum temperature treatment was necessary to achieve maximum green density
and sintering density for each salt chlorides.
In this study the salts were used for formation the Fe-hydroxide compounds.
The compound obtained after chemical deposition of chloride salts were analysed
using DSC method. In compare with literature data (3) , it can be noticed that the
reaction in case of chemical deposition from Fe-chloride was followed by exothermic
effect at 322C as a result of formation of wustite (FeO) and magnetite (Fe304)
mixture (fig. 2) .
272
100
.. . _. -t- ~---t-- . " - - -+-- - ........... -- -----t--- .....-------t- - - --+- -- ~----+----t-- ... ...
. ---r ,
80 322.5 C
t
60
3
. 40
s:0
iL
16
a> 20
:I:
- 20
-40
240 260 280 300 320 340 360 380 400 420 440 460
Temperature 1C)
F igure 2 C haract eristic DCS d iagram of oxide powders o btained by che mical dep osit ion of ch loride
sa lt s
(104)
100 (110)
r
I
80
(116)
~
en
.,.... 60
(J)
M
40 (102)
20 \.~. I . I I
'",-'<A~~-~L~ULJl
10 20 30 40
,1"'.1,-. "
.~ ~.L P I
F igur e 3 C haract er ist ic difract ogr am of oxide a fter therma l treatmen t at 750 C
273
The results of DSC and X-ray diffraction analysis are in aggreament. Obvi-
ously, results from X-ray diffraction analysis indicated that the powders, obtained by
chemical deposition Fe chloride salts and thermaly treated at 500C, give a mixture
of Fe-oxides. It was observed that the oxides mixture consisted from lepidocrocite
(FeOOH), magnetite (Fe304) hematite (Fe203) and wustite (FeO) (1). Increasing
the temperature up to 750C, the previous chloride salts brought to formation only
the hematite, aFe203 (fig. 3).
The results of specific surface area showed that after thermal treatment of previ-
ous compounds obtained by chemical deposition of chloride salts, the visible decrease
of values appeared (Table 1)
Table 1 Specific surface area

2 34.35 40.4
SPO m / gr
SP5000 m2/gr 9.2 16.3
2 5.3 10.3
SP7500 m / gr
It can be assumed that the change of specific suface area is cause by change of
oxide mixture compositions before and after thermal treatment.
In order to investigate the electrical properties of Fe203 ceramics, the screen
printed sample was measured using LCR meter. The temperature dependence of
electrical conductivities is presented in fig. 4.
Ro
[JL]
I
550 600 650 700 750 800 850
T [C]
Figure 4 The temperature dependence of electrical conductivities of screen-printed Fe203
Obtained resultes indicate that Fe203 obtained by chemical deposition of chloride

salts can be applicated as electrical component by screen-printed thick film technology.
274
CONCLUSION
Fe 20 3 powder s were prepared by che mical deposition from chloride salts . It was
noticed that t he temperature of thermal treatmen t had to b e 750C to obtain pure
aFe203 without any pr esence of other kind of oxides. It was shown that the scree n
printed thick film technology can be used for production of electrical com po ne nt based
on Fe203 powders
REFERENCES
1. V .Z. Pejovic, B .D. St ojanovic, T .S. Srecckovi c, K in etics of Fe203 ceram ic s obtained from chloride
salts Ninth CIMET IC, Florence , june, (1998) 14 - 19.
2. D.P. Uskokovic, H. Palmour III, R.M. Spriggs , Science of Sintering , Plenum Press, New York and
London, (1989) , 519 - 527.
3. C.R. Buchan an, Ceramic Mat erials fo r Electronics, Mar cel Dekker, New York and Basel, (1986)
301 - 305.
4. Meckenzie and Berggen, Oxid es and Hidro xid es of High er - Valen cy El ements, New York , (1957) .
275
EVOLUTION OF THE SURFACE AND INTERNAL
STRUCTURE OF SILICA AEROGELS DURING
THE ISOTHERMAL SINTERING PROCESS
1. 1. Hinic, G. M. Stanisic and Z. V. Popovic
Institute of Physics
Pregrevica 118, 11080 Belgrade, Yugoslavia
INTRODUCTION
The surface of the silica aero gel in equilibrium with humidity is covered by silanols
(vicinal, geminal and isolated) [1 , 2, 3]. At th e fully hydroxylated sur face, hydroxyl
groups are sites where phy sical ad sorption of wat er occurs . Water covers all available
OH sites forming water clusters [1 , 4]. The dehydration of the porous silica surface
depend s on the sur face curvature. Small positive radius of the curvat ur e facilitates
dehydrat ion while small nega tive radius of th e curvature makes it very difficult [1 ,2].
Fir st ste p in dehydration of th e silica gel sur face is removal of the physically adsor bed
wat er. It is followed by progr essive removal of th e H-bonded silanols, and finally
isolat ed silanols [1, 5]. Silanol s are removed by condensat ion. It is very inter esting
that fully hydroxyla ted sur face has 4.9 OH / n m2 and th is amount of OH groups is
indep end ent of the typ e of silica (synthesis condition, drying condition, density, and
sur face area) [6]. However, abili ty for hydroxyla tion dep end s on the struct ure of ring s
at the gel surface. In both cryst alline and amorphous phases, it is generall y accepted
that th e basic S i0 4 te trahedral bu ilding blocks are linked with some bridging (Si-O-
Si) bond angle, 0, to form ring s [7]. In amorphous silica a wide range of ring typ es
exis ts [7]. In the gels three memb ered rings are ab sent at low temperatures. They
form at int erm ediate temperat ur es primarily on th e gel surface by condensation of
isolated vicinal silanol groups [1, 8].Then angl e ofSi-O-Si bond decreases from 148 0 to
137 o . The siloxane bonds cont ained in the three-membered rings are very susceptible
for hydrol ysis [1]. As temperature is increases, the reduced viscosit y allows formation
of five-membered or higher ord er rings at the exp ense of less st able, smaller rings. The
five and higher orde r rings are not so sus ceptible for hydrolysis as three memb ered
rings. For all lar ger rings molecular orbital calculations predict optimum angles of
Adva nced Science and Technol ogy of Sintering, edited by Stojanov ic et al.
Kluwer Academ ic/Plenum Publisher s, New York, 1999 277
e= 148 0 . Vibrational spectroscopy (infrared (IR) and Raman spectroscopy) is
very sensitive to water-related species and gives information about hydrogens binding
state in the glass [9, 10]. In this work we examine changes in OH contents in silica
aerogel during isothermal sintering process by IR and Raman spectroscopy. Using
obtained results we explained changes in the pore morphology at the surface of the
gel during sintering. Changes in average Si-O-Si bond angle pointed that beside pore
morphology, the ring distribution influence on (de)hydroxylation of the gel surface
and internal structure.
EX PERIME N TA L P RO C ED U R E
Samples of silica aerogel with initial bulk density of 0.21 glem 3 were prepared by
mixing tetraethylorthosilicate (TEOS), water and ethylalcohol at molar ratio 1:2:6.
Two step catalysis method was used. In the first step 10-3 moles of HCI was added
and then 0.2 moles of the N H30H in the second step. Samples were neutral (pH=7)
and dried by supercritical extraction (T c = 243.1 C and Pc = 63.1 at) in cylindrical
Teflon tubes . The series was sintered isothermally for 0,2,4,6...24 hours at 1000 C
in air . Bulk densities were determined from the mass and dimensions of the cylin-
drical monolithic samples. Specific surface areas of the samples were measured using
a one chamber sorptometer with nitrogen as an adsorbate. Experimental data were
analyzed using BET (Brunauer , Emmet, Teller) approximation. IR reflection spectra
were measured using a Per kin-E lmer model 180 spectrometer in the spectral range
between 400 and 4000em -1 . The samples were immersed in paraffin oil, because stud-
ies of hydroxyl content or adsorbed water in KBr-prepared sample may be unreliable.
Raman spectra were measured using 514.5 nm line of Ar ion laser as an excitation,
Jobin-Ivon U1000 monochromator and photomultiplayed tube as detector. Raman
spectra were measured in spectral ranges 350 - 1300 em -1 and 2900 - 4000 em -1 .
RESULTS
Infrared spectra of nonsintered sample is presented in Fig. 1.

AS
o experimenta l data
0.35
I - - fit
0.30
0.25
B
I p=O.21 g/cm 3 I
!
>.
:~ 0.20
13
Q)
~ 0.15 HO-H
0::
0.10
0.05
0.00 I I
600 900 1200 1500 1800 32003400 3600 3800 4000
Wave number (crn-t)
Figure 1. IR spectra of nonsintered silica aerogel samp le. Stars denote paraffin oil modes ,
B is Si-O-Si bending mode , S is Si-O-Si symmetric stretching mode, AS is Si-O-Si antisymmertic
stretching mode and ASO are overtones of AS.
278
Exp erim ental data are given by circles and fit curve by solid lines . A part of 2000 -
3000em - 1 is extracted becau se of a very st rong mode of paraffin oil at about 2900em - 1
which overlaps th e spec tra of silica aerogel. Reflect ivity data were analyzed by re-
flectance curve fitting procedure. We used complex dielectric function C modeled as
follows
S
c(w)=coo+ L 2 ; . (1)
j Wj - W - Ifj W
where Coo is high frequ ency dielectric const ant , Wj is resonance frequency, rj is damp-
ing par ame ter and Sj is oscillator st rength . In Fig. 2 is pr esented Raman spec tra of
nonsintered sample.
2500
~s r
S
I IjA
I j\w\ \
2000
~ 1500
;je
~
I Si-OH SiO-H, surface
N'Ur-
.?;-
\ I AS AS
\)
.~ 1000
-.SiO-H, internal
E S iO-H , isolated
V0 ~ '~
500
o
/
500 750 1000 1250 3500 4000
Raman shift (em")
Figure 2. Raman spe ct ra of non sint ered aerog el sa mple. Designations are the same as in Fig. 1.
In Fig. 3a is present ed par t of spectra 3100 - 3800 em - 1 where O-H vibration

mod es are post ioned , for each sample of the series. In Fig . 3b are given Raman
spec tra of each series sample in spectral range from 3100 to 3800 em - 1 . Positions
of th e modes in the Raman spectra were determined by modeling using Lorent zian
profiles. The assignments of O-H vibration IR and Raman modes are summarized
and referenced in Table 1.
Tabl e 1
IR (ern 1) Raman (em '1) Assignment Ref.
3425 - bonded H20 symmetric stretching [9]
3450 - bonded H 2 0 antisymmetri c stretching [9]
3540 3470 vicinal SiO-H stretching [9] [11]
- 3595 shoulder of 3470 em - 1 mode [1]
3660 3690 internal SiO-H stretc hing [9] [1]
3750 3750 isolated SiO-H stretching [1) [11]
279
t (h), p(g/cm 3 ) \ p (g/cm 3 )
2 0, 2 .05 ~1 .87
15 , 1 .93
13 , 1 .8 7
11, 1 .74
9, 1 .65
6, 1 .22
4, 0 .40
'2 , 0 .30
~ -- - -~- '0 0 .21

3250 3500 3750 '
3200 3400 3600 3800
Wa ve number (c rn-t ) Raman shi ft (crrr")
F ig u r e 3. a) IR sp ect ra of sint ered samples in spectral range from 3100 to 3800 em -1 . Time of
sinte ring (in hours) and bulk densities (in g/ em 3 ) are given right of the each spectra.
b) Raman sp ect ra of sintered samples in sp ect ra l range from 3100 to 3800 em -1 . The bulk densiti es
(in g/ cm3) are given right of the each spectra.
Th e oscillator strengths of OH vibration modes obtained by fitting, versus bulk

density are presented in Fig . 4a, the specific surface area versus bulk density in Fig .
4b and average Si-O-Si bond angle versus bulk density in Fig . 4c.
D I SC U SSION
As it. can be seen in Figs 4a, 4b, and 4c during isothermal sintering silica aerogel
surface passing by three phases. In the first phase , during first four hours at th e
sur face and inside the gel all kinds of silanols are presented.It can be seen from
Raman spectra in Fig. 3b where the modes at 3470 and 3595 em -1 assigned to
vicinal silanols , mode at 3660 em - 1 to internal and at 3750 em - 1 to the isolated
silanols are presented. As it can be seen in Figs. 3 and 5a in the IR spectra modes of
molecular water bonded to the silanols are presented to . The strengths of the modes
connected with silanols and modes of molecular water are comparable. Since specific
sur face area hardly decreases during th e first phase it is expected that amount of
the vicinal surface silanols decreases too . As in the silica aerogel made by two step
catalysis method percentage of silicones which are bonded in three-membered ring
approach 20% [1] , formation of three-membered rings lowers average Si-O-Si bond
angle () , and their ability to hydro lysis maintained amount of surface silanols . During
the first phase strength of molecular water IR modes rises (Fig . 4a) which means
tha t amount of the molecular water insid e the pores increases.
280
:i
~
.<:
e
II
'------
0,
c
~ e- --'"
(jj -e - HO-H, bonded
o -A- SiO-H , surface
~ -'.-' SiO-H, internal
13
o
(/)
:l600
1 b)
~ 400
co
(IJ
~ 200 e
'to
:J
(J)
o
1479
1476 c)
1473
0-
- 1470
a:>
1467
1454
146 1 I---,.-J--,---.--,...-........--,---I,.---,-......
0.0 0.5 1.0 1.5 2.0
Bulk density (g/cm 3 )
Figure 4. (a) The oscillator strength of O-H vibration modes of silanols and water bonded to silanols versus
bulk density. (b) specific surface area versus bulk density (c) Average Si-O-Si bond angle versus bulk density
(according to [12]) .
This is a consequence of the pores closing when their radius of curvature decreases
and at room temperature water can not be removed . During the second phase, up
to 9th hour of sintering specific surface does not change significantly, amount of the
silanols stays remain . We can see in Fig . 3b that Raman modes connected with vicinal
silanols at 3470 and 3595 ern -1 are dominant. Water bonded to them stays capted
inside the pores. During the second phase average Si-O-Si bond angle increases due
to formation of five or high order rings . Above nine hours of the sintering starts third
phas e when densification leads to the elimination of the surface pores. The decreasing
of specific surface area causes elimination of the vicinal surface silanols. However, as
we can see from Fig. 4a strength of the internal pores mode arises . The closing of
th e por es silanols and molecular water is cap ted inside them . This " bloating" of the
gel is often happens when samples are sintered in air. It can be seen in Fig. 3b that
vicinal silanols modes decrease in intensity and mode connected with internal silanols
is dominant .
CONCLUSION
IR and Raman spectra of isothermal sintered silica aerogel series were examined. This
study reveals the following:
1. During the first four hours Si-O-Si three-membered rings were formed which rises
hydroxylation of the gel surface. In the same time the pores close and radius of the
por e curvatur e decreases which dehydration make difficult.
281
2. From 4th to 9th hour of sintering specific surface area does not change signiffi-
cantly. In Raman spectra mode assignated to vicinal surface silanols are dominant.
In IR spectra dominate modes connected with molecular water bonded to the surface
silanols.
3. After nine hours of sintering, during third phase , densification leads to smooting
of the gel surface , molecular water has been eliminated and surface silanols disapear.
Because of "bloat ing" of the gel internal silanols dominate.
References
[1] C. J.Brinker and G. W.Scherer, (Sol-Gel Science, Academic Press, Boston), (1990).
[2] R. K. lIer, (The Chemistry of Silica, John Wiley & Sons , New York), (1979) .
[3] T . A. Michalske and B. C. Bunker, J . Appl. Phys., 56, 2868; (1984).
[4] W . Hertl and M. L. Hair, Nature, 223, 1151; (1969).
[5] C.ls and M.Ge, J .Am. Ceram. Soc., 118,401, (1996).
[6] L. T . Zhuravlev, Langmuir, 3, 316; (1987).
[7] R. A. B. Devine, J . Non-Cryst. Solids, 152,50; (1993).
[8] S. Wallace, J . K. West and L. L. Hench, J. Non-Cryst. Solids, 153, 101; (1993).
[9] A. Agarwal, M. Tomozawa, J .Non-Cryst. Solids, 209, 166; (1997).
[10] T. Oshaka and S. Oshikawa , Phys. Rev. B, 57, 4995; (1998)
[11] B. Riegel,!. Hartmann, W. Kiefer, J . GroBand J . Fricke, J . Non-Cryst. Solids, 211,

294; (1997).
[12] 1. 1. Hinic, G. M. Stanisic and Z. V. Popovic unpublished.
282
SINTERING CONDITIONS AND HYDRAULIC ACTIVITY OF 4CaO.3AlzO).SO)
Marcela I.Muntean,' Florica GPaul,' and Carmen Novae'
University "Politehnica" Bucharest

1
Building Technical University Bucharest
2
3Metav S.A. Bucharest
Romania, PO.Box.12-46, Bucharest 78100
INTRODUCTION
4CaO.3AI203.s03 is the most important ternary compound of the CaO-Alp3-S03

system. It has a significant role in the behaviour of calcium sulfoaluminate belite cements
and also, in expansive sulfate aluminate cements 1.3. The cements based on calcium
sulfoaluminate can be produced at temperatures much more lower than those required by
Portland cement':'. There are economical and ecological advantages of obtaining such
cements: lower consumption energy at decarbonation corresponding to a lower lime
saturation factors, lower burning temperatures at clinkering, higher grinding ability, a
reduced carbon dioxide emission and the possibility to use different types of wastes in the
raw mixtures 3,4.
The water reactivity of calcium sulfoaluminate compound depends on sintering
conditions, especially the temperature and the duration of synthesis . Hydraulic properties of
4Ca0.3AI203.S03 binder, particularly its compressive strengths can be a measure of water
reactivity', The sintering conditions can affect the hydraulic properties of the calcium
sulfoaluminate binders and as a consequence their mechanical behaviour.
EXPERIMENTAL
Chemically pure, finely ground CaC03, AIP3 and CaS04.2H20 (average dimension
of particles under 40 11m) were used in stoichiometric ratios to obtain calcium
sulfoaluminate. The synthesis of 4Ca0.3AI203.S03 was carried out at 1000, 1050, 1100,
1150, 1200, 1250, 1300 and 1350 "C. The burning time was the same for all samples,
namely one hour. The samples were air cooled. For samples burnt at 1200, 1250 and 1300
DC, which represent optimum temperatures of the synthesis, tree different burning time
were used: 30, 60 and 90 minutes .
Free lime content (extraction with diethylene glycol) used to calculate the
transformation degree, X-ray analysis, density and hydraulic properties - chemically bound
Ad vanced Science and Technology of Sintering , edited by Stojan ov ic et al.

Kluwe r Academi c/Plenum Publishers, New York, 1999 283
water and compressive mechanical strengths have been used to characterize the resulted
4Ca0.3AI 23"S03
RESULTS
The X-ray data show that, in the stoichiometric mixture of CaC03-Alp3-CaS04.2H20,

corresponding to 4CaO,3AI 203.S03, the formation of calcium sulfoaluminate takes place
with a higher rate above 1150 C and the transformation is completed at 1200 - 1300C.
Also, in the first stages of the of solid state reaction, under 1150 C, 4CaO.3AI203.S03is
present in equilibrium with calcium monoaluminate (CaO.AIP3)' alumina and anhydrite.
These last tree phases disappear above 1200 C, when in the system the equilibrium is
practically achieved and exists only 4Ca0.3AIP3.S03' -Fig. 1.
100
80
~
0
-0- Calc ium sulfoaluminate
~ 60
'iii ... Calcium monoaluminate
c
Ql
E 40 -D- AI203
20
Figure 1. X-ray intensity of calcium
0 sulfoaluminate (d=3.72 A), calcium
monaluminate (d=2.97 A), alumina
1000 1100 1200 1300 1400
(d=2.085 A) and anhydrite (d=3.498 A) vs.
Temperature, C degree sintering temperature.
The dimension of 4Ca0.3AI203.S03 crystals increases from about 1 11m at 1200 C to

1.5 -2.0 11m 4,6 at 1250 - 1300 C.
Above 1300 - 1350 C begins the decomposition of calcium sulfoaluminate which is
confirmed by the presence of free lime and free anhydrite in the reaction mixture.
In good correlation with the above mentioned facts, the transformation degree* of the
stoichiometric mixture of 4CaO .3AIP3.S03' calculated from the free lime values, show
that the formation of calcium sulfoaluminate in the same mentioned range of temperatures
(1200 - 1300 "C) is practically total-Fig.2.
The hydraulic behaviour of the calcium sulfoauminate shyntesised in the range of
1200-1300 C, at different burning times, depends on the samples density and crystal
dimensions -Table I .
Transformation degree, % ex = (CaO r - CaO r) / CaOr. 100

in which, CaOr - total free lime content of the sample
and CaO r - current free lime content of the sample
284
100
80
<fl.
60
.~ -0- Free lime
c
ttl
:l 40 ..- Transformation degree
0
20
Figure 2. Free lime content of the samples and 0

the transformation degree of the mixture vs. 1000 1100 1200 1300 1400
burning temperature. Temperature, C degree
Generally, the increase of the temperature and as well as the time of burning has a
favourable influence upon the sample density. Some variations of the density values appear
above 1300 DC, due to the phases transformation, particularly due to the decomposition of
the calcium sulfoaluminate.
The hydraulic activity of calcium sulfoaluminate decreases when the samples density
increases -Table 1.
There is a strict dependence between the kinetics of hydration and the structure
development of the hardened system. A higher hydration rate and as a consequence,
a higher internal tension, which often determines the expansion of the samples, can
induce smaller compressive strengths. Thus, the calcium sulfoaluminate samples burnt
at 1200 C for 30 and respectively, 60 minutes have smaller density and the best water
Table 1. Density and chemically bound water of 4CaO.3Alp).SO) pastes with water/binder ratio of
0.5, at different burning duration and burning temperatures.
(Blaine specific surface area of 4CaO.3Alp).SO)= 3300 crrr/g)
Temperature Burning Density, Chemically bound water, %

time, after... hardening, hours
C minutes g/cm3 24 72 168
30 1.89 15.20 19.72 24.15
1200 60 2.09 14.36 19.03 23.24
90 2.16 14.40 18.88 23.00
30 2.19 14.03 17.66 22.80
1250 60 2.21 13.93 17.00 18.96
90 2.23 13.54 15.97 18.77
30 2.24 12.06 15.19 17.01
1300 60 2.20 10.03 11.97 16.19
90 2.17 9.11 11.03 14.65
285
reactivity'. In the same time they have higher expansions (1.7 - 2.3 %) due to the
accelerated kinetics of hydration and as a consequence, compressive strengths, after 28
hardening days, not much more than 23 MPa -Table 2.
Table 2. Mechanical properties of standardmortars
Temperature Burning Expansion Compressive strengths , MPa

time, after...days of hydration
C minutes % 1 7 28
30 2.30 21.6 19.4 16.9
1200 60 2.13 20.8 22.7 21.1
90 1.70 18.3 20.5 23.0
30 1.13 16.1 23.7 33.4
1250 60 0.72 14.8 28.0 35.5
90 0.35 13.7 21.4 30.9
30 0.21 12.3 20.6 24.2
1300 60 0.07 11.6 18.8 21.7
90 - 9.8 16.5 18.9
A good correlation between the sintering condition, the hydraulic activity and the
mechanical behaviour presents the calcium sulfoaluminate samples synthesized at 1250 C
for 30 and respectively 60 minutes. In these cases the sample expansion is under 1.13 %
-see Fig.3.
40
~
'"
o,
1 day
30
.r:;, 7 days
c o 28 days
~III 20
Q)
>
"iii
III
Q)
C. 10
E
0
u
o
1200.00000 1250.00000 1300.00000
Temper at ur e, C deg ree
Figure 3. Compressive strengthof samples burnt 30 min. at different temperature
The samples burnt at 1300 C for 30, 60 and 90 minutes have a lower hydraulic activity
in comparison with the same samples burnt at 1200 or 1250 C, although their density is
286
smaller. The special behaviour of samples burnt at 1300 C can be explained if one takes
into consideration the decomposition of 4CaO .3AlzO).SO) which is followed by some
phases transformation. As a consequence the compressive strengths decrease when the
burning duration increases.
CONCLUSIONS
The calcium sulfoaluminate starts being formed at temperatures below 1000 - 1050 C.
The maximum rate of formation is in the range of 1200 - 1300 C.
Above 1300 C the decomposition rate of 4CaO.3AI 20 ).SO) is higher than its formation
rate.
The calcium sulfoaluminate synthesized at about 1250 CI 30 min. shows a good water
reactivity and also good mechanical properties, an interesting fact if one takes into
consideration the clinkering conditions for low temperature clinkers.
For the rate of the hydration process of calcium sulfoaluminate, especially in its early
stage, the most impotant sintering factors are the time and temperature of the solid state
reaction.
REFERENCES
1. S.Sahu, Developments in low energy clinkers, Ceramic-Silikaty, 38, 191 (1994)

2. I.Teoreanu, Marcela Muntean, Expans ive sulphataluminate cements, Cement
Concrete Research . 13: 711 (1983) .
3. J.Beretka, L.Santoro, N'Sherman and G.L.Valenti, Synthesis and properties of low
energy cement based on C4A3S , in Proceedings of 9th Intern. Cong.Chem.Cem., New
Delhi, vo!.3: 195 (1992) .
4. C.D.Lawrence, J.H.Sharp , Marcela Muntean. Low energy consumption cements,
2nd.Int.Symp.Constr.Industry Building Mater. and Urban Development, Hanoi, vo!.2:
25 (1995) .
5. I.Teoreanu, Marcela Muntean, Hardening processes in 3(CaO.AI 20 ).CaS0 4-water
system, Revue Rouma ine Chimie, 30: 575 (1985) .
6. Marcela Muntean, 1. Sharp. Calcium sulphoaluminate and calcium sulphoferroaluminate
compounds and their hydraulic activity . 5th COPERNICUS Meting -Bratislava 9-13
January 1997.
287
THERMAL SHOCK BEHAVIOR OF SINTERED
ALUMINA BASED REFRACTORIES
Tatjana D.Volkov-Husovic l , Radmila M. Jancic' , Zvonimir V. Popovic' ,

Mihailo Muravljov', Dragica Jevtic/, Tihomir Kovacevic 2
I Faculty of Technology and Metallurgy,

Karnegijeva 4, POB 494, 11000 Belgrade, Yugoslavia
2 Faculty of Civil Engineering, Institute for Materials and Structures,
Bulevar revolucije 73, 11000 Belgrade, Yugoslavia
INTRODUCTION
In many applications, refractories are subjected to rapid temperature changes, which

generate thermal stresses. If these stresses are sufficiently large, they can cause catastrophic
crack propagation and resultant failure. Many theoretical treatments and experimental
measurements have been presented to describe the thermal shock behavior of brittle ceramic
materials. D.P.H . Hasselman 1,2 and 1. Nakayama 3,4 applied fracture mechanic concept to
refractory thermal shock problems . For the prediction of the thermal shock behavior of the
refractory resistance parameters were proposed . Those parameters are based on thermal and
mechanic properties . Two groups of resistance parameters were proposed : fracture and
damage resistance parameters . In Table 2. equations for calculation resistance parameters
are presented 1-4.
One of the most popular thermal shock tests is water quench test. Thermal shock
resistance of ceramic materials was based on observed critical temperature difference.
General form of equations for thermal stresses generated by cooling or heating, including
effects of specimen size and heat transfer rate is 5:
(J = E a LJTf(Bi) (1)
Critical temperature difference required causing a substantial loss in strength during

cooling or heating was used for thermal shock ranking of ceramics. It is commonly assumed
that a critical value of LJTc is achieved when thermal stress, generated by the thermal
gradients equals or exceeds the fracture strength, afor a material.
Advanced Science and Technology ofSintering , edited by Stojanovic et at

Kluwer Academi c/Plen um Publishers, New York, 1999 289
If it is assumed that maximum tensile stress equals the tensile strength, and t1T =t1Tc,
then critical temperature difference can be calculated using 6:
(2)
For critical temperature difference calculation simple equation can be also used, which
is based on the relationships of maximum stresses and heat transfer rate proposed by
Bradshow, Buessem, Chang and Manson 7:
l /(Jmax zA/Bi (3)
And following equation for temperature difference calculation is presented 8,9:
(iJTch= Bi/A Ea (4)
For Biot number usual equation was used:
Bi = ah/k (5)
where a is characteristic length, h the heat transfer coefficient and k thermal conductivity.
Heat transfer conditions are considered in coefficient of heat transfer calculations and
quenching medium. For water, as a quenching bath, the heat transfer coefficient is given by
equation given by Holman 6,
k
h = 0 53(N . N )0.25.-.L
Gr Pr d (6)
where NGr is Grashov number, N pr is Prandtl number, and ICj is thermal conductivity of the
fluid, and d is specimen diameter.
MATERIALS
The five sintered alumina based refractories used in this investigation are commercial
products. The general properties were measured using standard laboratory procedures.
Thermal stability of the materials was measured using water quench test (JUS. B. D.8.319.).
The test was carried out on cylinders 50mm wide and 50mm high. The samples were
dried at 110C and then transferred into electric furnace at 950C for 15 minutes. The
pieces were then removed into water and left 3 minutes before returning to the furnace at
950C. This ~as repeated until failure. The number of quenches to failure was taken as
measure of thermal shock resistance of the samples. In Table I relevant material properties
were presented, which lists materials in order of increasing Ah03 content.
290
Table 1. Thermal and mechanic properties of sintered alumina based refractories.
Samples
Property II III IV V
AI203 + Ti02, ( %) 28 42 60 60 78
Density, P (kg/m") 2.62 2.93 3.05 3.05 3.16
Thermal conductivity, k ( W/ mK) 1.7 1.35 1.62 1.7 1.7
Heat capacity, c (JlkgK) 1.05 1.03 1.06 1.06 1.06
Thermal expansion coeffic ient, a ( % ) 0.7 0.7 0.8 0.8 0.8
Compressive strength , o ( MPa) 51 43 54 172 54
Flexural strength , o ( MPa) 7.8 7.4 11.7 18.0 9.2
Young modulus , E (GPa) 25.5 19.9 16.70 35.77 18.06
Poisson ratio, v ( - ) 0.2 0.2 0.2 0.2 0.2
Heat transfer coeffic ient, h ( J/m2sK ) 3118.5 3118.5 3446.1 3446.1 3446.1
Biot number , Bi ( - ) 9 1.72 115.5 106.35 101.35 101.35
Water quench test, ( No. of cycles ) 6 II 18 28 15
RESULTS AND DISCUSION
Usual expressions for fracture and damage resistance parameters, and calculated
values of resistance parameters are listed in Table 2.
Table 2. Fracture and damage resistance parameters
Equation Unit Samples
II III IV V
R =cr( I-v) /Ea C 24.69 22.86 30.53 48.08 29.90

R' =kR J I ms 33.34 33.85 49.47 81.74 50.83
R'" = E/cr2(I-v) m2/MN 13.45 12.25 7.16 1.51 7.74
R"" =yR'" m 0.11 0.18 0.1 om 0.03
Rst = ( y/a 2E ) 112 m l120C 9.32 10.95 11.85 5.61 6.2
Calculated values of resistance parameters were compared with the number of quench
experiments, (N). Result s of the linear regression analysis are presented in the Table 3.
Table 3. Results of the correlation of "R" parameters with number of quench experiment
Compar ison "R" paramet er with number Multiple R Standard Error

of quench experiments
R -N 0.9646 2.51486
R' -N 0.9591 2.69965
R"' -N 0.9464 3.08291
R"" -N 0.8393 5.18748
R-N 0.5826 7.75758
st
291
Fracture and damage resistance parameters were calculated using compressive
strength. From the results presented in Table 3 linear dependence was shown for all
proposed cases. The best results were obtained in comparison first fracture resistance
parameter, R' with number of quench experiment. Fracture resistance parameters could be
correlated with the number of quenches experiment with better results for the coefficient of
correlation, then damage resistance parameter. For the Rst parameter liner correlation with
N is not acceptable.
Critical temperature difference using two equations was calculated, also, and results
are presented in Table 4.
Table 4. Calculated values of temperature differences
Samples
Temperature Equ . Unit II III IV V

difference
(~Tc )1 2 c 56.23 54.15 74.80 119.23 75.05

(~Tc )2 4 C/MPa 20.70 12.84 19.9 8.85 17.52
Calculated values of temperature differences presented in Table 4 were compared to

results of water quench test, also. Linear regression analysis was used to determine
correlation between temperature difference and water quench test. Only for correlation
equation given by Hencke et al. (equ. 2.) or (LH c)1 with results of water quench test
values of coefficient of correlation ( 0.9645) was acceptable.
CONCLUSION
Thermal stability of refractory materials could be expressed using many different

methods and experimental procedures. In this paper resistance parameters and two
equations for temperature difference were used as criteria for thermal shock stability.
Standard experimental procedure for measuring thermal stability was used,
(JUS.B.D.8.319.), also. Calculated values of resistance parameters and temperature
differences were compared with results of water quench test. Results of linear regression
analysis showed that:
fracture resistance parameters R and R', as well as damage resistance parameter R'"
could be compared with results of water quench test,
if equation (2.) given by Hencke, for temperature difference is used, than linear
correlation with results of water quench test is acceptable.
Results presented in this paper could be useful for prediction of thermal shock stability
of sintered alumina based refractories using material properties (resistance parameters)
and/or heat transfer conditions and material properties of quench medium (temperature
difference). Obtained results for predicted thermal shock behavior could be correlated with
the thermal shock stability expressed using standard laboratory procedure, water quench test
(JUS.B.D.8.319.) which is often used as criteria for thermal shock stability of the refractory
material.
292
REFERENCES
1. D.P.H.Hasselman, Elastic energy at fracture and surface energy as design criteria for thermal Shock, 1.
Am.Ceram.Soc. 46(11): 535 (1963).
2. D.P.H. Hasselman, Unified theory of thermal shock fracture initiation and crack propagation in brittle
ceramics,1.Am.Ceram.Soc. 52 (I): 600 (1969).
3. J.Nakayama, Direct measurements of fracture energies of brittle heterogeneous materials, .LAm.Ceram .Soc .
48(11) : 583 (1965) .
4. J.Nakayama, M.Ishizuka, Experimental evidence for thermal shock damage resistance, Amer.Cer.Soc.Bull.
45(7): 666 (1965) .
5. P.F.Becher, D.Lewis III, K.R.Cannan, A.C.Gonzales, Thermal shock resistance of ceramics: size and
geometry effects in quench test , Ceram. Bull. 59(5) (1980).
6. H.Hencke, J.R.Thomas, JR, D.P.H.Hasselman, Role of material properties in the thennall-stress fracture of
brittle ceramics subjected to conductive heat transfer , .LAm.Ceram.Soc. 67(6): 393(1984).
7. W.D.Kingery, Factors affecting thermal stress resistance of ceramic materials, 1.Am.Ceram.Soc.38(1) :3
(1955).
8. T.D.Volkov-Husovic, Rlvl.Janci, Z.V.Popovic," Vzairnozavisimost parametra soprotivleniya razruseniyu i
kriticeskih velicin raznosti temperatur dlya keramiceskih materialov ", Ogneupory u tehniceskaya
keramika, 2:22 (1997).
9. T.D.Volkov-Husovic, R.MJancic, Z.V.Popovic, Poredjenje parametra otpomosti na lorn sa kriticnim
vrednostirna temperaturske razlike kod vatrostalnih materijala odabranog sastava, Metalurgija, 2(3):215
(1996).
293
SINTERING OF SULPHOALUMINATE CLINKER
B. Zivanovic' , Lj. Petrasinovic-Stojkanovic', S. Prokic' , T. Milovanovic 2
, Center for Multidisciplinary Studies.University of Belgrade, Yugoslavia

2 Cement Factory "Novi Popovac", Popovac, Paracin, Yugoslavia
INTRODUCTION
Sulphoaluminates or expansive cement clinker, which contains 4CaO3A1203S03

(C4A3S) as the predominant crystal phase, can be synthesized at a significantly lower
temperature (l100-1200C) than Portland cement clinker (approx. 1500C). We have
investigated the process of dynamic sintering of sulphoaluminate clinker using dilatometry
analysis with the purpose of establishing the mechanism of mass transport. Considering the
fact that sulphoaluminate clinker is obtained at lower temperatures, it was useful to
establish whether clinker of this cement could be ground more easily, as a high amount of
specific energy is used for this operation.
However, besides the reduced consumption of heat energy during sintering,
expansive or sulphoaluminate cements have other advantages such as: fast bonding,
expansion rather than shrinkage during hardening, and also good mechanical
characteristics, especially after short hydration times. This type of cement, which has not
been produced up till now in FR Yugoslavia, is a hydraulic material in great demand for
setting concrete in winter conditions, urgent rebuilding work (turmels, bridges, water
towers) etc. [1-5].
EXPERIMENTAL WORK, RESULTS AND DISCUSSION
Domestic natural raw materials were used as raw material components : bauxite,
limestone and anhydrite. The chemical composition of raw material components is given in
tab. 1.
Considering the fact that the sulphosilicate modulus [6] was 1.8 and 3.0 and the
saturation degree was 0.67, and taking into account the data given in tab. 1, the ratio of
starting components was obtained as: for sulphoaluminate clinker (SAK) 1: limestone -
50.46% bauxite1 - 35.96% and anhydrite - 13.58%, for SAK2: limestone 47.72%, bauxite2
- 33.01% and anhydrite - 19.27%, respectively.

Kluwer Academic/PlenumPublishers, New York, 1999 295
Table 1. The chemical composition of raw material components, (%)
Limestone Bauxite 1 Bauxite 2 Anhydrite Phosphogypsum
Lost ofIgnition 43.67 11.27 12.39 4.81 10.51
sio, 0.61 7.85 18.02 4.75 1.95
Alz0 3 0.20 46.46 41.38 1.78 0.20
FeP3 0.11 29.71 24.20 0.79 0.13
CaO 54.84 2.12 0.85 35.33 37.47
MgO 0.40 1.00 0.41 2.41 0.23
S03 trace 0.73 0.48 50.53 49.88
KzO 1.20 1.44
Nap 0.50 0.55
~ 99.83 99.84 99.78 100.80 100.37
The sintering process was observed on a high temperature dilatometer at a heating

rate of 30C/min. in the non-isothermal part to maximal temperatures of 1100, 1150 and
1200C. Isothermal sintering was observed in the time period of 140 minutes. Results
obtained for both investigated sulphoaluminate clinkers are given in fig. 1. From the
phenomenological viewpoint, the sintering process of investigated materials can be divided
into several stages. Up to the temperature of 500C (fig. 1), there are practically no
dimensional changes - this would be stage I. The second stage takes place in the
temperature interval of 500-800C, where thermal decomposition of the bauxite mineral
and carbonate decarbonisation occurred. This process is accompanied by expansion of the
material for maximally 0.3-0.6% at 700-800C. Intensive material shrinkage occurred in
the temperature interval from 800-1150C, which is the consequence of the predominance
of the sintering process in the presence of a liquid phase and the formation of clinker
minerals (stage III). Shrinkage was about 2-3% depending on the maximal sintering
temperature and partly the mineralogical composition of the starting raw material mixture
(SAK 1 and 2). Finally, in the temperature interval of 1150-1200C, further, though
insignificant shrinkage occurred, but with an almost constant rate (stage IV or the
stationary sintering stage).
During sintering of a starting raw material mixture, whose composition corresponds
to the formation of sulphoaluminate cement clinker, a liquid phase formed. Its amount was
15-30% and depended on the temperature [4]. The melt or liquid phase enables a change of
the space distribution of crystals of clinker minerals, leading the system by rearrangement
and suitable packing to a minimal total energy.
Butensky and Hyman [8], and also Sherrington [9], performed experiments where
they investigated what happened if a certain amount of melt was added to a powder
material (in a small rotation vessel, which was a model for a rotation furnace). It was
established that granules formed under the influence of capillary forces of the liquid phase.
This model is schematically presented in fig. 2.
296
- - - - SAK 1
- - SAK 2
- 5.0 Istage 11 stage III suge
- 4.0
moO(
- - -=- 0- - - -0- - - -0- - - -0-
- -3.0 1I50 0
(
't-
o
-" 1100(
')-
<l
-20

u
co
~
~ Sintering in the presence of

~u -1.0 Liquid phase (rearrangement)
.~
...
Ii
l>:
Decarbon isation
1.0,--~~~~~- ~ _ _ --.L._-'- ~~ __
100 500 1000 1200 30 50 70 90 110 no
Temperature Ts {O ( ) fs
Time (min)
Figure 1. Dynamic and isothermal sintering of sulphoaluminate clinker (SAK-l and SAK-2)
Based on this experience, it is logical to expect the occurrence of rearrangement

during sintering of the sulphoaluminate mixture, which will lead to the formation of a
skeletal structure in materials containing solid particles and the melt. After sintering in a
rotation furnace (capacity 50 kg of clinker per hour), clinkers were obtained. They did not
differ significantly regardless of the mineralogical composition of the starting raw material.
Microphotographs of cross-sections of granules of cement clinker in dependence on the
sintering temperature are shown in fig. 3.
It can be noticed, that besides small pores, very large pores, which even grow with
the increase of the sintering temperature, exist in granules of sulphoaluminate clinker. This
is probably the consequence of the fact that the melt which is in between solid state
agglomerates, leaves the pores between them, due to the action of capillary forces, and thus
leads to the formation of the previously mentioned large pores. The amount of these large
pores in investigated sulphoaluminate clinkers, depending on the sintering temperature, is
between 17-25%.
Structural investigations were also performed, using X-ray diffraction. Analysis of
diffractograms obtained (fig . 4) established that the investigated clinkers contained
4CaO3AI 20 3S03 (C 4A3S) and 4CaOAI203Fe203 (C 4AF) as dominant phases,
accompanied by small amounts of anhydrite (CaO S04-CS), portlandite (Ca(OHh -CH)
and free CaO (C) .
297
" So lidl:mJ Li q uid
t:::JPore
Figure 2. Granule structure model (2a) and rearrangement structure model (2b)
a) b) c)
Figure 3. Microphotographs of SAK clinker sintered at: a-I 100, b-1150 and c-1200C
Table 2. The participation of phases present in investigated samples (%)
Phases
No . T(C) SAK C4A3S C4AF CS CH C
I ll50 I 35 23 27 6 3
2 1200 I 45 38 5 4
3 1150 2 40 28 20 4 2
4 1200 2 42 34 15 2
The results presented up to now indicate the fact that we have successfully
synthesized sulphoaluminate or expansive cement clinker, as the crystal phase content,
C4A3S, which causes expansion during hydration was even 45% (at 1200C), and 35-42%
after sintering at 1150C. The free CaO content was low indicating successful synthesis of
sulphoaluminate cement clinker.
Optimal conditions for obtaining expansive cement clinker for the raw materials used
are: maximal synthesis temperature of 1200C, saturation degree of 0.67 and sulphosilicate
modulus1 of 3.0. It is obvious that the mineralogical composition of the starting raw
material mixture does not have a great influence on the phase composition of
sulphoaluminate cement clinker, though a higher content of bauxite (SAK 1) had a
favourable influence. The content of large pores in sulphoaluminate cement clinker (fig. 3)
is another advantage of this clinker, as significantly less energy is required during grinding
of this material. The mechanism of mass transport during sintering of investigated
sulphoaluminate cement clinkers is very complex and is associated with the process of
diffusion-reaction sintering in the presence of a liquid phase.
298
200
150
100
Figure 4. X-ray diagram ofsulphoaluminate clinker (SAKI) sintered at 1200C
CONCLUSION
Based on domestic mineral raw materials, sulphoaluminate cement clinkers (SAK)

were synthesized. The content of the component which leads to expansion during hydration
(4CaO3AI203S03) was 35-45% after sintering at temperatures of 1150 and 1200C. The
sintering process of this hydraulic material is very complex and can be defined as reaction
sintering in the presence of a liquid phase.
Sulphoaluminate clinker can be ground more easily that ordinary Portland cement
clinker as it contains large pores. The mineralogical composition of the starting mixture
does not have a significant influence on the dynamics of the sintering process of expansive
cement clinker.
REFERENCES
1. W. Kurdowsky, C. M. George and F. P. Sorrentino, Special cements, Proc. 8th Int. Cong. Chern. Cement,
Rio de Janeiro , VoU, 292-318 (1986).
2. P.K. Mehta, Investigations on energy-saving cements, WorldCement Technology, May, 166-177 (1980) .
3. G. Sudoh, T. Ohta and H. Harada, High strength cement in the CaO-AI 203-Si02-S03 system and its
application, Proc. 7th Int. CongoChern. Cement, Paris, Vol. 3, Theme V, 152-157 (1980).
4. L. Santoro, R. Garofano and G. L. Valenti, Calcium sulfoaluminate made from phosphogypsum and its
hydration properties, Proc. 8th Int. CongoChern. Cement, Rio de Janeiro , Vol. 4,389-394 (1986) .
5. G. A. Mudbhatkal, P. S. Parmeswaran, A. S. Heble, B. V. B. Pat and A. K. Chatterjee, Non-allitic cement
from calcium sulfoaluminate clinker: optimisation for high-strength and low-temperature application,
Proc. 8th Int. Cong. Chern. Cement, Rio de Janeiro, Vol. 4, 364-370 (1986) .
6. Lj . Petrasinovic, M. Stefanovic, B. Zivanovic et all, Synthesis of sulphoaluminate clinker on the basis of
domestic raw materials, Materialsand constructions, 35, 1-2, 44-48 (1992) .
7. W. D. Kingery, Kinetics and mechanism of liquid phase sintering, J. Appl. Phys, 30, 301-306 (1959) .
8. A. H. Egoloev, 1. F. Petersen, Die mechanischen eigenschaften von klinker bei hoher temperatur, J.
Zement-Kalk-Gips, 34, 591-594 (1981).
9. E. B. Allison, P. Brock, J. White, The reology of aggregates containing a liquid phase with special
reference to the mechanical properties of refractories at high temperatures, Trans. Brit. Ceram. Soc, 58,
495-529 (1959) .
299
PROGNOSIS OF THE MINERALOGICAL COMPOSITION
OF SINTERED PORTLAND CEMENT CLINKER
Ljiljana Petrasinovic-Stojkanovic' , Mirjana Djuric2,

Branislav Zivanovic', Miroslav Komljenovic' and Snezana Omicl
1 Center for Multydisciplinary Studies University of Belgrade

2 Faculty of Technology University of Novi Sad
INTRODUCTION
Th e possibility of evaluating the composition of cement clinker obtained by

sintering raw materials with a known composition is the basic prerequisite for
synthesis of products with desired properties.
Different, more or less precise experimental methods (microscopic and X-ray
structural analysi s) are used for determining the composition of a system. How ever,
the composition is often evaluated empirically (Bogue's equations). Application of
the thermodynamic principle of minimization of total Gibbs energy for the
evaluation of the mineralogical composition of sintered Portland cement clinker in
equilibrium is also possible.
In this paper a comparison is made between these methods on a selected
example and points out their advantages and shortcomings.
RAW MATERIALS USED IN THE PRODUCTION OF PORTLAND CEMENT
Cement belongs to a complex, multi component system: A12032Si022H20 -

CaCOrCaO-AI20rSi02- Fe20rNa20-K20-MgO-P20S-S03(g)-C02(g)-H 20(g) .
Customary raw materials used in its production are : A12032Si022H20
(kaolinite), CaC03 (calcite), Si0 2 (quartz), A1 203 (corund) and Fe203 (hematite).
The system whose composition is given in tables 1 and 2 was selected as a
typical example for our analysis .
CHEMICAL MODEL OF RAW MATERIALS CONVERSION INTO PRODUCT

The principal cement phases (cement minerals) are formed during sintering.
Their formulas are: 2CaOSi02, 3CaOSi02> 3CaOA1203, 4CaOA1203Fe203
12CaO7Al 203 and 2CaOFe203'
Advanc ed Science and Technology ofSintering, edited by Stojanovic et al.

Kluwer AcademiclPlenum Publishers , New York, 1999 301
Table 1. Starting phase composition of raw materials
PHASE Quantitative composition

Raw material
Kmol Kg Mol. Wt.%
%
K 2OAI2OJ6Si02 0.01 5.56 1.11 8.41
(microcline)
Na20AI20J6Si02 0.01 5.24 1.11 7.92
(albite)
AI2OJ2Si022H2O 0.015 3.33 1.66 5.03
(kaolinite)
F~OJ 0.03 4.80 3.32 7.26
(hematite)
Si0 2 0.08 4.77 8.81 7.2
(quartz)
CaCOJ 0.758 42.45 84 64.2
(calcite)
IN TOTAL 0.903 66.15 100 100
Table 2. Starting oxide composition of raw materials
OXIDE Quantitative composition

Raw material
Kmol Kg Mol. % Wt. %
K20 0.01 0.94 0.93 1.42
Na20 0.01 0.62 0.93 0.94
Al 20J 0.035 3.57 3.26 5.40
Fe20J 0.03 4.8 2.80 7.25
Si0 2 0.23 13.8 21.40 20.82
CaO 0.758 42.45 70.7 64.17
IN TOTAL 1.073 66.15 100 100
The reaction most often starts as:
(calcite) (kaolinite) (metakaolinite)
Formation of dicalcium-silicate 2CaOSiOz :
When metakaolinite forms, the following reactions are possible:
302
Formation of three-calcium-silicates 3CaOSi02 :
The formed 2CaOSiOz can react (in a solid state) in all temperature regions
producing 3CaOSiO z :
2CaOSiO+CaO:::}3CaOSi02
Also, 3CaOSiOz can form at the same time as CaO-Al z03:
Formation of calcium-aluminate 12CaO7AI203 :
Formation of 12 CaO 7Al 203 is more probable than the formation of

3CaO SiOz in the previous reaction:
40 CaC03+7 (Al z032SiOz):::}
12CaO 7Alz03+14 (2CaOSiO z)+40 COz(g)
At temperatures above 1100 (K), the following reaction is possible :

7 (CaO AI203)+CaC03:::} 12CaO7Al z03+C02(g)
Formation of calcium-aluminate 3CaOAI203 :
Formation of this substance from CaOAI 203 and CaO or CaC03 is not
possible, so it can be concluded that 3CaOAlz03 forms from the melt.
Formation of calcium-ferrite 2CaOFe203:
2CaOFe203 forms from CaO (or calcite) and iron oxide in all temperature
regions:
2CaO+Fe203:::}2CaO Fez03 and
2CaC03+Fe203:::}2CaOFe203+COZ(g)
Formation of calcium-alumoferrite 4CaOAI203Fe203:
This substance forms from 2CaO Fe203, aluminium oxide and calcium oxide (i.
e. calcite), but only for certain temperatures, which indicates the presence of a liquid
phase :
As far as the selected example is concerned, after sintering at the temperature

of 1723 (K) a product was obtained whose phase composition was determined using
X-ray diffraction analysis and the presence of basic cement minerals was
established. Evaluation of the final product composition was also performed using
Bogue's correlations based on the oxide content of the raw material .
303
DETERMINING THE EQUILIBRIUM COMPOSITION OF THE PRODUCT
General thermodynamic sintering model
Establishing the equilibrium composition of a system in which chemical

reactions take place is based on minimization of the total Gibbs energy, taking into
account certain limitations, most often balances of individual atoms:
n
Goal function: Gtot = IXiGi ~ min (1)
i=l
n
Limitations: I Vi,jXi = Nj.. .,... j = Lrn (2)
i=l
Abbreviations used: G-Gibb 's free energy, x-equilibrium molar number for a
certain substance, v- the number of individual atoms in one substance molecule, N-
the total number of substances, m- the total number of atomic types in the system
and n-the starting number of one type of atom.
Sintering model of the selected example
Having in mind the substances potentially present in the system (marked as

in Table 3) the mathematical model of the selected example is given by eq. (1) for
n=27.
Limitations are:
Calcium balance:
3x I +2x 2 +3x3 +4x4 +XS +12x 14 +X 16 +2X 19 +x 20 +X 21+2X 22 +X 23 +X 25 +3X26 = 0.758
Silicon balance:
XI + x 2 + 6x 5 + 6x 6 + 2x 7 + X9 + 2XI5 + X20 + X22 + 2x 23 + 2X24 + 2X25 + 2X26 + X27 = 0.2295
Aluminium balance:
2x 3 + 2x 4 + 2x 5 + 2x 6 + 2x 7 + 2x IO + 14x'4 + 2XI5 + 2x 21+ 2X22 + 2X23 + 6X24 + 4X25 + 2X27 = 0.07
Oxygen balance:
5x] +4x 2 +6x3 +10x4 +16x 5 +16x6 +7x7 +X S +2x9 +3xlO +3x ll +X 12 +x 13 +33x 14 +9X 15 +
+3X 16 + 2Xl 7 + XIS + 5Xl9 + 3x 20 + 4x 21+ 7X22 + 8X23 + 13x24 + 7X25 + 7X26 + 5X27 = 2.978
Iron balance: Potassium balance: Sodium balance:
2x 4 + 2x ll + 2XI9 = 0.06 2x 5 + 2x 13 = 0.02 2x 6 + 2x 12 = 0.02
Carbon balance: Hydrogen balance: CO 2 balance: H 20 balance:
Xl6 = 0 4X15 = 0 XI1 = 0.758 XIS = 0.03
Gibbs free energy values were determined for all reactants and products
using enthalpy and entropy values in the standard state and corrected by
temperature contributions, based on known values of specific heat capacity. The
total Gibbs energy of the system is the sum of:
Data given in table 3 was used for the calculation of Gibbs energy values.
304
Table 3. Thermodynamic substance data
SUBSTANCE term Mt'Z98 "'S0298 a bxliY cx lO5

(k Ilkwo1) (kT'kwo! K)
3CaOSiO z XI -3929482 -669.8 267.9 37.9 -69.5
2CaOSiO z Xz -2309583 .6 -384.9 151.7 37.0 -30.3
3CaOAlz03 X3 -3562286 -535.0 260 .7 19.2 -50.6
4CaOAlz03Fez03 x4 -5082641 -977.1 374.6 72 .8
K zO Alz036SiOz X5 -7933307 -1510.1
Na zOAlz036SiOz X6 -7868005 -1498 .3 548.3 87.7 -153.6
Al z032SiO z X7 -3380028 -688.1 295.5 21.3 -20.4
CaO X8 -635853 -104.5 48.8 4.5 -6.5
sto, X9 -910874 -182.1 60 .3 8.1
Al z03 x lO -1676409 -313.4 114.8 12.8 -35.5
FeZ03 XII -821750 -272.0 98.3 77.9 -14.9
NazO x\2 -416100 -131.9 64.5 22.6
KzO X13 -361670 -131.5
12CaO7Al z03 XI4 -19423710 -3237 1264 247 -231.5
Al z032SiO z2HzO XI5 -4119024 -1075 .6 240 .6 147.8 -32.9
CaC0 3 XI6 -1207452 -308.3 104.6 21.9 -25.9
COz X17
HzO XI8
2CaOFeZ03 XI9 -2125232 -461.8 248.0 48.9
CaOSiO z Xzo -1631493 .5 -322.5 108.2 16.5 -23.7
CaOAl z03 XZI -2328169 -394.4 150.7 41.8 -33.3
2CaO Al z03SiOz xn -4006421 -667.2 266.8 33.5 -63.3
CaOAl z032SiO z X23 -4241799 -757.4 269 .7 57.3 -70.7
3Alz032SiOz xZ4 -6829961 -1286.6 485 .2 46.9 -154 .9
CaO2Alz03 x25 -4006253 -695.1 276 .7 22.9 -74.5
3CaO2SiOz X26 -3929482 -669.8 268 .0 37.9 -69.5
Al z03SiO z XZ7 -2593520 -495.1 172.5 26.1 -51.1
* Note: the expression for specific heat capacity is: cp=a+bt+cr2 (kJlkmol)
Table 4. Solutions of the thermodynamic mode l
SOLUTION A SOLUTIONB
Optimal Optimal
Substance composition (kmol) Substance composition (kmo l)
3CaOSiO z 0.194 3CaOSiO z 0.134
2CaOSiOz 0.0355 2CaOSiOz 0.0955
3CaOAl z03 0.035 3CaOAlz03 0.035
4CaOAlz03Fez03 4CaOAlz03Fez03
FeZ03 0.03 FeZ03
NazO 0.01 NazO 0.01
KzO 0.01 KzO 0.01
COz 0.758 COz 0.758
HzO 0.03 HzO 0.03
2CaOFez03 0.03
G101(kJ/kmol) -651430 GI01(kJ/lunol) -657824 "
* Note: the total Gibb s energy ofthe system without CO2 and H 20
SOLUTION METHOD AND MODEL RESULTS OBTAINED
If the assumption is made that all CO 2 and H 20 are released during thermal
treatment, the mathematical model becomes linear, so linear programming can be
applied . Results obtained are given in table 4.
305
The model is solved using two methods. The first one assumes that only basic
cement minerals are formed during sintering and the reactants do not need to
completely react (solution A in table 4); the second method assumes that the
number of potentially present substances is all 27 given in table 3 (solution B in
table 4).
The second solution was adopted from the two alternative ones (the one with
the smaller G to t ) '
Table 5. Comparison of results obtained using different methods
PHASE Quantitative product composition in (wt.%)

Experimental Thermodynamic According Experience interval
(XRD) (equilibrium) to Bogue for Portland cement
3CaOSi02 44 46.19 62.5 35-55
2CaO Si02 42 24.83 13.7 15-35
3CaOAI20 3 9.5 14.29 10 7-15
4CaOAI203 Fe203 3 10.7 5-10
2CaO Fe203 12.34
IN TOTAL 98.5 100.1 96.9
ANALYSIS OF SOLUTIONS AND CONCLUSION
Product compositions determined experimentally (X-ray diffraction method)

and evaluated using the thermodynamic principle for reaction equilibrium as well as
Bogue's correlations are comparatively given in table 5. The following conclusions
can be made after analysis of results:
* Differences exist in mineralogical compositions obtained by diffraction
analysis and thermodynamic calculations. These differences can be explained
primarily by the fact that in the case of real clinker the equilibrium state planned by
thermodynamic calculations was not reached. Also , thermodynamic calculations are
based on strict weight balance, which need not be the case in real systems.
* The interrelation between three-calcium- and dicalcium-silicate, according
to thermodynamic predictions is approx. 2:1, which corresponds to real clinker.
* As far as the three-calcium content is concerned, a lower content was
established by diffraction analysis than the thermodynamically expected one .
* The total participation of the ferrite phase in real clinker is also lower that
the thermodynamically predicted one .
* Bogue's correlations evaluate the composition in this case less successfully
than the rigorous thermodynamic method.
* The mineralogical composition of sintered Portland cement clinker as well
as the composition of the raw mixture can be evaluated based on the described
method.
REFERENCES
1.V.!. Babushkin, G.M. Matveyev, O .P.Mchedlov-Petrossyan Thennodynamics of SiJicates, For th

Ed ., Striizdat, Moskva, 1986 (in russian) .
306
EDS ANALYSIS OF SINTERED MATERIAL DEGRADATION
IN AN AGGRESSIVE ENVIRONMENT
Sasa Miletie,l Marina IIie,l and Predrag Jovanie2
lInstitute for Materials Testing, Bul.vojv.Misica 43, Belgrade,

Yugoslavia
2ITNMS, Franse d'Eperea 86, Belgrade, Yugoslavia
Abstract
The behaviour of Portland cement with and without 30% fly ash addition in
aggressive solution was studied. This paper considers the ammonium-sulphate
corrosion of the hardened cement paste as the main constituent of the portland
cement concrete. The cement paste test samples were prepared, cured in water for
21 day and then exposed to the influence of aggressive environment (10%
(NH 4hS04 solution). The measurements of several properties were carried out and
the results were analyzed.
The image of the surface composition and morphology of the cement paste test
samples was made by scanning electron microscopy (SEM) . Concentration gradient
of sulphate ions in cement paste depth was obtained by energy-dispersive analysis
(EDS) and this method was found very useful for studying the portland cement
concrete corrosion.
INTRODUCTION
Unless it is resolved successfully, as a part of the integral environmental

management, the problem of wastes might become one of the burdens on the future
generations. Besides environmental pollution, this also concerns some important
economic reasons connected with the growing price of raw materials and energy.
Thermo-power stations, which are using coal as the fuel, mostly have installed very
efficient equipment for preventing the emission of solid particles (fly ash) to the
atmosphere. For our country it is about 10,000,000 t per year of this material. Wetted
material is then transfered to deposit places which presents very big ecological
problem. By definition, fly ash is a fine powder of mainly spherical, glassy particles
Advanc ed Science and Technology ofSintering , edited by Stojanovic et al.

Kluwer Academic /Plenum Publishers , New York , 1999 307
having pozzolanic properties and consisting essentially of Si02 and A1203. Because
of that, the aim of our first investigations was to establish procedure for deposits of
waste fly and bottom ash utilization in building materials production. Reaching this
aim means reducing enormous ecology problem so as the getting equal quality
products (cement, mortar, concrete, bricks, etc.). Concrete has been widely used as
the most important constructional building materials in the world.
In practise, concrete buildings suffer simultaneously mechanical , chemical and
physical attacks. Therefore, the effect of mechanical stresses must be taken into
consideration when durability and corrosion resistance of a concrete are estimated,
i.e., the study of stress corrosion of concrete is necessary and very important for
durability.
Primarily, the types of chemical corrosion of sintered material (cement) in
concrete can be divided into two groups, i.e., expansive corrosion and dissolving
corrosion, with respect to the cause of failure of concrete. The attack of sulphate
ions on sintered material can cause expansion, in general due to the format ion of
ettringite C3A3CaS0432H20, in the shape of prismatic crystals. The consequences
are damages to the concrete and destruction at worst. The concrete corrosion by
ammonium sulphate, for example, covers the most aggressive corrosion on concrete,
neither balancing nor creation of protective gel takes place. In this case concrete is
damaged not only by expansion, but also by dissolving the sintered material.
In recent years, there has been an increasing need to devel0v, new testing
methods for monitoring the sulphate attack on concrete structures ,2. There are
many test methods available for the assessment of the quality and degradation of
concrete structures. The basic ideas of this work was to test the possibillity for
application EDS analysis in our case. The aim was to investigate sulphate attack on
concrete structures, i.e. to obtain concentration gradients of sulphate ions through
the sample of cement paste. This was done by monitoring concentration of
elementary sulphur through cross sections of the sample, in line, because EDS is a
technique which determines the elemental content in a very small surface area. The
advantages of this method are that it is non destructive and does not require any
additional sample preparation.
EXPERIMENTAL
Portland cement and Portland fly ash cement manufactured in Yugoslavia were
used:
Portland cement B (PCB)-according to the European cement standard EN 197-1:
CEM-I
Portland fly ash cement B (cement clinker B) with 30% fly ash (PCBP)-
according to the European cement standard EN 197-1: CEM IIIB-V
All materials have been chemically analyzed and their physico-chemical and
mechanical properties have been investigated. The resistance of the cement to the
aggressive solution was tested on mortar prisms. First results were already
published". The testing methods used in this part are: determination of standard
strength (EN 196-1), chemical analysis (EN 196-2), determination of setting time
(EN 196-3), determination of the sieve residue (EN 196-6), determination of specific
surface (EN 196-6), calculating the potential phase analysis (ASTM C 150).
To analyse the degradation process caused by sulphate attack, samples were
prepared as follow. The chemical resistance of the cements was tested with cement
paste lxlx6 em test prisms prepared with water/cement ratio needed for the
standard consistency. Before having been exposed to aggressive solution prisms
308
were cured 1 day in the mould and 20 days in water. As aggressive environment a
10% (NH4hS04 solution was used .
The concentration gradient of sulphate ions in prepared cement paste samples ,
dimensions lxlx6 em and broken on halves (lxlx3 ern approximately), was
performed by an energy-dispersive method on an Edax 9900 apparatus at the cross-
section of the broken sample. For this purpose, samples were mounted on stubs and
pumped to a vacuum level of 1.33.10-6 Pa. Monitoring of elementary sulphur content
was done in 20 points on 1 em width of samples, so the monitoring on the centered
line of the cross-section was obtained. Simultaneously, morphological analysis was
performed by scanning electronic microscopy, and the images were obt ained by
secondary electrons on a Philips 515.
The selected aggressive environment represents a very strong aggressiveness to

ensure fast results for the real conditions which can be present in underground
waters in Yugoslavia.
The potential phase analysis of the Portland cement clinker is given in Table 1. It
can be seen tha t the cement have usual C3A content in clinker of 13.3% influencing
the sulphate resistance. The ordinary Portland cement, such as the investigated one,
is not resistant to the attack of sulphates because it has a considerable content of
tricalcium aluminate - C3A, whose hydrates react with sulphate ions, giving
expansive compounds. According to the literature the difference in the ~S content
could be significant regarding sulphate resistance also.
Table 1. Potential phase composition of Portland cement clinker.
Potential phase composition, %mass Portland cement clinker B

57.5
13.5
13.3
8.7
Table 2 presents the chemical composition of fly ash. According to the high
content of SiOz, Al 203 and Fe20 3 and the low content of CaO, MgO, alkalies and
S03 the fly ash is suitable for cement and concrete production though loss on
ignition was relatively high and especially hydrated (bonded) water.
The chemical composition of the cements meet Yugoslav standard JUS B.C1.011.
Portland fly ash cement PCBP has a higher insoluble residue and loss on ignition
than Portland cement PCB, as it was expected. The addition of fly ash raises the
water demand for standard consistence and sieve residue and extends setting time,
but has no significant influence on other characteristics. All characteristics are in
compliance with Yugoslav standard JUS B.C1.011. The Portland fly ash cement
PCBP had lower strengths even after 28 days than the corresponding Portland
cement PCB 3-6.
The content of sulphur, i.e. content of sulphate, as determined by the EDS
method, is given in Figs. 1-5. The distance, given on X-axis, means the distance from
one side of the cross-section of the broken half to the other one (10 mm at all)
through the centerred line of the cross-section. It is important to emphasise that ,
309
Table 2. Fly ash chemical composition
Chemical composition , %mass Fly ash

LOI 5.7
SiOz + Alz0 3 + Fez03 84.2
CaO 6.5
MgO 2.7
S03 0.05
S 0.02
NazO 0.3
KzO 0.7
Hydrated (bonded) water 34.6
Insoluble residue 76.6
c::
0
-p
~c::
4
\ E-3days I
I
I
\
B 3
c::
!
0
(J
"0 2
.:
Q.)
.!::l
\
ca

0
Z /' _ cr~ /'
0
0 2 4 6 8 10
Distance (mm)
a)
c::
0 4
I -O-3days I
-...
-p
~
cQ.)::
\
3
!
(J
c::
0
(J
"0 2
Q.)
N
~ 0
\0 /
Z
0
-, p-o...o
0
0 8 10
Distance (mm)
b)
Figure 1. Concentration gradient of sulphur through the depth of sample after 3 days
in aggressive environment, determined by EDS method, for:
a) Portland cement PCB
b) Portland fly ash cement PCBP
310
5
I
o~
\ I -O-7days
I
!J
4
.::;:

~
g3
82 \ \
~
~ 0
\ oYO,
o-~ -~
/
cr
0 2 4 6 8 10
Distance (nun)
a)
I
'0-, ! -0-7days
c:
.g 4 0
!
~e \
g3
0
0
\

2
~
N
~
\
~0 0'0-0 ,
0 2 4 8 10
b)
Figure 2. Concentration gradient of sulphur through the depth of sample after 7 days
in aggressive environment, determined by EDS method, for:
311
s::
I ---e- 14 days I /J
I
0 4
.~
t:l
&3 3
/
t)
s::
0
t)
2
]
Z
~

0
0 2 4
A~j 6 8 lO
Distance (mm)
a)
~
s::
\6 - 6- 14 days
I
~
4
\ ' I:>..... 6A
0
...s::
.~
6
I
I
I
o 3
0)
~
e 6
\
0
o
~ 2
!
0)
N
~ 6
E \6
z0 0 '6'~A.. /
6
0 2 4 6 8 lO
Distance (mm)
b)
Figure 3. Concentration gradient of sulphur through the depth of sample after 14
days in aggressive environment, determined by EDS method , for:
312
5~~..---------------"~
O'--~--'--~---'-~---'---~---L_~-'
o 2 4 6 8 10
Distance (nun)
a)
5 -,
'V 'V - v
\ I- 'V- 2 1 days
- /
l:::
.9 4 ~\ / 'V
~ 'V" ;'V
l::: /
'V~
Q)
o 3 'V 'V
l::: -, /
0 'V ~
o 'V 'j7
\
"Cl
Q)
2 /
.~ 'V
Cii /
'V,-'V _'V/'V

0
Z
0
0 2 4 6 8 10
Distance (nun)
b)
days in aggressive environment, det ermined by EDS method, for:
313
c
.g 4
e
i::
Q)
o 3
C
0
u
"0
Q)
2
.~
";
E
0
z
0
0 2 4 6 8 10
Distance (mm)
a)
c
.s 4
~
i::
o 3
Q)
c
0
o
"0
Q)
2
.~
";
E
0
z
0
0 2 4 6 8 10
Distance (mm)
b)
days in aggressive environment, determined by EDS method, for:
comparing two tested cements, all obtained curves are very similar. This means that
the behaviour of both cements in aggressive environment is similar. But, regarding
maximum normalized value, 5, it could be seen that Portland fly ash cement PCBP
has less points at that level in all terms of investigation, meaning that sulphate
content through depth of test sample is lower. The repeated testings showed the
same results, so it could be concluded that this method has the high accuracy. Such
results were got also by previous investigations meaning that Portland fly ash cement
PCBP is more suitable for use in aggressive environment than the ordinary Portland
cement PCB.
CONCLUSION
The results of testing the attack by aggressive sulphate solutions allow the
following conclusions:
3 14
1. The selected aggressive environment represents a very strong aggressiveness to
ensure fast results for the real conditions which can be present in underground
waters in Yugoslavia.
2. Testing results showed that EDS itself couldn't represents the degradation
process, but combined with other significant characteristics such as SEM, mass
change, XRD, bonded SO/ content and flexural strengths (degradation and/or
corrosion coefficients derived from them), represented valuable characteristics.
REFERENCES
1. I. Biczok, Concrete corrosion, concrete protection, Eight Edition, Budapest
(1972).
2. V.M. Moskvin, Korozija betona i zelezobetona, Moskva (1980).
3. S. Miletic, and M. Ilic, Sulphate corrosion of Portland cement with various
mineral compositions, Proceedings ofthe ts" International Corrosion
Congress, Melbourne, Australia, II:188 (1996).
4. S. Miletic, M. me, J. Ranogajec, R. Marinkovic-Neducin, and M. Djurie,
Ammonium - sulphate corrosion in Portland cement and Portland ash cement
concrete, Proceedings ofthe EUROCORR '97, The European Corrosion
Congress, Trondheim, Norway, 1:573 (1997).
5. S. Miletie, M. me, J. Ranogajec, R. Marinkovic-Neducin, and M. Djuric, Portland
ash cement degradation in ammonium-sulphate solution, Cement and Concrete
Research 26:5, 713 (1998).
6. S. Miletic, and M. Ilic, Effect of ammonium-sulphate corrosion on the strength of
concrete, Proceedings ofthe ldh ICCe, Goteborg, Sweden, 4:4iv023 (1997).
315
EVOLUTION OF THE PHASE COMPOSITION
DURING SINTERING OF THE MgOAh03-SiOz SYSTEM
l z
Mila Atanasovska', Maria Vesna Nikolic , Stamenka M. Radic
I JointLaboratory for Advanced Materials of the Serbian Academy of

Sciences and Arts
zlnstitute of Technical Sciences of the Serbian Academy of Sciences and
Arts, Knez Mihailova 35, 11000 Beograd, Yugoslavia
INTRODUCTION
Cordierite ceramics is widely applied in modern technology and the establishment of

optimal technological conditions in the obtaining procedure is of special importance. From
l z
this viewpoint, the work of P. P. Budnikov and A. S. Berzhnoi can be considered pioneer
3
research in this field . C. S. Pereira and S. Pracidelli and J. R. Casarini" investigated the
method of obtaining cordierite from talcum and clay.
The evolution of the phase composition during sintering of a non-activated and
activated mixture of pure MgO, Ah03 and SiOz oxides in the molar ratio of 2:2 :5 was
investigated in this paper. It was shown that mechanical activation of starting mixtures
leads to obtaining of ceramics with a cordierite content of over 90% .
EXPERIMENTAL
MgC0 3, Ah03 and SrO, (p.a.) powder, with particle sizes bellow 20 um were mixed
in the molar ratio, which corresponded to the stoichiometric composition of cordierite:
2MgO 2Ah035SiOz. Part of this mixture was activated by grinding in a "HUMBOLT
WEDAG MN 953/3 " vibro mill for 560 minutes. Characteristics of the activated and non-
activated powder mixtures are given in table I.
Table 1. Characteristics of the starting powder mixture
Powder Specific surface (m 2/g) Average particle diameter (11m)

non-activated (C-N) 2.33 5.16
activated (C-A) 7.69 3.68

Kluwer Academic /Plenum Publishers, New York , 1999 317
Obtained powders were pressed under the pressure of I MPa, resulting in samples
with IOx5 mm, and then sintered for 120 minutes in the temperature interval of 1100-
1450C in air. The measured density of sintered samples is given in table 2.
Table 2 Density of sintered samples
Sintering temperature Density (g/crrr')

(0C) C-N C-A
1150 1.51 1.59
1250 1.53 1.64
1350 1.62 1.80
1450 1.78 2.11
Sintered samples were investigated on a "Philips PW 1710" X-ray powder

diffractometer, with CuKa radiation and a graphite monochromator. The working voltage
of the tube was 40 kV and the current strength was 30 rnA. The samples were investigated
in the range 10-20 28, with a step of 0.02 and a holding time of 0.5 s for each step.
Semiquantitative analysis of was performed of X-ray pictures and results obtained are
given in table 3.
Table 3 Phase composition of sintered samples of the 2MgO-2Ah03-5SiOz system (wt. %)
Sample Phase Sintering temperature (0C)

1150 1250 1350 1450
cordierite 0 0 9 15
spinel 7 15 8 3
forsterite 0 2 2 2
C-N Quartz 68 52 16 42
crvstobalite 5 16 20 24
corundum 14 II 10 9
periclase 6 4 5 5
cordierite 23 25 47 92
spinel 18 15 26 4
C-A Quartz 17 18 0 0
crvstobalite 39 37 27 4
corundum 3 5 0 0
DISCUSSION
Based on an analysis of experimental results (figures I and 2) it can be concluded that

evolution of the phase composition during sintering of the 2MgO-2Ah03-5SiOz system is
the consequence of the activity of the starting oxide mixture. In the case of the sample C-N
it is obvious that practically two processes take place simultaneously during the complete
temperature interval:
- the phase transformation quartz-ecrystobalite and
- the reaction of cordierite formation .
In the case of sample C-A, the same processes take place, though the amount of
crystobalite reduces with the increase of the amount of cordierite . Spinel formed in both
cases, though its amount is very small, at 1450C.
The sintering mechanism can be assumed having in mind the performed analysis of
experimental results. It consists of the following:
- quartz is transformed into crystobalite,
- magnesium oxide reacts with aluminium oxide giving spinel,
- spinel reacts with crystobalite giving cordierite.
318
Co - cordierite
%
5 - spinel
F - forsterite
70 Q - quartz
Cr - cristobalite
C - corundum
P - periclase
50
Q
40
30
Cr
20
Co
10 C
P
5
F
1150 1250 1350 1450 reo
Figure 1. Evolution of the phase compo sition during sintering of sample C-N
Of course, these reaction s occur simultaneously, so the mechanism of reaction

sintering of the 2MgO-2AIz03-5Si02 system can be presented in the follow ing way:
n-quartz-e-Cr (crystobalite) (I)
(2)
2(MgOAIz03) + 5 Si02 (Cr) ~ 2MgO . 2AIz03 5Si0 2 (3)
It can be assumed that the following processes take place in place of reaction (2):
a) c1inoenstatite formation :
MgO + Si0 2 ~ MgO . Si0 2 (4)

or
b) forsterite formation:
2MgO + Si02 ~ 2MgO . Si0 2 (5)
The free energy of these reactions is - 1464 kl/mol and 2062 kl/mol, respectively,
while the free energy of reaction 2 is 2149 kl/mol .5 Taking this into account, and also
considering principles of solid state thermodynamics", it is justified to assume that the
reaction of spinel formation is more probable.
Reactions I and 3 are justified, having in mind that reaction I is the consequence of
mechanochemical activation? This is also seen in figure s 1 and 2.
319
%
90
80
70
60
50
Co - cordierite
S - spinel
40 Cr - cristobalite
Cr
C - corundum
Q - quartz
30
Co
20
S
Q
10
C
1150 1250 1350 1450 T 1C)
Figure 2. Evolution of the phase compo sition durin g sintering of sample C-A.
CONCLUSION
Evolut ion of the phase compos ition of the non-activated and activated powder mixture
of MgC03, Ah03 and Si02 during sintering. Activation was performed by grinding the
powder mixture in a vibro mill. It was established that sintering of the activated mixture at
I450 C results in the formation of ceramics with over 90 % of cordierite .
ACKNOWLEDGMENT
This work was performed as part of the project "Prognosis of Materials Properties
from the Viewpo int of the Triad SSP (Synthesis -Structure-Properties)" financed by the
Ministry for Science and Technology of Serbia and the project "Investigation of the
consolidation process of materials" financed by the Serbian Academy of Science s and Arts.
REFERENCES
1. P. P. Budnikov , V. G. Avetikov , A. A. Zvyagil skii, DAN SSSR , 81(1951) , 883

2. A. S. Berzhnoi, L. I. Karyakin , DAN SSSR, 80(1950) ,423
320
3. C. S. Pereira, C. Pracidclli, Ceramica, 27(1981), 397
4. J. R. Casarini , Cerami ca , 28 (1982 ), 3 1
5. V. P. Prya shnik ov, Sistema kremen ezema, Stroi zdat, Moskva, 1991 (in Russian)
6. N. M. Bobkov a, Fizicheskaya him iya si/ikatov i tugoplavkih soedinenii, Vysheyshaya shkola, Minsk, 1984
(in Russian)
7. V. V. Boldyrev, Kinetika i katali z: 13(1992), 1411
321
EXPERIENCES IN THE CHEMICAL GYPSUM -PHOSPHOGYPSUM
PREPARATION FROM THE TRIAD "SYNTHESIS-STRUCTURE-
PROPERTIES" VIEWPOINT
Milos B. Rajkovic, Dragan Simovic , and Goran T'Vladisavljevic
Institute of Food Technology and Biochemistry, Faculty of Agriculture,

University of Belgrade, 11080 Belgrade, Nemanjina 6, FR Yugoslavia
INTRODUCTION
The production of phosphoric acid, by dihydrate process so-called "wet process" at

low temperatures 1OOC), which is used later for manufacture of phosphoric and other
mixed fertilizers, is followed by separation of enormous quantities of phosphogypsum :
about 4.5 t of phosphogypsum proceed to 1 t of fertilizers (P 205 equivalentj v" . Besides
enormous quantities, due to mineral impurities and high water content, phosphogypsum as
waste-product is usually deposited close to phosphoric acid plants or into rivers and
oceans. Phosphogypsum represents ballast, but from the ecological viewpoint is of
particular concern due to its toxic comonents such as fluorides, uranium and from the
uranium series the most important are 22 Ra, 222Rn and 11OPO.
In our previous papers, investigations of phosphogypsum have been carried out, and
its characteristics were compared to natural gypsum':" and detailed possibilities of
phosphogypsum usage as a sem iproduct and a final product have been analysed.
This work is focused on the application of instrumental techniques for
characterisation of phosphogypsum from the triad "synthesis-structure-properties"
viewpoint in order to investigate their potential use as a substitute for natural gypsum.
EXPERIMENTAL
Phosphogypsum - waste product obtained from phosphoric acid plant IHP Prahovo
were used for all investigations'. The phosphogypsum were analysed by following
procedure 't": samples were sieved on vibrat ion screen and only fractions less than 200 J..1m
were taken . The sample was rinsed with distilled water, ethanol and ether, and then it was
dried at 60C to constant mass. After calcination at 160C during 2-3 hours the analysis
were repeated.
Phosphogypsum samples were analysed using scanning electron microscopy SEM,
JSM - 840A, JEOL, Japan . The x-ray diffraction analysis was carried out with
Advan ced Science and Technology ofSintering, edited by Stojan ovic et al.
Kluwer Academic/Plenu m Pub lishers, New York, 1999 323
diffractometer for powder SIEMENS D-SOO with Ni-filtered CuKe radiation.
Identification of crystalline phases in recorded samples has been carried out by position
and intensity comparison of diffraction profiles with IC PDA data . Thermogravimetric
analysis of phosphogypsum was performed on Dermatograph STANTON, England, with
heating speed of up to 7C/min in air stream in mixture with Ab03, samples were
analysed in ceramic crucible at temperatures up to SOOC.
The phosphogypsum samples and their radioactive contamination were analysed by
the following procedure'" : phosphogypsum samples were previously dried at lOSoC for 24
hours to remove moisture which is the result of process technology, so that all
measurements are calculated to dried substance. Samples were packed in small plastic
vessels and hermet ically closed to retain evolved radon . Time for measurements of each
spectrum was about 24 hours, and all measurements were repeated after 20 days to obtain
radioactive equilibrium of evolved radon". Low phonon measurements were carried out
using CANBERRA Hp Ge coaxial detector with a relative efficiency of 14%, FWHM of
1.7 keY, placed in vertical cryostat and protected with 2 em of iron and IS ern of lead.
Total measured speed of phonon counting in energetic range of 20-2880 keY was 0.9
impulses/sec. Spectrometer was connected with CANBERRA 8k ADC "MCA 3S+"
multichannel analyser which was connected with HP Vectra ES/12 computer and analysis
- treatment of gamma spectra was performed using a "MicroSAMPO" software. Time for
sample measurements was about 160 ks, while measurements of phonon spectra were
significantly longer and were carried out regularly between sample measurements. Radium
and potassium activity was determined by comparison with the standard SRM694
(Standard Reference Material 694, National Bureau of Standards, US) WPR (West
Phosphate Rock), a phosphate rock with known uranium concentration (l41.40.6 ppm)
which is in equilibrium with its decay products.
The analysis has been carried out with previously dried sample of phosphogypsum at
60C, and then classification of particles was performed . It is necessary to remove extreme
fractions since they contain the highest contents of contaminants. Phosphogypsum particle
sizes were in the range of 20 to 200 11m with an average value of 80 11m. The elimination
of impurities has been carried out by screening on the screens or by foaming agents , such
as alkyl aryl sulphonates (dodecyl benzene sulphonate, tetrapropyl benzene sulphonate,
etc) .
Scanning electron micrograph of phosphogypsum sample is shown in Figure1. It can
be seen that phosphogypsum has well-defined crystalline structure with a majority of
rhombic and hexagonal crystal systems . It leads us to conclude that phosphogypsum has a
more complex composi tion than natural gypsum , which is in accordance with literature
data 78. The identification of the crystal phases in the surveyed samples has been
perfo rmed by comparing the position and the intensity of the diffraction profiles with the
IS PDS data. The all complexity of phosphogypsum stems from its crystalline structure
and caused influence on chemical behaviour.
Thermogravimetric analysis of phosphogypsum sample was performed in air stream
with speed of heating of 7C/min, and the obtained results are presented in Figure 2,
showing the percent change of sample mass as a function of temperature. The mass loss
for phosphogypsum is 17.S3% (gypsum loses 2 molecules of water), that would
corresponds to gypsum portion of 84% in sample . For natural gypsum, which is a
hemihydrate (CaSOd/2HzO) the mass loss is S.7S% that would corresponds to gypsum
portion of93%.
The x-ray diffraction analysis was carried out with diffractometer for powder and
324
identification of crystalline phases in recorded samples has been carried out by position
and intensity comparison of diffraction profiles with JC PDA data. The following
crystalline phases were identified for phosphogypsum: CaS042H20 (33-311) ;
CaS04,1/2H20 (33-310) spectra were corresponded to natural gypsum, CaHP04 (9-80) or
CaHP0 4,2H 20 (9-77) spectra were also corresponded to natural gypsum. The
diffractogram obtained by X-ray analysis of phosphogypsum sample is given in Figure 3.
Figure 1. Scanning electron micrograph (SEM)

showing crystalline structure of phosphogypsum
(XSOO)6
The results of the investigation of phosphogypsum have been compared with the
results obtained by the investigation of natural gypsum'" where a similarity but also a
difference has been noticed in comparison with natural gypsum. In phosphogypsum P20 5
can be found , which the natural gypsum contains in a very small quantity (P205 /tot ""
0.014% in relation to phosphogypsum with 0.67%) . The presence of the fraction P 20 5/sin
is unfavourable only if phosphogypsum is applied in construction, while in agriculture it
can have a positive effect on the treatment of the soil. A positive attribute of
phosphogypsum is the presence of CaO (11.97 % more than in natural gypsum) and of
S03 (1.22 % more). The advantageous feature of phosphogypsum is high portion of CaO
and S03 , that indicates on presence of other salts with sulphur (MgS0 4, Ah(S04)3,
FeS04).
The fluorine is an unfavourable component though, and phosphogypsum has it 300 %
more than natural gypsum. Fluorine in phosphogypsum is originated from natural
phosphates, wh ich are the basic raw material for the production of the phosphoric acid .
From the total distribution of fluorine durin the production of the phosphoric acid, up to
f
1/3 belongs phosphogypsum (cca. 27.80 %) . Before the direct, the removal of the fluorine
is necessary, by means of various additives which with fluorine build insoluble
compounds.
Organic substances cause great difficulties in process of phosphoric acid production.
The method of organic substance determination is the calculation to carbon portion, which
is in the order from 0.1%.
The investigations obtained with different phosphogypsum samples'? showed that
chlorides are only in traces, K 20 is presented in 0.0084%, Na20 in 0.445%, that is
expected value since it is not presented in significant portion in phosphates.
325
100 r - - - - - - - - - - ---,
~ NATU RAL GYPSUM
- - PHOSPHOGYPSU M
95
90
&5
100 200 300 ~oo 500

rc
Figure 2. Thermogravimetric analysis of phosphog ypsum samples
,..;
::; 6
.,;
-:; ...
~ '"
'" -o oD
:r- .., ~
.....,'"
N
0
~ ~
~
oD
'" '"
..#
0
.-;
0
0
-r
N
.;
:!:
....
8 ... ~
~
~ ..,.0
'" ...'"
..; 00
.,;
....
oD
'" ~ ,.; '"
'" '" '"
....
'" ~ '" 0
0
00
'"
'" '" :3 :3
'"
oD
0 00
'"
'0 ~
~
0
0 0 0 0 0 0 0 0
0> 0> 0> 0> 0> 0> 01 en
~ @ d
0> 01
ad
0>
<6
0>
...;
0>
N
en
d
N N M -.# III ID
Figure 3. The characterist ic diffractogram (X-ray) of phosphog ypsum
The main obstacle, though is the presence of radionuclides in phosphogypsum. The

quantitative presence of uranium has been established in samples of phosphogypsum and
326
the specific activity originates from 226Ra 18. The analysed samples of phosphogypsum
show that the distribution of uranium and 226Ra in relation to the initial phosphate ore is
such that the basic component of phosphogypsum is 226Ra. In no sample of
phosphogypsum has the radioactivity originated from 232Th been superior to 10 mBq/kg
(the legally permitted limit of radioactive contamination from 232Th is 2.6x 102 Bq/kg)18,
while the radioactivity originated from 40K was not superior to 25 Bq/kg (the legally
permitted limit of radioactive contamination from 40K is 4.8x103 Bq/kg)18.
Process for reducing radioactive contamination in waste product phosphogypsum will
be apparent from the following description of the work. 19,20 It has now been discovered
that the foregoing objects are accomplished for reducing the radioactive contamination in
waste product gypsum in a process which comprises:
a) admix ing waste product phosphogypsum containing radioactive contamination
with dilute sulphuric acid containing barium sulphate at an elevated temperature to form
an acid slurry, having a solid component comprised of a fine fraction and a coarse fraction;
b) separating fine fraction of solids from coarse fraction ;
c) whereby fine fraction predominates in barium sulphate and radioactive
contamination;
d) whereby coarse fraction predominates in phosphogypsum of reduced radioactive
contamination.
Example of this process constituted on the next way : an aqueous sulphuric acid
solution (eea. 2.97 dnr') having a concentration of28 % was admixed with a concentrated
sulphuric acid solution (30 em") containing disolved therein 3 grams of barium sulphate at
a temperature of 105C. Waste product phosphogypsum (750 grams containing a radium
concentration of cea. 26 pico Curies per gram)14,17 was agitated with the solution of
sulphuric acid and barium sulphate for a period of 12 minutes, while maintaining the
temperature of the resulting slurry in the range of 98-1 05C. At the end of this period , the
slurry was cooled at a temperature of 30-35C, and then filtered . The filter cake was
washed with 6.2 dnr' of water and the solids were dried at a temperature of 60C. The
weight of the dry solids was 695 grams . 50 grams of the dried solids was slurried with 1
dm 3 of water and then wet screened on a 200 mesh (75 micron) screen . The solid gypsum
material retained on the 200 mesh screen was collected and dried at 60C. Analysis of the
purified gypsum product showed that it had a radium concentration of 1.42 pico Curies
(cca. 95 % less than initial sample) .
CONCLUSIONS
The investigations presented in this work showed onto complexity of structure and
content of phosphogypsum, which is of the same chemical formula as natural gypsum,
CaS042H20, and also phosphogypsum is typical raw material due to its impurities.
Scanning electron micrographs showed different crystalline content of
phosphogypsum in comparison to natural gypsum.
X-ray diffraction analysis pointed out on the similar spectrum of phosphogypsum in
comparison to natural gypsum, that could be decisive concerning potential usage of
phosphogypsum as subst ituent of natural gypsum.
Thermogravimetric analysis indicated on significant presence of humidity in mass,
which pointed out that portion of CaS04 in phosphogypsum is in order of quant ity up to
84% (in natural gypsum up to 93%) .
The investigations of radioactivity indicated on presence of 226Ra and 40K in
phosphogypsum, that on the aspect of deposition (radon liberation) is not a problem , but if
phosphogypsum is used without any treatment, that could influence higher radioactivity in
environment.
327
This purified phosphogypsum - chemical gypsum material was suitable for use in
preparing plaster, gypsum, gypsum wallboards and other constructional materials . Also,
chemical gypsum can be useful as a soil meliorate in agriculture and in production of
amonium-sulphate, as a substitute for natural gypsum.
REFERENCES
1. F. Habashy, The recovery ofuranium from phosphate rock, progress and problems, 2nd Int.Conf. Phospho
Comp., Boston, USA, April 21-25, Proceedings, pp.629-660 (1980).
2. Uranium Phosphate Resoures and Technology and Economics of Uranium Recovery from Phosphate
Resources, United States and Free World, Edited by RH. Voto and D.N. Stevens, Report to US
Dept.ofEnergy, GJBX-110 (79), Earth Sci., Inc., Grand Junction, Colorado (1979).
3. F.J. Hurst and F.A Posez, Long Term Potential of Uranium Recovery from Phosphoric Acid and
Sulphuric/Phosphoric Acid Plant Operations, pp.184-194, N.Y. (1982).
4. MB.Rajkovic i KKarljikovic-Rajic, Prilog ispitivanju mogucnosti zamene prirodnog gipsa otpadnim
fosfogipsom iz industrije, Jug.konf. Teorija i tehnologija sinterovanja, TEOTES'93 , Beograd, 15-
17. septembar, Izvodi radova, P-24 (1993).
5. M.B.Rajkovic and K'Karljikovic-Rajic, The waste phosphogypsum from industry. Part II. The parallel
analysis of phosphogypsum and natural gypsum, Archiv ofPharmacy (Belgrade). 44(6): 671 (1994)
(in Serbian).
6. M.B.Raikovich, KKarlikovich-Raich, and I.Chirich, Comparative-studies of phospho-gypsum and rock
properties, Russ. J. Appl. Chern. 67(3): 454 (1994).
7. MB. Rajkovic , Fosfogips sa aspekta njegove primene, II Jug. konf. Teorija i tehnologija sinterovanja,
TEOTES'95, Cacak, 4-9.septembar, Izvodi radova: 42 (1995).
8. MAxMe.llOB n T.A Axaayues. r[Jocr/Jozunc, ll>AH, Tauncerrr, CCCP, (1980).
9. MB.Rajkovic and P.Ban, Phosphoric acid purification to small amounts of fluorine, Chemical Industry
(Belgrade) . 38(9): 266 (1984) (in Serbian).
10. M .B. Rajkovic, V. Hadzic and I. Molnar. The waste phosphogypsum from chemical industry - term,
application, perspective -, Institute ofField and Vegetable Crops, Novi Sad (1995) (in Serbian).
11. S.Wuwyler. Uranium Recoveryfrom Phosphates and Phosphoric Acid, Wuerentingen, Swiss, Federal
Ins. for Reactor Research. (1981).
12. H.Bodowska , Cement.Wapno.Gisp. 3: 72 (1975).
13. M.B. Rajkovic and K Karljikovic-Rajic, The waste phosphogypsum from industry. Part III. The
investigations of interest in contamination of life environment, Archiv of Pharmacy (Belgrade).
45(1-2): 31(1995) (in Serbian).
14. M.B.Rajkovic and K'Karljikovic-Rajic, Supplement to the study of the contribution of waste
phosphogypsum from industry to the contamination of life environment from the aspect of
radioactivity, II Symposium : Chemistry and Environment, V.Banja, 9-13. June, Book of Abstracts :
551 (1993) (in Serbian).
15. AKukoc, RStevanovic, D. Cokesa and M'Markovic, Distribution of uranium and 226Ra in production of
phosphoric acid by dihydrate wet process, II Symposium: Chemistry and Environment, V.Banja, 9-
13. June, Book of Abstracts : 583 (1993) (in Serbian).
16. V'Smiljanic i H. Dzaferi, Proces preciscavanja fosfogipsa u cilju dobijanja pecenog gipsa, NPK -
"Agrohemija", 11-12 : 29 (1979).
17. M.B. Rajkovic, R Stevanovic and G. Vladisavljevic, Phosphogypsum as the isolated category of
radioactive waste, International Symposium on Hazardous Waste and the Environment, V. Banja,
13-15. May, Proceeding : 405 (1996) (in Serbian).
18. Sluzbeni list SFRJ. Pravilnik 0 maksimalnim granicama radioaktivne kontaminacije covekove sredine i 0
vrsenju dekontaminacije, 8: 226 (1987).
19. Palmer et al. Process for reducing radioactive contamination in phosphogypsum, U.S. Patent, Ser. No.
330,550, filed Dec.14, (1981).
20. P.H. Lange, Jr. Process for reducing radioactive contamination in waste product gypsum, U.S. Patent,
Ser. No. 4,146,568, filed Mar.27, (1979).
328
MODEL OF DRAWING THIN GLASS SHEET FROM A RECTANGULAR
PREFORM AND ITS APPLICATIONS
l
Aleksandra D. Milutinovic-Nikolic', Nadezda M. Talijan and
Radoslav R. Aleksie
IInstitute of Chemistry, Technology and Metallurgy

11000 Belgrade , Yugoslavia
2Faculty of Technology and Metallurgy
11000 Belgrade, Yugoslavia
INTRODUCTION
Glass sheets of uniform thickness, thinner than lmm , are commonly used, for example,
in microelectronics, as small parts of electronic devices, and components in light
microscopes , etc . Drawing glass from rectangular preforms into thin sheets is one of the
manufacturing possibilities. In this paper the advantages of using a previously developed
mathematical model 1-3 in the investigation and improvement of the process of drawing thin
glass sheets from rectangular preforms are presented.
MODEL OVERVIEW
Several processes are simultaneously involved when a thin glass sheet is drawn from a
preform . The cold glass block is moved into the furnace at an appropriate velocity . The glass
block is heated in the furnace until it softens and becomes drawable and stretchable. The
drawn glass is cooled so that it hardens into a thin glass sheet.
To be able to obtain an appropriate model all these processes were considered as
engineering phenomena . The drawing process was regarded as a steady state one . After
justifiable simplifications' ", heat and momentum balance equations were obtained in the
form of ordinary differential equations and solved using the Runge Kutte method" .
In this model the glass properties were considered with utmost care, none of them was
considered as a constant. The glass density, viscosity and specific heat depend on the
chemical composition of the glass, as well as on the glass temperature. A Vogel-Fulcher-
Tammann 's (VFT)5 type of equation was used to express the temperature dependence of the
glass viscosity. The Gardons theory" was used to calculate the glass emissivity as functions
of both temperature and glass thickness.
Advanced Science and Technology of Sintering, edited by Stojanovic et al.

Yes
Calculating
Co, P20, AvBv, Tv
as functions of chemical
composition
Input the process

parameters :
Fdr' Vinit. ai, bj, tinit
Where: s R
u u
b n
P20 - density at room temperature r g
Co - specific heat at OC o e
Av. Bv and Tv - VFT coefficients
t
F dr - drawing force
i K
Vinit- starting velocity of glass
entering the furnace
n u
tinit _ starting temperature of glass
e
Subroutine for
a 1 - starting thickness of glass temperature profile
b l - starting width of glass e of furnace
Dependences:
c( t )-specific heat of temperature Formation of data

matrix suitable for
p(t) -densiry of temperature
graphical presentation
T](t) - viscosity of temperature
E(t,a) - emissivity oftemperture
and glass thickness
Printing or
graphical
presentation of
results
Figure 1. Program algorithm
330
The model allows three options for the type of glass used for the preform: window
glass, glass of known composition or glass with known characteristics. These characteristics
include : density at room temperature (P20); specific heat at OC (eo); and VFT coefficients.
All these values depend on the glass composition, and can either be measured or
obtained from the glass producer, and than directly inputted into computer code. For
common window glass , the values given in the literature' were used . For glasses of known
composition, the glass properties are calculated from the chemical composition using the
most appropriate equations given in the literatures.
The computer program includes three different parts. The first part involves setting the
initial and boundary conditions and the glass properties, the second part calculating the
temperature, viscosity and dimensional changes during changes in the z-direction and the
third part presenting the calculated data graphicall y. The algorithm used in this model is
given in Fig. 1.
RESULTS OF MATHEMATICAL SIMULATION
The model predicts the changes in the glass thickness with axial distance from the
entrance into the furnace . The changes in the temperature and viscosity of the glass during
drawing, together with the axial temperature profile of the furnace are presented graphically.
In this way it is possible to compare different assumed experimental conditions, and also to
make a comparison between the simulat ion results and actual experimental results.
Using the established model, the following variables which influence the shape of the
glass sheet were investigated:
the entry velocity of the preform into the furnace;
the axial temperature profile of the furnace;
the temperature of the glass before entering the furnace (how much the glass preform
was preheated);
the length of the furnace;
the drawing velocity and its direction (upwards and downwards);
the type of glass (window glass or glass of known composition);
the dimensions of the glass preform.
The model was used to provide useful data for the construction of the furnace. The use
of the model enabled the optimization of the process with a reduced number of experiments.
All simulated drawing conditions were within real, potential experimental conditions.
The additional limitation was that the final thickness of the drawn glass must be in the
interval O.I-1.0mm. In this thickness interval the drawn glass sheet is as thin as it should be
for its future applications .
Only a part of the performed investigations is presented in this paper. The influence of
entering velocity, dimensions of the glass preform and type of glass were presented
previously' r' . Here, the influence of the temperature profile of the furnace is given as an
illustration of the different possibilities of using the model. This part of the investigation was
focused on the influence of the length of the heating zone of the furnace on the drawing
process.
It is very important to have an adequate furnace to achieve better productivity.
Obviously it is much easier to calculate the characteristics of a new furnace than to build
new ones with the sole purpose of determining the most suitable one .
Figures 2 and 3 illustrate the influence of the axial temperature profile of the furnace
and the length of the heating zone on the drawing process.
To enable the comparison of the data the majorit y of process variables, except for
temperature profile of the furnace, were kept constant. The simulation was performed for a
common window glass block having dimensions Jmm x 150mm x IOOOmm. The temperature
331
'"
N . . . . . ........ . . . . .... 1
'" 900 - 10 "
18
800 10
, 17
I; 10
-, 16
~
700 til 10
~ <'<l 15
,,
'I 0- 10
600 "
, ,. -0 14
U , 10
0 , 500 13
" , i- 10
Q) ' r;;
... -, 12
,": , 0
400 I (.) 10
til
... ... 1011
~ I
, ;; 10
8' 300 10
---- -
Q)
-- - 9
E-< 200 10 - - - - Temperature of glass
8
,, ,
I
. 10
100 7 - - - Temperture in furnace
I
. 10
6 . . . Viscosity of glass
0 .... 10
+
0 5 10 15 20 25 30 35 40 45
0,20
Q) Distance from the furnace entranc e, ern
_ 0,15
0. E
(.)
:::' 0,10
-~
::: 0
8 15 0,05
Q) .-
..c:: ...
eoOb ~ 0,00
<t:: Q) -0,05
Q) .;;
Drawing direction
(.) '+-<
0 -0,10
ti
15 -0,15
\. ..0,20 I ' I 'i' i 'i I i I iii ' I

o 5 10 15 20 25 30 35 40 45
Distance from the furnace entrace, em
Figure 2. The changes in dimensions, temperature and viscosity within a glass block in the drawing direction for the furnace
with a short heating zone.
900 . 19
10
18
800 , 10
17
- , ,
, . , 10
, I 16
700 , , gj 10
I
, ,
oU , , Cl. 15
I , 10
v' 600 , t - , , "0 14
, , - -,:_- ~ 10
13
500 " ~ - - -
00 10
' 12
~... 0(,)
8. 400 :'
J , , en
10
I , 1011
,. , ;; 10
~ 300 .. 10
.: , 9
200 , 10 - - - - Temperature of glass
I ,
'. 8
10
1 - - Temperture in furnace
100 " 10
.. 6
0 . . .... .... . ... . ......... 10 Viscosity of glass
0 5 10 15 20 25 30 35 40 45
Distan ce from the furnace entrance, cm
0,20
~ 0,15 -+---------..
]' 8, 0,10
g J 0,05
- --- ------.--.--.--
.s '~ 0,00 l -------- - - - --==---.--------------------- .--
- --
.--
-------.- .--
s ~ Drawing dir ecti on
.g : -0,05
v
-0,10
~
.s'0
en
-0,15
is
-0,20 I I I i i i I i
o 5 10 15 20 25 30 35 40 45
Distan ce from th e furnace entrace, em
Figure 3. The changes in dimensions, temperature and viscosity within a glass block in the drawing direction for a furnace
v.>
v.> with long heating zone.
v.>
of the glass preform entering the furnace was room temperature (25C). Both furnaces were
200mm long but had different axial temperature profiles in the z-direction as presented in
Figures 2 and 3. The maximal temperature in each furnace was 800e. The glass ribbon was
drawn with a drawing ratio of 100, pulling the glass downwards. The drawing ratio (E) is
the ratio between the drawing velocity (Vdr) and the velocity oflowering the preform into the
furnace (Vin it) .
The changes in dimensions, temperature and viscosity within the glass block in the
drawing direction on heating the glass preform in the furnace with a shorter heating zone are
shown in Fig. 2. In the furnace with same temperature profile as this one, the experimental
investigations were performed . The glass preform was drawn with a drawing force of
5.165N . The drawing velocity was Vdr = 6.066 x 1O-3m/s, while the velocity of lowering the
5
preform into the furnace was Vinit= 6.066 x lO- m/s.
If the same process parameters were used for the second temperature profile (longer
heating zone) the glass would shrink ending up as a glass fiber instead of a glass ribbon. To
achieve the desired glass ribbon, one of the process parameters had to be altered . The
possibilities were : to decrease the maximum temperature in the furnace, to reduce the
drawing force while keeping the drawing velocity unchanged ; to increase the drawing ratio
by increasing only the drawing velocity or to increase simultaneously Vdr and Vinit and keep
the drawing ratio unchanged .
At constant drawing velocity, the drawing force can be reduced only up to certain point
after which the gravitational force is dominant and drawing process is hard to controll . On
increasing the drawing ratio by increasing the drawing velocity, the drawn glass ribbon
becomes a lot thinner than O.lmm and its dimensions are outside defined width and thickness
interval.
According to previous results':", either the lowering the drawing temperature or the
increasing the drawing velocity lead to more uniform glass sheets . The effect of surface
tension on the edges of the drawn thin glass, which makes the edges more round and thick,
is smaller when the drawing process is performed at lower temperatures.
It has been selected to present the results of the numerical simulation for the long
heating zone where all process parameters except for Vdr and Vinit have the same values as for
the experiment with the short heating zone (Fig. 2.).
In the case of the temperature profile presented in Fig. 3, the lowering velocity was
increased to Vinit= 2 x 10-4m/s, increasing at the same time Vdr up to 2 x 1O-2m/s . This change
in the temperature profile, or more precisely the selection of a different type of furnace
construction, increases the productivity 3.3 times.
COMPARISON OF RESULTS OF SIMULATION WITH EXPERIMENTAL
A laboratory device for drawing thin glass sheets from rectangular preforms enabled the
verification of the mathematical model. The first step was to establish the temperature profile
of the furnace. The drawing process was fully controlled". An appropriate mechanism
allowed the glass block to be lowered into the furnace with a controlled velocity. The
temperatures in the furnace at different positions and the drawing velocities were controlled .
All the controlled process parameters were measured and the values collected using a data
acquisition system HP 3497 A connected to a HP 9386 computer.
Direct measurement of the dimensions of the glass block inside the furnace is very
difficult. To enable the measurement of the changes in the dimensions of the glass block
during drawing, the process was "frozen". Abrupt lowering of the temperature in the furnace
resulted in the glass cooling rapidly and so be "frozen" in the shape it had inside the furnace.
The so-called "frozen cone" was used to measure the changes in the dimensions of the glass
block during the drawing process .
334
R - - - - - Results or numerical simulation
- 0 - Experimental results
6
4
,,
E
u :2
.s
"0 0
.~
Vl -2 Drawing direction
Vl
'"
G -4 /
/
vd,=6.066 x 1O-3m/s
-6
Tmax=800C
-8
0 2 4 6 8 10 12 14 16 18
Distance from the pointwhere stretching begins, cm
Figure 4. Comparison oftheexperimental data with theresults ofthe numerical simulation
The comparisons of the experimentally obtained data (from the "frozen cone", and the
data acquisition system) with the results of the numerical simulation given in Fig. 2. are
shown in Fig.a. The change in the width of the glass ribbon in the z-direction from the point
where shrinkage of the glass begins is presented for the same experimental conditions.
There are certain deviations between the two data, but the agreement is good enough
to plan experiments and so reduce the number of required experiments. Future experiments
should be performed in the furnace with the longer heating zone because, according to the
results of the numerical simulation, better productivity is to be expected .
CONCLUSION
Using the established model, it is possible to investigate the influence of various

variables, i.e. the entry velocity of the preform, the temperature of the glass before entering
the furnace (how much the glass preform was preheated), the drawing velocity and its
direction (upwards and downwards) , the type of glass (window glass or glass of known
composition), the dimensions of the glass preform, on the shape of the glass sheet
The influence of the temperature profile of the furnace was presented as an illustration
of the different possibilities of using the model. It has been shown that by using the furnace
with the longer heating zone, under the constant drawing conditions (chemical composition
and dimensions of the glass block, drawing ratio, temperature and force), the drawing
velocity can be increased 3.3 times and in this way at the same time the productivity.
The validity of the numerical simulation was confirmed by experiments. Comparison of
the results of the numerical simulation, obtained by this model, and the experimental data
established that good agreement between them exists.
REFERENCES
1. A. Milutinovic-Nikolic, MSc Thesis, TMF, Belgrade (1992) (inSerbian).

2. A. Milutinovic-Nikolic, R. Jancic and R. Aleksic, Modeling ofdrawingthin glass sheet from a preform, 1.
Serb. Chern. Soc. 63(3):21 9 (1998).
3. A. Milutinovic-Nikolic R. Jancic and RAleksic. Mathematical modeling and simulation of drawing thin
glass sheet from a rectangular preform, Glass. Technol . 39(5) (1998) (in press).
4. V. Simonovic, Numericke Metode, Masinski fakultet, Beograd (1983).
5. W.Vogel, Kemija Stakla, SKTH & Kemija u industriji, Zagreb, (1985).
6. R. A. Gardon, Review of radiantheat transfer in glass. 1. Amer. Ceram. Soc. 44(7): 305 (1961).
335
7. F.G.Salinov, Proizvodstvo Listovoga Stekla, Stroiizdat, Moskva (1976).
8. M.B. Volf, Mathematical Approach to Glass - Glass Science and Technology 9, Elsevier, Amsterdam -
Oxford-New York -Tokyo (1988).
9. A. Milutmovic-Nikolic and R Aleksic, Ispitivanje uticaja brzine i temperature izvlacenja na ravnomemost
staklene trake dobijene vertikalnim izvlacenjem iz predoblika, Zbornik. XXXIV Savel. Srpskog Hem.
Drus. 32 (1992).
10.S. Milinkovic, R. Aleksic, D. Mitrakovic and A. Sadibasic, Characterisation of the optical fibre drawing
process, Glass Techno/. 34 (4): 148 (1993).
336
CRYSTALLISATION KINETICS OF LAYERED SILICATES IN GLASS
Mihajlo Tosic', Radovan Dimitrijevic Z, Tatjana Sreckovic \ Jelena Nikolic 1

and Mirjana Duricic'
'Institute for Technology of Nuclear and Other Mineral Raw Materials,

Belgrade
2Faculty of Mining and Geology, Belgrade
3Joint Laboratory of SASA, Belgrade
ABSTRACT
In this paper. the results obtained by investigation of crystallisation kinetics in

aluminosilicate glass containing 1.63-% wt of fluorine are presented. The following
parameters of this process are determined: nucleation temperature. Tn=660C.
crystallisation temperature. Tc=1000C. activation energy. Ea=3379 kJlmol and Avrami
parameter. n=2.51. The values of the kinetic parameters indicate that homogenous
nucleation and volume crystallisation proceed in this glass. The formed crystal phases are
identified as Ksphlogopite, diopside and clinoenstatite.
INTRODUCTION
Mechanical properties are often the main factor , which determines in pract ical
application of the glass-ceramic materials. In these materials, they would depend very much
on the composition of the crystal phases and their microstructure 1. It was found out that
mechanical properties of the glass-ceramic materials are very much improved with
format ion of the layered crystal structure 2. If the material is exposed to stress, the presence
of layered crystal phases enables development of microcracks along the (001) plane of the
sheet crystal, which are further transferred onto the neighbouring crystal 3. In this way,
deflection of cracks occurs in stressed materials, contributing to their high fracture
toughness, high bending strength and enables their safe processing without destruction.
The aim of this work was to investigate kinetics of segregation of phyllosilicate phase
in aluminosilicate glass with low content of fluorine. The investigations were performed
under both isothermal and non isothermal crystallisation conditions.
EXPERIMENTAL
To obtain glass , the following starting materials were used: quartz flour, AIP3' CaO ,
MgO,CaF 2, K 2C0 3 (analytical grade). Preparation of the melting mixture was performed in
Advanced Science and Technology ofSintering , ed ited by Stoja novic ct al.

Kluwer Academ ic/Plenum Publishers. New York, 1999 337
the Reich mill. Melting of glass was performed in electric furnace, in the platinum crucible,
at T= 1500C, for t=60 min.
The transformation temperature, T, and softening temperature (To) were determined on
the basis of the dilatation curve, recorded in the temperature range of 20-850C, at the
heating rate v=lOoC/min, using the sample 03x38 mm.
Investigations performed under nonisothennal conditions were carried out by DTA
method, using Netzsch STA 409 EP device. Experiments were performed with powdered
samples of the granulation 500-630 urn, at the heating rates of: 2.5; 4; 5; 7.5 and lOoC/min .
Experiments performed under isothermal crystallisation conditions were carried out in
two steps: heating at the temperature T=660C, for t=1200 min., followed by heating at
T=IOOOC, for t=180 min. Qualitative determinat ion of the crystal phase was performed by
the x-ray powder diffraction method (XRPD) , using Philips automated diffractometer PW
1710.
The results of the chemical analysis show the following chemical composition of
obtained glass: 9.47 K207.46 CaO3.35 CaF2"lO.27 MgO18.10 A1P350.70 Si0 2 (%Wt).
Determination of the nucleation curve was based on DTA measurements and the
following relation 4:
In(I) = Eo (_1 _ _ 1_) + const. (1)

R Tp TOp
where I is nucleation rate, T, is the peak temperature of the sample heated isothermally
during DTA, T", is the peak temperature of the sample quenched in air after melting, E. is
activation energy of the crystal growth and R is the gas constant. E.value was calculated
according to equation (2). In Fig.l , nucleation curve for this glass is shown. As can be seen
from this figure, its maximum is at Tn=660C.Comparing certain T g and T. values , it was
found out that these temperatures are in relation: T.~Tg. Since this condition is satisfied in
this case, nucleation proceeding in this glass is homogenous.
0.45 Tn = 660 0(
0.44
0.43
0.42
0.41
c
0.40
0.39
0 .3e
o
0 .30 T \
') 'r----,.....--,--....--..--~
eGO 610 620 650 660 6 70 eso 690 700
T [O( 1
Figure 1. Logarithm of the nucleation rate, In (I), as a function of temperature
338
Analysis of the crystallisation kinetics was based on equation (2) 5:
vn -mE
In(-2-) = _ _0 + const (2)
T p RTp
where n is Avrami parameter, m is dimensionality of the growing crystal and Tpis the peak
temperature . In Fig.2, DTA curves recorded at different heating rates, with the samples of
the granulation 500-630 urn, are shown. As can be seen from this figure, crystallisation
peak is present at each curve, shifting in the temperature range T=944 .8-994.8C with the
temperature increase. In equation (2), the value of parameter n is also unknown. Its
calculation, based on the results from Fig.2, was performed by a method Ozawa 6 and the
calculated value is n=2.51. This value indicates that in investigated a glass volume
crystallisation process is present The value of activation energy of the crystal growth
determined according to equation (2) (n=rn), by square method is E.=3379 kJ/mol.
OTA (}lvi
'1:2 ." C/min
...
o
V:4C/m in
"oJ. r, C/min
~l
V :10 o(jmin
200 ~oo 600 800 1000

- - - - - - - T('C) - - - -
Figure 2. DTA traces obtained using particles size 500-630 urn of glass at a various hearing rates
339
Crystallisation under isothermal condition was performed with compacted samples in
two steps, under isothermal conditions. Identification of formed crystal phases showed that
K-phlogopite as primary whereas diopside and clinoenstatite as secondary phases where
obtained (Fig.3).
35 . , - -- - - - - -- - - -- - - - - - - - - - - - - - - - ----,
30
25
20
~
c
15
:1
o
J
10
0+----,.----,----..------,------.-----.-------1
o 20 40 60
-- 2 8 (degree]
Figure 3. X-ray powder diffraction pattern for sample heat-treated in two steps: at 660C for t=1200 min and
at 1000Cfor t=180 min
CONCLUSION
Results obtained by investigation of crystallisation kinetics in alumosilicate glass

containing 1.63-% wt of fluorine showed that layered phase phlogopite was obtained during
this process . The parameters of this process were as follows: nucleation temperature
Tn=660C, crystallisation temperature Tc=IOOOC, activation energy E.=3379 kllmol and
Avrami parameter n=2.51. The values of the kinetics parameters indicate that homogenous
nucleation and volume crystallisation proceed in the glass. The crystal phases formed
during this process was identified as K-phlogopite, diopside and clinoenstatite.
REFERENCES
l.P.W. Mc Millan : Glass-ceramics, 20d ed., Non-MetallicSolids: A Series of MonographsNol.,Edited by
J.P. Roberts and P.Popper,AcademicPress,London, 1979
2.D.S. Baik, S.N. Kwang, J.S.S. Chun, J.Am.Ceram. Soc. 76:1217 (1995)
3.W. Vogel, W. Holand, Angew. Chem. Int. Ed. Engl. 26:527 (1987)
4.A. Marotta, S. Saiello, F. Branda,A. Burl, Thermochim.Acta 46:123 (1981)
5.x.J. Xu , C.S. Ray, D.E. Day, J.Am.Ceram. Soc. 74:909 (1991)
6. T. Ozawa, Polymer 12:150 (1971)
340
THE EFFECf OF ATMOSPHERE ON HDS CATALYST SINTERING
R.Marinkovic-NeduCin I , LKiurski', E .Kis!, R.MiCic3
'Faculty of Technology, But. Cara Lazara 1,21000 Novi Sad,

Yugoslavia
ZFaculty of Sciences, Institute of Physics, Trg D. Obradovica 4, Novi
Sad,
3NIS Refinery, Put Sajka skog odreda bb , Novi Sad
Abstract: Intensive sintering processes and disturbances of microstructure of NiO-

MoO/y-Al20) and CoO-MoO/y-Al20J hydrodesuliurizetion catalyst systems have
been established as one of the main causes of catalyst deactivation. Segregation of
MoO) from the complex active structure during processing, with consecutive melting
in regeneration cycle, has been proposed as the main reason ofintensive sintering of
the catalyst. That leads to essential change in porous structure depending on
regeneration atmosphere in order:nitrogen>air>steam.
INTRODUCfION
The sintering process of catalyst support and/or active phase might be one of the
causes of catalyst deactivation. Prolonged processing brings about gradual changes of
phase composition, porous structure and distribution of act ive metals in cataly st
grain, with consecutive causing irrev ersible catalysts act ivity decline, known as aging.
The hydrodesulfurization process (HDS), as one of the basic catalytic processes
in petroleum processing, is directed to the removal of sulfur and nitrogen compounds
from crude oil fractions. Classical NiO(CoO)-MoO/y-Alz0 3 HDS catalysts belong to
the group of highly resistant catalysts, which may sustain several activation and
regeneration (i.e. sulfiding/re-oxidation) cycles during its lifetime, dep ending on th e
type of feed being processed. New environmental regulations, concerned with low
sulfur fuels, impose advanced HDS processes with improved catalysts. Increased
scope of heavier fraction processing in more rigorous processing conditions, in
addition to previous reasons, bring about the new interest for HDS catalyst aging
investigations' .
The commercial industrial HDS catalysts of NiO(CoO)-MoOh-Al z0 3 type are
characterized by complex structure of molybdenum active phase with Ni/Co as the
promoter, in interaction with high surface of y-Al z0 3 as the support. Possible
mechanisms of catalyst restructuring, lead ing to more or less pronounced activity
Advanced Science and Technology ofSintering , edited by Stojanov ic et aJ.

Kluwer Academic/Plenu m Publishers, New York , 1999 34 1
declines, include phase transformations, solid state reactions between the active
phase and support, segregation of the phases of the catalyst and sintering Z,3 . Better
understanding of these processes during deactivation and regeneration represents the
prerequisite for the design of highly resistant catalyst. Thermal stability of catalyst is
one of the main characteristics for its long-term usage.
In this work the influence of regeneration regime (temperature, atmosphere) on
NiO(CoO)-MoO/y-Al z0 3 catalyst deactivation was investigated . The estimation of
relative rate of HDS catalysts sintering was based on textural changes in conditions of
accelerated aging in various atmospheres (nitrogen, air, steam) at higher
temperatures and extend treatment duration.
EXPERIMENTAL
Two types of standard commercial industrial catalysts were chosen:

NiO-MoO/y-Alz0 3 = NiMo
CoO-MoO/y-Alz0 3 = CoMo
Three different atmospheres: air, steam and nitrogen were applied in simulation
of accelerated catalyst aging in laboratory conditions. The choice of atmospheres was
based on the real conditions of the regeneration processes of HDS catalysts.
Comparatively high temperature (500-800C) was applied taking into account the
exothermal character of the regeneration reaction, and possible appearance of the
hot spots in catalysts bed.
The thermal treatment were performed in a flow system, with sample (cca. 3 g)
located in the quartz U-tube (~=15 mm) in the vertical muffle furnace with controlled
temperature ( lOC).
The structure of the catalyst was characterized by SEM (lEOL, ISM 35), and for
textural examination was applied low-temperature adsorption (Micromeritics, ASAP
2000).
In laboratory conditions of accelerating aging the structural changes of HDS

catalysts in temperature range of 500-800 -c 4 were followed by significant textural
changes, which pointed out sintering as important mechanism in deactivation process
(Table 1 and 2).
Table 1. Surface area of catalysts thermally treated in air atmosphere
Catalyst Treatment
sample duration Surface area (m2/g)
(h) 500C
NiMo 1 260.3 248.3 179.4 76.8
255.3' 9 228.3 180.9 115.1 47.4
CoMo 197.2 194.4 179.8 77.6

196.3' 9 195.6 192.2 119.0 57.9
, surface area of the fresh saample
The intensity of surface area decline depend both on treatment atmosphere and
temperature regime, the 800C being the break-point for rapid sintering onset in all
the applied atmospheres (Table 2).
342
These changes are accompanied with pore volume decrease and significance
average pore diameter changes (Table 3).
Table 2. Relative surface area decline depending on tretment atmosphere
Surface area decline (%)

Treatment NiMo CoMo
atmosphere 700DC 800DC 700DC 800DC
nitrogen 17.4 73.3 11.0 63.1
air 54.9 81.4 39.4 70.5
steam 55.8 85.9 41.9 76.5
Table 3. Pore volume and average pore diameter of catalysts thermally treated in air
atmosphere
Catalyst Treatment
sample duration Pore volume (cm 3/g)
(h) 500C 600C 700 DC 800DC
NiMo 1 0.487 0.483 0.472 0.450
0.496' 9 0.475 0.475 0.483 0.378
CoMo 1 0.467 0.463 0.477 0.430
0.468' 9 0.483 0.479 0.462 0.397
Average diameter (nm)
500C 600C 700C 800C
NiMo 1 7.48 7.79 10.52 24.43
7.77' 9 8.33 10.03 16.79 31.87
CoMo 1 9.48 9.64 10.61 22.17
9.53' 9 9.34 9.82 15.52 27.41
, fresh saample values
The rates of textural changes of both catalysts types are somewhat lower in inert
(nitrogen) in comparison to oxidation (air, steam) atmospheres, particularly at 700 DC
(Table 2). The changes in porous structure (Fig. 1) show the similar trend concerning
the atmosphere type, with more pronounced shift of pore size distribution maximum
towards macropore range in both air and steam atmosphere. Comparing two
oxidation atmospheres, it is obvious that steam atmosphere is the most critical
concerning rate of undesirable changes of catalyst texture (Table 2, Fig. 1). Complete
loss of mesopores in catalyst influence not only the active area of the catalyst, but
also diffuse characteristics of catalyst grain and therefore the transport phenomena in
reactor catalyst bed.
The results confirm that the regeneration process of HDS catalyst is a critical
phase concerning possible undesirable textural changes. Parallel structural changes in
active phase, with segregation of molybdenum phase accompanied with simultaneous
decrease of promoter concentration (Co/Ni) in surfaces layer due to their
accelerating migration in support lattice, contribute to catalyst activity decline 5.
Besides the temperature regime, the choice of regeneration atmosphere is very
important for preventing catalyst aging in this critical phase. Steam is recommended
in regeneration processes because of high heat capacity value, but there is possible
damage effect on both catalyst structure and mechanical characteristics 6. The
reaction between molybdenum oxide phase and steam, accompanied with forming of
MoOiOH)2 volatile compound, with consecutive loss of active component 7. Our
results confirm that textural changes might be even more important, being
pronounced at lower temperatures than critical for considerable structural
disturbance.
343
bO 1.8
---
"E _
CoMo
I h, air
.'I
I
I
u
......- 1.4 _ 9 h, N, I
w 3 h, air
I
I
~ I
:3 1.0 __ 6 h, air I
I
o I
I
> I
w 0.6 t
I
cr:: I
'\1',,
o
0... ,
10 100 10 100
PORE DIAMETER (nm) PORE DIAMETER (nm)
0.8
.
,--, :', r - - - - - ,
!:J)
i-- ,'. NiMo CoMo
E
o
, "_ FRESH ~ FRESH
0.6 ~_ N1TROGH _ NITROGEN
W _ AIR r-- AIR
~ ___ STEAM ___ STEAM
~ 0.4
0
>
u..: 0.2
cr::
0c,
0.0
I 10 10 100
PORE DIAMETER (nm) PORE DIAMETER (nm)
Figure 1. Pore size distribution depe nding on treatment atmosphere (800 C)
CoMo N iM 0
300
300
tlII
~ Me 200
ME 200
VJ
.;:
100
~:---: Q.
VJ 100
0
0 0 5 10
0 5 10
Duration, h
Du r ation, h
Figure 2. Surface area depending on treatm ent dur ation
344
The dynamics of isothermal surface area changes of two catalyst types (Fig. 2)
give more insight in both, the effect of temperature and sintering mechanisms. As
mentioned earlier, the critical temperature for rapid sintering is 800 DC, with obvious
change of sintering kinetics in early period of thermal treatment. The investigations
of catalyst microstructure confirmed expressed sintering at 800 DC in air and steam
atmosphere (Fig. 3). That type of behavior might be explained by intermediary
presence of liquid phase in the system. Based on our previous investigations 2,4, the
liquid phase could be attributed to MoO) (melting point 795 DC) segregated from the
disturbed active structure of the catalyst in oxidizing atmosphere.
Based on surface area changes as a function of isothermal treatment duration in
air (Fig. 2), relative thermal stability of two catalysts types could be estimated, with
some preference of Co-based catalyst in the temperature region beneath the critical.
The lower temperature of spinel-type structure formation in Co-promoted catalysts,
as shown in our previous investigations 8. 9, with consecutive stabilizing effect on
catalyst structure could explain such differences.
FRESH (x 10000) NITROGEN (x 10000)
AIR (x 10000) STEAM (x 10000)
Figure 3. SEM micrographs of NiMo catalyst thermally (800C) treated in various atmospheres
345
CONCLUSION
Besides active phase restructuring, considerable textural changes and sintering

of catalyst support play important role in hydrodesulfurization CoO(NiO)-
MoO/y-Al z0 3 catalyst aging. The complex processes taking place in catalyst grain are
interfering, depending both on temperature regime and surrounding atmosphere.
The temperature of intensive sintering onset do not only coincides with the melting
point of Mo03, segregated from active phase, but also define the governing
mechanism of sintering process. Possible overheating in "hot spots", created in
exothermal HDS reactions due to disturbed hydrodynamics in catalyst bed,
contribute to irreversible loss of catalyst activity. Oxidizing atmosphere, applied in
regeneration of the catalyst, is most critical concerning catalyst sintering. The choice
of regeneration atmosphere is of importance, the catalyst being most sensitive to
temperature fluctuations in steam. The role of promoter is to stabilize the catalyst
structure, with some preference of Co concerning thermal stability.
REFERENCES
1. M.Absi-Halabi, A Stanislaus, H.Qabazard, Trends in catalysis research to meet

future refining needs, Hydrocarbon Processing, February: 45(1997)
2. R. Marinkovic-Neducin, P.Putanov, The role of metal-support interactions in
sintering and thermal deactivation of HDS/HDN catalysts, IndJ.Eng.&Mat.Sci.
2:831995)
3. J.M.Ammus, G.AAndroutsopoulos, AH.Tsetsekon, An investigation of the
deactivation phenomena associated with the use of commercial HDS catalysts,
IndEng.Chem.Res.26:1312(1987)
4. J.S Kiurski, Mechanism of Hydrodesulphuriation Catalyst Aging, Ph.D. Thesis,
University of Novi Sad, Faculty of Technology, Novi Sad, Yugoslavia (1997)
5. R.Marinkovic-NeduCin,.E.Kis, J.Kiurski, R.MiCic, Deactivation studies on
industrial NiO(CoO)-MoO/y-AlzO) hydrotreating catalyst, Petroleum and Coal
38/4:30(1996)
6. AArtega, J.L.G.Fierro, P.grange, B.Delmon, CoMo HDS catalysts: Simulated
deactivation and regeneration.Role of various regeneration parameters, Catalyst
Deactivation., Elsevier, 59 (1987)
7. E.Furimsky, F.E.Massoth, Regeneration of hydroprocessing catalysts,
CatalToday17: 537 (1993)
8. D.Z.Obadovic, J.Kiurski, R'Marinkovic-Neducin, Electronic states of nickel(II) in
spinel-type structures, Polyhedron, 15/20: 3631 (1996) .
9. J.Kiurski, D. Z.Obadovic, R.Marinkovic-Neducin, E.Kis, Dteremination od spinel
structure formation in conditions of Co-based catalyst aging, 1sl Int. ConI. on the
Chem.Soc. ofthe South-East European Countries, Halkidiki, Greece, P0316
(1998)
346
Part V. ELECTRONIC CERAMICS
THE STABILITY OF POROUS ALUMINA CATALYST SUPPORT
AGAINST SINTERING
Tatjana B. Novakovic, Zorica M. Vukovic, and Nadezda N. Jovanovic
IChTM - Center for Catalysis and Chemical Engineering,

Njegoseva 12, 11000 Belgrade, Yugoslavia
INTRODUCTION
The high surface area alumina with well developed open porosity of nano-scale
pore diameter, which is used as a catalyst, catalyst support or a membrane top -layer,
has in recent years been obtained by a sol-gel process, using aluminium alcoxide as a
precursor'".
The application of high surface area alumina as a support for a catalyst to be
used in high temperature oxidation requires thermal stability of its structure at
temperatures up to 9OOe. During prolonged exposure at high temperatures the
pore growth and surface area loss in alumina support occurs, causing the
deactivation of the catalyst. Therefore, one of the most serious problems is to
improve the stability of alumina support against sintering. It was previously reported
that addition of polyvinyl alcohol to the boehmite sol reduces the thermal stability
of alumina, while addition of 0.03 mol La' t/mol Ae+ to the boehmite sol stabilizes
the structure of alumina obtained by the sol-gel method'. The results in our previous
paper have shown that the addition of polyethylene glycol (PEG 5600) or
polyethylene glycol + 0.03 mol La3 +/ mol Al" to the boehmite sol improves the
thermal stability of porous alumina produced by the sol-gel method'.
This paper presents the results of studies on the influence of addition of
polyethylene glycol (PEG) or polyvinyl alcohol (PVA) combined with La3 +(0-0.045
mol La't/mol AI3 +) to the boehmite solon both the properties and the sintering of
porous high surface area alumina obtained by sol-gel process.
EXPERIMENTAL
The alumina samples were prepared from 0.5 Mboehmite sol, which is obtained
from aluminium isopropoxide according to the procedure given by Yoldas'. AO-
alumina sample has been prepared from a pure boehmite sol. An exact amount of
Adv anced Science and Technology ofSintering, edited by Stojano vic et al.
lanthanum nitrate solution combined with polyethylene glycol (PEG, mol wt. 5600,
mol radius 2.3 nm) or polyvinyl alcohol (PVA, mol wt. 72000) was added to the
boehmite sol with vigorous stirring in order to obtain a homogeneous doped
boehmite sol. The doped boehmite sols were then gelled at 40C. The thermal
treatment of doped alumogel samples thus obtained was carried out in an electric
furnace with a programmed heating regime (120CIh). The gels were dried at 120C
for 24h, calcined at 5000C for 5h and at the final temperature ranging from 500 to
1200C, for 5 h. The kinetics of the sintering was studied by determining the specific
surface area and phase composition of alumina samples after calcination in air at
1000Cfor different periods of time.
The specific surface area, SBET' the pore volume, Vp , and the pore size
distribution were evaluated for each alumina sample from the nitrogen adsorption-
desorption isotherms determined at -196C in a high vacuum volumetric apparatus'.
The samples were previously outgassed at 250C and a pressure of 1 mPa, for 4 h.
The pore size distributions in the macropore region were determined by the method
of mercury porosimetry, using a commercial porosimeter Carlo Erba, Model 2000.
The phase composition was detemined by the X-ray diffraction analysis (XRD)
performed on a Philips PW 1710 diffractometer, using CuK a radiation.
The effects of the adding of pure polyethylen glycol or pure polyvinyl alcohol,
and combined PEG+Lah or PVA+La3+ to the boehmite solon the some properties
of alumina samples prepared by sol gel method and calcined at 500C are shown in
Table 1.
Table 1. Properties of alumina samples prepared by sol-gel method and

calcined at 500C, for 5 h
Sample Organic Laz03 v; SBET' clmax,

designation additives mol % cm3/g m2/g nm
AO 0 0 0.360 290 3.0
APEGO PEG 0 0.445 295 3.2
APEGLal PEG 1.5 0.440 290 3.3
APEGLa2 PEG 2.9 0.435 285 3.3
APEGLa3 PEG 4.4 0.425 280 3.3
APVAO PYA 0 0.425 280 3.3
APVALal PYA 1.5 0.420 278 3.3
APVALa2 PYA 2.9 0.410 270 3.3
APVALa3 PYA 4.4 0.395 260 3.3
The prepared alumina samples have a high specific surface area in range from
260 to 295 m2/g. The values for SBET indicate that heating of PEG-doped with respect
to PYA-doped alumogel produces alumina samples with higher surface area . A
gradual decrease in the value of the specific surface area of alumina calcined at
500C with rising Laz03 content was observed. The smaller surface area of La 203-
doped alumina due to the presence of Laz03' which has a small surface area (about
25 m2/g). As shown data in Table 1, the addition of PEG, PEG+La3+, PYA or
PVA+La3+ to the boehmite sol results in a higher cumulative pore volume in doped
alumina compared to the non-doped one. This is effected by the specific action of
348
PEG- or PYA-molecules as alumina gel network modifiers, which after calcination
at 500C are burn out, leaving some micro-cavities in the alumina.
In the X-ray diffractograms of all alumina samples calcined at 500C were
evidenced a very diffuse reflection [111] at 28 = 19.3, the splitting of the strongest
reflection [400] and[440], as well as the intensity ratio of reflections [311] and [222],
approximately equal to 1.7, point to the presence of y-AlzOt The shape of the
diffraction maximum in the 25<28<40 range indicates that this phase has a slightly
ordered structure. The X-ray diffractograms of La.Oj-doped alumina samples did
not show any lantanum compounds, indicating a very well dispersion of La't-ions on
the surface of alumina crystallites.
The diagrams depicted in Figure 1 present the effect of the amount of La 3+
added to the boehmite solon the surface area and the pore volume of alumina
samples calcined at different temperatures.
300~-------------, 0 .50 r - - - - - - - - - - - - - - - ,
~_-o-_~a) b)
250 J--e----e- _
o 500C 0.40
I> 1000C
200 llOOC
* 1200C 0.30
till till
<, 150 <,
S "ec 0.20
N
t 100 o 500C
lJ. 1000C
III
CIJ >""0 .10 HOOC
50 -~ ------- -*--------. .1200C
-- --
00 1 2 3 4 5 0.00 0 1 2 3 4 5
Amount of La203 added, mol ~ Amount ot La203 added, mol a
Figure 1. Effects of amount of LazOJ added and calcination temperature on the a) specific surface
area and b) specific pore volume of alumina samples obtained from PYA-doped boehmite sol
(Table 1)
Increasing the calcination temperature from 500C to 12ooC decreases the

surface area and the pore volume of the alumina samples (Figure 1). The adding of
La 3+ to boehmite sol inhibits the surface area loss and the pore volume loss of
produced alumina during its calcination at high temperatures.The diagrams show
also that with rising amount of La3 + added increases gradual the stability of alumina
at high temperatures, but the content of 1.5 mol% La Z03 in alumina already
improves its thermal stability.
The influence of the calcination temperature on the surface area and the pore
volume for four prepared alumina samples are presented in Figure 2.
The diagrams in Figure 2 show that increasing the calcination temperature,
especially at high temperatures ranging from 1000 to 12ooC, decreases the surface
area of the La't-doped aluminas less than La't-nondoped one. It should be
emphasized that the aluminas prepared from PEG-doped in respect to PV A-doped
boehmite sol keep higher surface area and pore volume in all the investigated
temperature ranges.
The pore size distribution curves presented in Figure 3 show the improvement
in the thermal stability for the La't-modified aluminas . From the diagrams (Figure
3) for alumina samples calcined at 500C it can be seen that the non-doped alumina
349
300..-----.-------------, 0.50 . . - - - - - - - - - - - - - - - ,
a) b)
250 0.40
200
0.30
bIl bII
<, 150
..s <,
"S 0.20
..0.10 " APEGO
(J
~100 " APEGO
APEGLa2 APEGLa2
rn o APVAO :> o APVAO
50 APVALB2 APVALB2
~OO 600 800 1000 1200 0 .01400 600 800 1000 1200
Temperature. DC Temperature. DC
Figure 2. Effects of the calcination temperature on the a) specific surface area and b) specific pore
volume of the four alumina samples, listed in the Table 1.
has a very narrow pore size distribution with predominant pore diameter, d.n..= 2.9
nm, and that the adding of PEG, PEG+La3+,PVA, PVA+ La3+ to the boehmite sol
results in forming of alumina with broader pore size distribution slightly shifted
towards the larger pore diameter, d,..~3.2 nm. The diagrams of alumina samples
calcined at llOOC exhibits that the non-doped alumina has a wide pore size
distribution with d;.. > 10 nm, while the La't-doped aluminas retains the pore size
distribution in the region of pores within 3 to 8 nm diameters.
The change of porous structure are correlated by the phase transformation of y-
Alz0 3 during calcination of aluminas. Namely, the non-doped alumina sample after
calcination at l()OOC contains mainly 8-Alz0 3 , and after sintering at llOOC only a-
Alz0 3 , whereas the La3+- doped alumina samples even after sintering at 1200C, for
5 h, contain mainly 8-Alz0 3 and minor amounts of 0- and o-Al.O, .
0.40 . . , - - - - , : - - - - - - - - - - - - - - - - - - ,
e
~0.30 AO
bIJ " APEGO
<, APEGLa2
"8 o APVAO
CJ APVALa2
_o.20
"d
~
>
<l0 .10
11
Pore diameter, nm
Figure 3. Derivative of the cumulative pore volume curves with respect to pore diameter for
alumina samples listed in Table I, and calcined at: 5000C (solid curves) and llOOOC (dashed curves).
350
For a study on the sintering kinetics, the five alumina samples (AD, APEGD,
APEGLa2, APVAD and APVA2 from Table 1) were also sintered at 1000C for
different period of time ( 0.5, 1,2,3,5, 10 and 21 h).
It was observed that surface areas decrease rapidly during the initial hours of
sintering and then more slowly as the time is further extended. Thus, for example
after sintering at 1000 for D.5 h, AD-sample has the specific surface area of 127 ml/g,
ALPEGO-sample 139,7 ml/g, APEGLa2-sample 138.8 ml/g, APVAD-sample 120
ml/g and APVALa2-sample 123.5 ml/g. As the sintering time at this temperature
was prolonged to 21 h the surface areas of samples reduced on 78 ml/g , 95 ml/g, 112
ml/g, 83 ml/g and 96 ml/g, respectively. It is known that the y-AIl 0 3 may lose surface
area by two processes, sintering and the phase transformation to a-AIl 0 3 The
results of X-ray analysis have shown that the samples calcined at 1000C contain
only 0- and 8- AI l 0 3 After sintering during periods of 0.5 h the La'<-non-doped
samples contained more 8-AI l 0 3 phase than the La 3+-doped samples. As the sinte-
ring time at this temperature was further prolonged the content of 8-AI l 0 3 phase in
the alumina samples was increased. Thus, the samples AD, APEGD and APVAO,
which were sintered at 1000during 21 h, consist of only 8-AI l 0 3 phase, whereas the
La.Oj-promoted samples (APEGLa2 and APVALa2) contain a mixture from 0- and
8-AI l 0 3 phase. The general equation for reduction rate of surface area" was used to
analyze the kinetic data for sintering of five prepared alumina samples:
(1)
where (So-S.)/So is the normalized specific surface area reduction, t is the isothermal
sintering time, B is a constant containing material properties, particle size, and
temperature, and K is a constant for a given set of conditions. The exponent y
depends on the diffusion mechanism that is reponsible for the material transport
during sintering. For viscous or plastic flow mechanism y",,1.1 , for volume diffusion
y""2.5 and for surface diffusion y""3.5 11. The kinetics of the sintering of the alumina
samples, evaluated by using relation (1) are shown in Figure 4.
The values of y were calculated from the slopes of the plots depicted in Figure 4
and were found to be from 3.4 to 3.8. The value of about 3.5 - 4 was found for y,
corresponding to the surface diffusion'P? . Therefore, the kinetic data show that the
sintering of aluminas prepared by the sol-gel method proceeds via surface diffusion.
-0.6
-0.8 .1' 1'=3.4
/ 1=3.5
-1.0 / 1=3.5
-:-1.2 ~ 1=3.7
rn , ')'=3.8
~-1.4
cf
-1.6
e-1.8
d'-2.0 * AO
to APEGO
- -2.2 .. APEGLa2
-2.4 o APVAO
APVALa2
-2 .6_ 0
1 123 4
In t
Figure 4. The kinetics of the sintering of alumina samples in air at lOOOC
351
The plots in Figure 4 demonstrate also that the addition of LaJ~ by mixing La(NOJ)J
with the PEG- or PVA-doped boehmite sol improves the thermal stability of
prepared aluminas, but it does not change the mechanism of sintering. Assuming
that the sintering of alumina proceeds by neck formation, via surface diffusion, the
presence of well dispersed La't-ions on the surface of alumina crystallites decrease
the surface diffusion, e.g. inhibit the sintering of alumina.
CONCLUSION
The porous, high surface alumina , which may be used as a catalyst support, was
prepared by a sol-gel proces, from aluminium isopropoxide as precursor.
Heating of PEG-doped with respect to PVA-doped alumogel produces alumina
with higher surface area and pore volume.
A gradual decrease in the surface area of alumina calcined at 500C and
increase in the thermal stability of the porous structure of doped alumina with rising
LazOJ content was observed. The content of 1.5 mol% LazOJ in alumina already
improves its thermal stability.
The kinetic data show that the sintering of aluminas obtained by sol-gel process
proceeds via surface diffusion.
ACKNOWLEDGMENTS
This work was supported in part by the Serbian Ministry of Science and Technology.
REFERENCES
1. B.E. Yoldas, A transparent porous alumina, Amer. Ccram.Soc.Bull., 54:286 (1975)
2. Y.S. Lin, KJ. de Vries and AJ. Burggraaf, Thermal stability and its improvement of the alumina
membrane top-layers prepared by sol-gel methods, J. Meter.Sci; 26:715 (1991).
3. Y.S. Lin and AJ. Burggraaf, Preparation and characterization of high-temperature thermally
stable alumina composite membrane , J.Amer.Ccram. Soc., 74:219 (1991).
4. T.Lopez, ARomero, AChavela, L. Razo and R.Gomez, New Alternatives for high specific area
y-A1203 synthesis, ReactKinet. Cstsl.Lett., 43:307 (1991).
5. N.N. Jovanovic, Z.M. Vukovic and T.E. Novakovic, The effects of additives on the thermal
stability of porous structure of alumina obtained by sol-gel process, Sci Sinter; 28:165 (1996).
6. F. Mizukami, K Maeda, M. Watanabe, K Masuda, T. Sano and K Kuno, Preparation of
thermostable high-surface-area aluminas and properties of the alumina-supported Pt catalysts,
in: Catalysis and Automotive Pollution Control II, A Crucq, ed., Stud SurfSci.Catal, 71:557
(1991) Elsevier Sci.Publishers BV., Amsterdam.
7. B.E. Yoldas, Alumina sol preparation from alkoxides, Amer.Ccram.Soc.Bull,54:289 (1975).
8. N.Jovanovic, T. Novakovic, J. Janackovic and A Terlecki -Baricevic, Properties of activated
alumina obtained by flash calcination of gibbsite, J.CollInterfSci,150:36 (1991).
9. B.C. Lippens, Structure and Texture ofaluminas, Ph.D.Thesis, Technische Hogeschool te Delft,
Delft 1961,The Netherlands.
10. R.M . German and Z.A Munir, The identification of the initial- stage sintering mechanism: a
new approach, in: Sintering and Catalysis, G.C.Kuczynski, ed., Plenum Press, New
York/London, p.259, (1979).
11. H. Schaper, E . B.M. Doesburg, P.H.M. de Korte and L.L. van Reijen, Thermal stabilization of
high surface area alumina, Solid State Ionics, 16: 261 (1985).
352
SYNTHESIS AND SINTERING OF PZT CERAMICS
J. A. Varela', M. A. Zaghete', A. Z. Simoes', M. Cilense! and E. Longo/
'ChemistIy Institute- Unesp- Araraquara/SP -CEP: 14.801-970, C.P.:355

2Chemistry Dept - UFSCar/SP - CEP: 13.565-905, C.P.: 676
ABSTRACT
Lead zirconate powder, with Zr/Ti ratio of 50/50 was rrepared by polymeric
precursor method and doped with 3, 5 and 7 mol% of Sr+2 or Ba+ , as well as by 0.2 to 5
mol% of Nb'". The powder was calcined at 750C by 4 hours and milled during 1.5 h in
isopropilic alcohol. Powders were characterized by surface area measurements (BET
method), by infrared spectroscopy and by X-ray diffraction to characterize the crystal
structure. Isostatically pressed samples were sintered in a dilatometer furnace by using a
constant heating rate of 10C/min from ambient to 1200C. Synthetic air and air with water
vapor were used as atmospheres. Both Sr+2 and Ba+2 substitute Pb+2 and favor the formation
of rhombohedral phase. Otherwise, Nb+5 substitute preferentially Zr+4 favoring tetragonal
phase. The concentration of dopants and the atmosphere influence the densification and the
microstructure of the PZT, which alters the dielectric and piezoelectric properties of the
ceramics.
INTRODUCTION
Lead Zirconate Titanate (PZn is a ferroelectric ceramic, largely used as a piezoelectric

material in sensor and actuator applications'? because of its large electromechanical
coupling coefficients, temperature stability, and high resistance to depolarization. In lead
zirconate titanate (PZn preparation, the control of some parameters is important to achieve
the desired material properties. These parameters include the absence of intermediate
crystalline phases, a defmed and fixed stoichiometry, as well as a homogeneous lead
distribution in the microstructure. In conventional processing'r' PZT are prepared by
mixture and calcining PbO, Zr02 and Ti02 powders. This process requires hi~ sintering
temperature and causes the PbO loss. In recent years sol-gel processing 9 and co-
precipitation 10 has becoming popular for producing ceramic materials with improved
compositional homogeneity and lower sintering temperatures. However, the sol-gel process
Ad vanced Science and Technology ofSintering, edited by Stoj anovic et al.

utilizes expensive precursors and a critical drying process. The co-precipitation process is
limited to cation solutions with similar solubility constants. Pechini's method!', which
employs complexing of cations in an organic media, makes use of low cost precursors and
results in a homogeneous ion distribution at molecular level 12 Because of the formation of a
polyester resin during the synthesis, there is no segregation of cations during the thermal
decomposition of organic matter.
The tetragonal and rhombohedral phases coexist in the morphotropic phase
boundary (MPB) where the dielectric constant and the electromechanical coupling
coefficients show maximum values I3.14 Zaghete et aIlS using the Pechini method for
preparation PZT, verified that MPB occurred for composition at 50/50 ofZr/Ti.
To enhance the properties of the PZT ceramic dopants like Nb, La, Ca, Ba are added
to PZT composition. Addition of small quantities of pentavalent element (Nb+S) produces
Pb vacancies (A - vacancy in AB03 perovskite) in PZT and enhances domain
reorientation'", resulting in square hysteresis loops, low coercivity, high remnant
polarization, high dielectric constant, and high electromechanical coupling factor.
Furthermore, Nb-doping reduces the temperature dependency of piezoelectric constants".
Nb-doped PZT (called PZ1N) is used in high-sensitivity devices, such as hydrophones,
phonograph pickups, sounders and loudspeakers.
The addition of barium or strontium ions as dopant in PZT results in lower values of
Curie temperature and remnant polarization. This dopant can cause either lower loss
dielectric, low values of d31 and high values for d33. The materials with these characteristics
are used in ultrasonic transductors", The doping favorably influences the dielectric loss
constant, the grain growth and the dielectric constant.
It has been reported that the loss of stoichiometry by PbO evaporation during
sintering, as well as the formation of lead-rich grain boundaries, generated by the
introduction of a lead excess in the initial composition, decrease the planar coupling
coefficient, kp, and piezoelectric strain coefficient, d33, values and affect their
reproducibility". Other factors such as defects, grain size, wall domain mobility and density
are reported to affect the piezoelectric and dielectric properties'",
This paper deals with phase development of PZT based ceramics prepared by
Pechini method. The influence of S?+, Ba2+ and Nb s+ addition to PZT composition on the
sintering behavior and on the microstructure development is also considered.
EXPERIMENTAL
The procedure of PZT synthesis, based on Pechini's method", makes use of the
capability that certain a-hydroxycarboxylic organic acids possess of forming polybasic acid
chelates with several cations. When mixing with a polyhydroxylic alcohol and heating, the
chelate transforms into a polymer, maintaining the cations homogeneously distributed. The
organic part is subsequently eliminated at temperatures as low as 300C, forming reactive
oxides with well-controlled stoichiometry.
Pure PZT with composition Pb(Zro.soTiO,SO)0 3 was prepared from the metal-citrate
complex polyesterified in ethylene glycol. Appropriate quantities of Zr, Ti, Pb and dopants
(Sr or Ba or Nb) solutions were mixed and homogenized by stirring at 90C for 3 hours.
Next, the temperature was increased to 130-140C, yielding a high viscous polyester resin .
Most of the organic matter was decomposed in a box furnace, by carefully heating
the polyester inside a glass beaker from room temperature up to 300C, followed by
increasing the temperature to 400C, with soaking time of 2 hours at each temperature.
Further calcining was conducted at 750C for 4 hours and the powder ball milled for 1 hour.
356
Thermogravimetric (TG) analyses of resins prepared at 140C was carried out in
atmosphere of synthetic air at a constant heating rate of 5C/min.
Powders were analyzed by X-ray diffraction (XRD) for phase determination and by
infrared (lR) for the presence of organic radicals. The powders were isostatically pressed
(230 MPa) into pellets. The pellets were sintered inside a dilatometer furnace using a
heating rate of lOoC/min from room temperature at 1100C in air and air plus 60 torr of
water vapour partial pressure. The pellets were sintered during 4 h at 1100C inside a box
furnace, in a closed system containing 10 ~Io of (PbZr03 + 5 ~Io PbO) powder relative
to the pellet mass, to generate a lead rich atmosphere. The density of fired pellets was
determined by the water displacement method. A scanning electron microscope (SEM) was
used to analyze the microstructure, shape and grain size.
The samples were coated on the parallel surfaces with silver paste to provide
electrodes and poled by applying a de electric field of30 kV/cm at lOOC for 30 minutes in
a silicone oil bath. The resonance and anti-resonance frequencies, fr and fa. were measured
in the HP Spectrum Analyzer, model 3585A, and k p was determined according to the
procedure described by Haertling'". The d33 was determined using an American Piezo
Ceramics apparatus calibrated with piezoelectric standards.
a) The Effect of Aditives on the Phase Formation and Reactivity ofPZT
There are controversies about the width of the morphotropic region when chemical
processes are used to prepare PZTZD-Z3. On one hand, there is agreement that the PZT
tetragonal phase is the first one to crystallize in conventionally prepared PZT, since titanium
is more reactive to form the lead titanate. However, XRD data Z4 obtained for samples
prepared by Pechini's method show an opposite behavior, since the rhombohedral phase is
the first one to be formed during calcination, independently of sample stoichiometry. Figure
I shows the XRD data for one composition (SO/50) where, up to 700C, peaks appear at 29
equal to 21 0 , 44, 50 and 54. characteristic of the rhombohedral phase. At 800C, these
peaks split into the characteristic peaks of the tetragonal phase.
700C 800C
600C
500C
",oooe
20 30 40 50 60
28 (degrees)
Figure 1. XRD data for PZT 50/50 powdercalcined for 3 hoursat the temperatures indicated
357
IR spectroscopy carried out on PZT samples showed two vibration peaks, one in the
800 - 400 cm- l region and the other at -1407 cm- l (Figure 2). The former is due to metal-
oxide binding; the latter refers to carbon-oxygen vibrations in carbonates. This is also in
agreement with Kumar et at2s, where the presence of carbonates was observed in BaTi03
prepared by the Pechini process.
4000 3200 2400 1600 800

Wavenumber {cm-~
Figure 2. IR bands for PZT SO/50 powdercalcinedat (a) 400C; (b) 500 C; (c) 600 C.
TGA analysis was carried out for PT, PZ and PZT resins, showing that PT
decomposition is slower than PZ decomposition (Figure 5). Above 465C there is no weight
loss for PZ but there is still a small weight loss (~2%) for PT around 727C. Thus, after
calcining PZT for 3h at 600C, there is less Pb/Zr carbonate left than Pb/Ti carbonate. This
leads to the formation of a zirconium rich PZT phase, since more zirconium ions are
available than titanium, from the carbonate decomposition.
o
--PZrresin
-20
- ,-PZresin
......... PT resin
5700C
\ -
7270C
! I , , I , I , I , I
200 400 600 800 1000
Terrperature,OC
Figure 3. TG CUIVes forPT, PZ and pzr resins, obtained in synthetic air atmosphere andheating rateof 5C/min.
358
Ba+2 or Sr+2 additionsto PZT composition displace Pb+2 from the lattice and change
the reactivityof the powders. The results in Table 1 show the influence of the dopant on the
surface reactivityof the powders calcined at 750C during 4 h and the behavior of these
Table 1. Surface area and green densityof the doped and undoped PZT
Surface Area Green Density

PZT (ml/g) (glcm~
Undoped 3.4 4.65
3 mol %Sr+ 1
6.1 4.47
5 mol %Sr+2 5.7 4.50
7 mol %Sr+2 4.4 4.53
3 mol %Ba+2 7.0 4.50
5 mol %Ba+2 4.5 4.54
7 mol %Ba+2 4.0 4.50
powders during processing. Higher reactivityis obtainedwith the addition 00 mol % of

either Ba+2 or Sr+2. The use of 7 mol % of these dopants decreases the reactivity due to
formation ofPbO liquid phase during calcining leadingto aggregationof particles.
The addition of Nb+s to the PZT displaces Zr02 from the lattice and changes the
PZT phase compositionas well as precipitatesmonoclinic zirconia as show in Table 2. This
table illustrates the results of quantitative phase analysis and lattice parameters obtained
with the Rietveld method. Increasing amount ofNb+s leads to increase in the concentration
of monoclinic zirconia and decrease of tetragonal phase. These results allow inferring that
Nb+S is substituting Zr+4 in the PZT lattice. Niobium doping also alters the lattice
parameters. The c parameter in the rhombohedral phase increases when Nb+S is introduced
in the PZT. This produces a positive effect for the piezoelectric properties.
Table 2. Quantitative phase analysis for niobium doped PZT sintered at 1100C. Lattice
parameterobtained with the Rietveld method.
Composition (% in mass) Lattice Parameters (A)

Sample Tetrag, Rhomb. z-o, Tetragonal (p4mm) Rhomboh.(R3m)
a b a c
PurePZT 78.1 21.9 0.0 4.0340 4.1330 5.7530 7.0480
0.3%Nb 76.4 23.1 0.5 4.0322 4.1402 5.7539 7.0541
0.5%Nb 73.2 25.0 1.8 4.0341 4.1345 5.7412 7.0599
0.7%Nb 73.3 24.6 2.1 4.0319 4.1382 5.7399 7.0624
b) The Effect ofSr+1 and Ba+2 on the Sintering ofPZT.
As mentioned before Sr+2 and Ba+2 are dopants that substitute A site of the PZT
lattice. Then the Pb+2 are displaced from the lattice and can form a liquid phase at the grain
boundaries. Figure 4 shows plots of the relative shrinkage and shrinkage rate of the
strontium and barium modified PZT. Addition of 3 mol% of strontium and barium lead to
359
displacement of shrinkage and shrinkage rate curves to higher temperatures. The effect of
Ba+2 is even more outstanding as shown in Figure 4c. Small amounts of both Ba+2 and Sr+2
substitute the lead vacancies created during calcining PZT (due to evaporation of PbO).
Then the rate mass transport will decrease in the system once Pb+2 should control the
sintering process. Considering that Ba+2 has ionic radius larger than Pb+2, this effect is more
dramatic with addition of Ba+2. For larger amounts of dopants, however, the tendency is to
decrease the temperature where the shrinkage starts. This should be related to the excess of
PbO forming a liquid phase that could rearrange the PZT particles during sintering. Since
Ba+2 is larger than Pb+2, the solid solubility of Ba+2 in the lattice is smaller than the
solubility of Sr+2 in the lattice and BaTi03 should precipitate at the grain boundaries,
decreasing the sintering rate (see Figure 4).
0.001- - ...
I- ~10 PZT pure
f~"
.....0.-
-o-PZT + 3%Sr
-PZT+5%Sr
PZT+7%Sr
~26+--..........,r__..,....__r-...-_r_ ..... - o r _......._ _ r -......_f

o X> llOO IKlO 1000 1200
T8 i ,*IlN'8,c
0 0
~ 2
~
l: ...
J
Air dry atmosphere
.E ~ -6,- PZT Pure
!1. ~
10
- - 0 - PZT 3% Ba
-PZT5%Ba
PZT 7% Ba
ex:
12
200 400 800 800 1000
Temperature rc
360
The effect of the 5r+2 and Ba+2 concentration on the microstructure can be seen in
Figure 5. Pure PZT shows an intragranular fracture, while doped PZT shows intergranular
fracture . The grain size increases with addition of 5r+2 up to 5 mol% and remains constant
for 7 mol%. The same behav ior can be seen with addition of Ba+2 leading to inhibiting grain
growth for concentrations higher than 5 mol% due probably to precipitation of BaT i03
second phase at the grain boundaries.
c) The Effect ofNb+5 Addition on the Sintering ofPZT.
The addition ofNb +5 to the PZT cerami cs affects the sintering behavior as shown in
Figure 6. As discuss ed earlier , Nb +5 replaces Zr+4 in the lattice and can generate Pb+2
0.00
- o .(),05
~
--
M .(),10
Pitdry &In i08PIWe
f~"
-IJ,- PZT pue
-<>-PZT+Sa (3%molar)
- PZT+Sa (5% molar)

.(),20 PZT+Sa (7%molar)
0 3Xl 400 lDl eoo 1000 1200
TeI1l8lltlJ'e,oC
0
0
.-
~ -6
~ ~dryatmosphere
j 10 -A-PZTpwe
f-"
-0- PZT +3% Sr
.S
-PZT +5% Sr ,
PZT+7%Sr ''
"
"
j'" "I
,
-25
0 200 400 eeo lDl 1000 1200
T8f1'1)er8hn,oC
Figure 4. Relative Linear Shrinkage and Shrinkage rate as function of Sr+2 and Ba+2 concentration in PZT
samples sintered in synthetic air.
361
vacancies, according to the following reaction:
(1)
Then the niobium ion can create extrinsic lead vacancies, increasing the rate of
sintering. Moreover, niobium will dislocate Zr+4 that precipitates as monoclinic Zr02. As
the concentration of niobium increases there is a solid solubility limit beyond niobium ion
precipitate and can react with Zr02 forming Zr~07' This solubility limit seems to be
above 3 mol % as observed in the sintering curves.
I
~ ~J . "
.
'. " . 'yf.'" .,-._.:.J...
. -_ . ''''
J' '-'
. .... , .'
~ ". (
, ~ 1 .... !
. , I ) . ~I
/ , '.J-,
' 5.., . I , "
,
)1.' .e.; '. I,
r.
' "r'
rJ
' J r'

i
A .,
\. .;. .~
' !.J
,....- H , ~ \(r
,
' 0./' . ...... ..

~'-"
: \'~~~~)
.." r-
. t
.r:J......
'.
/
ir:
trI .,
r .
' (' 1
\\ Q .
1.....,;
,n... '(WI, )' -.;: .".
, . . 1' r i. ~ r . /,
'-:.: '. .." i.
\.. .~ ' ..
(a) (d)
(b) (e)
(c) (f)
Figure 5. SEM micrographs on fractured surface of PZT sintered in a dilatometer furnace using heating rate
of lOoC/min in syntheticair up to lIOOC: (a) Pure PZT; (b) PZT with 3 mol% Sr+2; (c) PZT with 5 mol% of
Sr+2; (d) PZT with 3 mol%Ba+2; (e) PZT with 5 mol% Ba+2; (t) PZT with 7 mol%Ba+2,
362
--o
..J
o,oo~ --"""
<! ~.015
-6- PZT Pl.fe

- 0 - PZT1.5%,.,.,
~.15
- PZT 3%"'"
PZT 7%,.,.,
. 2r-------------------.
o
..... or ....
~ -2
~ SyntheticAJr Atmosphere
...... -4
J~
1: PZT Pure
-o-PZT 1.5% Nb
.E ~ -PZT3%Nb
~ -10 PZT 7% Nb
B .12
1- 14
-18!--r-r--r-r--r-r--...,....-.--...,....-..-......- 1
o 200 400 800 800 1000 12C
Temperature fC
Figure 6. Relative Linear Shrinkage and Shrinkage rate as function of Nb+5 concentration in PZT samples
sintered in synthetic air
363
(a) (b)
(c) (d)
Figure 7. SEMmicrographs on fractured surface ofPZT sintered in a boxfurnace at 1100 Cduring 4 hours:
(a)purePZT; (b) PZT with 1.5mol % Nb+5; (c)PZT with 3.0mol % Nb+5; (d)PZT with 5.0mol % Nb+s.
The increase of diffusion rate of Pb+2 justify both, densification and grain growth of
PZT for concentrations up to 1.5 mol %. Above this concentration, two concurrent
mechanisms occur, that is, increasing in the rate of mass transport and pining of grain
boundaries by second phase precipitation that inhibit grain growth (Figure 7). For
concentrations above 5 mol % of Nb+5, inhibiting grain growth by pining dominates the
microstructure of niobium modified PZT ceramics
CONCLUSIONS
The rhombohedral phase is firstly formed at low calcining temperature when Pechini
method is used for synthesis. This is due to the difference in stability of the citrate
complexes. Zirconium citrate is less stable and decomposes first leading to formation of
PbZr03 .
Both Ba+2 and Sr+2 affect significantly the sintering ofPZT by replacing the Pb+2 ion
of the lattice. Low concentration of these ions retards the sintering rate due annihilating of
lead vacancies by Ba+2 or Sr+2. Larger concentrations of these ions inhibit grain growth due
to precipitation of second phase, probably BaTi03 or SrTi03
Nb+5 substitute the Zr+4 in the PZT lattice and affect the microstructure during the
sintering. Addition of Nb+5 up to 3 mol % favors grain growth. However, higher
concentrations ofNb+5 inhibit grain growth due to segregation of niobium oxide at the grain
boundaries and precipitation of a second phase, probably Zr~07.
364
Acknowledgment
The authors acknowledgeFAPESP, FINEPIPADCTand CNPq for granting this research.
REFERENCES
1. B. Jaffe, W. R. Cook Jr and H. Jaffe, Piezoelectrics Ceramics, Academic Press, New
York, 1971, p 135.
2. S. Troiler-McKinstry and R. E. Newnhan, MRS Bull. 2827 (1993)
3. K Uchino, Problem Solving Piezoelectric Actuators, Morikita Publ., Tokyo, 1991.
4. S. S. Chantratreya, M. R. Fulrath, and J. A. Pask, Reaction mechanisms in the formation
ofPZT solid solution. J. Am. Ceram. Soc. 64 (7), 422 -425 (1981)
5. B. Jaffe, W. R. Cook Jr and H. Jaffe, Piezoelectrics Ceramics, Academic Press, New
York, 1971, p 253.
6. X. Yang, T. K. Chaki, J. Mater. Sci. 32 4661 (1997).
7. M. S. Multani, S. G. Gorkam, V. R. Palkarard, and R. Vijayaraghavan, Morphotropic
phase boundary in the system Pb (ZrxTh.x) 0 3 Mater. Res. Bull. 17 (1) 101-104
(1982)
8. L. M. Sheppard, "International Trends in Powder Technology", Am. Ceram. Soc. Bull.,
68(5),979-85 (1989).
9. G. Tomandl, A. Stiegelschmitt, and R. Bohner, "Lowering the Sintering Temperature of
PZT Ceramic by Sol-Gel Processing"; pp. 3-173 in Science Of Ceramics Chemical
Processing, Edited by L. L. Hench and D. R. Ulrich. John Wiley & Sons, New
York, 1986.
10. A. Kato, "Study on Powder Preparation in Japan", Am. Ceram. Soc. Bull., 66(4), 647-
50, 1987.
11. M. P. Pechini, "Method for Preparing Lead and Alkaline-Earth Titanates and Niobates
and Coating Method Using the Same to Form a Capacitor" U. S. PATENT
n" 3330697, 1967.
12. P. A. Lessing, Mixed cation oxide powders via polymeric precursors. Am. Ceram. Soc.
Bull. 68 (5) 1002-1007, (1989).
13. R. Gerson and H. Jaffe, Dielectric properties of lead titanate zirconate ceramics at very
low frequencies. J. Phys. 31(9) 1615-7, (1%0).
14. B. Jaffe, R. S. Roth, S. Marzullo, J. Appl. Phys. 25 809 (1954).
15. M. A. Zaghete et al, J. Am. Ceram. Soc. 75225(1995).
16. L. Wu, C.-C. Wei, T.-S. Wu and C.-e. Teng, "Dielectric Properties of Modified PZT
Ceramics", J. Phys. C : Solid State Phys., 16, 2803-12 (1983).
17. T. Yamamoto, "Optimum Preparation Methods for Piezoelectric Ceramics and their
Evaluation", Ceramic Bull., 71(6),978-85 (1992).
18. S. C. Chiang, M. Nishioka, F. M. Fulrath and J. A. Pask, "Effect of Processing on
Microstructure and Properties of PZT Ceramic", Ceramic Bull., 60(4), 484-89
(1981).
19. G. H. Haertling, "Piezoelectric and Electrooptic Ceramics"; pp. 3 in Ceramic Materials
for Electronics, R. C. Buchanan, Marcel Dekker Ed., New York, (1986), cp.3
20. P. Ari-gur and L. Benguigui, "X-ray Study of the PZT Solid Solutions Near the
Morphotropic Phase Transitions", Solid State Commun., 15(6),1077-79 (1974).
21. S. A. Mabud, ''The Morphotropic Phase Boundary in PZT Solid Solutions", J. Appl.
Cryst., 13,211-16 (1980).
22. A. Barbulescu, E. Barbulescu and D. Barb, "Phase Transitions in PZT Solid Solutions"
Ferroelectrics, 47, 221-30 (1983).
365
23. J. F. Fernandes Lozano, and C. Moure, "Sinterizacion a Baja Temperatura y Desarrolo
Micro-Estrutural de Materiales PZT Obtenidos a Partir de Diferentes Precursores",
Bo/. Soc. Esp. Ceram. Vidr., 27(1) 17-23 (1988).
24. M. A. Zaghete, C.O. Paiva Santos, J.A. Varela, E. Longo and Y. P. Mascarenhas,
"Phases Characterization in PZT Obtained from Organic Solutions of Citrates", J.
Am. Ceram. Soc., 75[8] 2088-93 (1992).
25. S. Kumar, G. L. Messing and W. B. White, "Metal Organic Resin Derived Barium
Titanate: I, Formation of Barium Titanium Oxycarbonate Intermediate", J. Am. Ceram.
Soc. 76[3] 617-624 (1993).
366
ADVANCES IN SINTERED ELECTRONIC MATERIALS
Center for Multidisciplinary Studies

University of Belgrade,
ABSTRACT
Although the use of ceramics is several thousand years old, developments in

the past three decades have created enormous interest in the field of sintered
electronic materials. Integration is technological goals in virtually all electronic
materials and the age of ceramic integration is upon us. Trend to smaller and smaller
sizes, as a characteristic of the age of integration and miniaturization, has led to the
development of complex sintered electronic materials. At the same time, a wide
variety of smart sensors, transducers, actuators, varistors, termistors, dielectric
insulators and capacitors, ferrite inductors and electrooptic ceramics are being
presently produced.
INTRODUCTION
Professor R.E.Newnham at the 89 th Annual Meeting of the American Ceramic

Society has been said in his lecture /1/:
.... ...For 30 years I have collected gemstones and crystals ; faceted stones oforange
sphlslerite, pink kunzite, pleochroic cordierite, purple apatite, and golden orthoclase
continue to fascinate and delight me ...Each gem is a beautiful piece of nature, cut
and polished in a way to appeal to the human eye. Collectors clsssity gems according
to the seven Seas; composition, colors, clarity, commonness, cutting, carats, and cost.
In many ways, thick film circuits, multilayer packages, and other electroceramics
strike a similar chord. Each is a small bit ofinorganic material carefully fashioned to
carry out an electronic function . Much of the excitement of present-day
electroceramics can also summarized by seven Seas; conducting cuprates, ceramic
circuitry, co-fired compatibility, composite connectivity, core-clad couplers .
Really, whether ceramics are used in components or as final products is only a
meter of applicability. But one trend is obvious: the growth trend observed in the
ceramic field is primarily due to advanced ceramics, whose development has

changed the entire industry structure. Advanced ceramics are known more
specifically as electronic and engineering materials. The high rate of growth for this
segment of the ceramic industry is due primarily to rapidly developing technology
matching the industrial demands for replacement of metals in many applications
from cutting tools and heat engines components to integrated circuits packaging,
electronic substrates and magnetic materials. At present, the field of advanced
ceramics has a more 20 % share of total ceramics market, and two third of this are
ceramics for electronics 12/. Estimated investments till 2000 in electroceramic
materials (Fig.I) could be approximately 24.109 $ in Japan, up to 15.109 $ in USA and
about 10 billion dollars in Europe 131 .
irrs
24.,.,----- - - - - - - - - - - - - - - --==---,
I EUROPE - USA JAPAN I
18 J+-- - - - - - - - - - - - - - - ----l
12J.1-- - - - - - - - - - - - -j
6 J.1-- - - - - - - ----:=
o
c::l Differences of various prognoses
Fig.l. Estimated investments till 2000. in electroceramic materials
The multibillion dollars electroceramic market includes ferrites, transducers,

multilayer capacitors, varistors, packages, optical fibers. Roughly speaking, rapidly
developing technologies can be identified as rapid evolving fields of a number of
sintered electronic materials. The golden age of electroceramics involves the
miniaturization and integration of ceramic components into a wide variety of
optoelectronic system .
STRUCTURE - PROPERTY RELAnONS
An overview of sintered electronic materials is given in Fig.2, which depicts

schematically the types of electronic and ionic phenomena in electronic ceramics 14/.
Many of the electroceramics utilize some bulk properties of the ceramic, such as the
presence of ferroelectric or ferromagnetic dipoles, electronic or ionic conductivity,
or a phase transition to provide useful function. It is well known that the presence of
ferroelectric domains is important for properties of capacitors and piezoelectric, as
also for thermistors with positive temperature coefficient of resistance (PTCR).
However, ferromagnetic domains have to be necessary for hard and soft ferrites or
368
magnets. Electronic conduction for thermistors with negative temperature
coefficient of resistance (NTCR), ionic conduction for gas sensors and batteries and
surface conduction for humidity sensors can describe above structure - property
relations. Grain - boundary phenomena gives significant information about
resistors, barrier layer capacitors, and PTC thermistors. So, in many materials
extraordinary responses can be engineered by suitably tailoring the thickness and
properties of a given boundary phase. Varistors and PTC thermistors, for example,
all rely on the preparation of the semiconducting grains and insulating grains
boundaries to create properties that cannot found in single crystals . In a similar way,
some of the porous ceramic materials utilized in humidity sensors rely on surface
properties then on a bulk response, to detect changes in the ambi ent humidity.
Finally, in materials for insulators or substrates, all of the otherwise interesting
phenomena depicted in Fig.2, must be eliminated. With the exception of the last
category, all the phenomena can be utilized in ceramic sensors.
Ferroelectric Domains: Electronic Conduction Surface Conduction:

Capacitors and NTC Thermistor Humidity Sensor
Piezoelectrics
PTe Thermistor
~tors
~ Substrates
r;::=:....
- I
~I:;~ID~ ~
mEl [~[JIciJ'.e@.II----
C~C
t
".. . .
___
r..:
+
l~'l
I
~
~
L.::::- ~ l.- I
Ferrimagnetic Ionic Conduction: Grain Boundary
Domains: Ferrite Gas Sensors and Phenomena:
Hard and Soft Batteries
Magnets Varistors, Boundry
Magnetic Tape Layer Capacitors,
M~tal - Semiconductor PTC Thermistors
Transition: Critical Tern -
pe rature NTC Thermistor
Fig.2. Ionic and electro nic phenomen a in electronic ceramic /4/
It is emphasized that several kind s of mechanisms are operative in thermistors

and other ceramics used as sensors. Most are based on changes in electrical
resistance, but the causes ar e differ ent.
The critical temperature thermistor involves a semiconductor metal phase
transitions. NTC thermistors make use of the semiconducting properties of doped
369
transition-metal oxides. For example, stabilized zircon is an excellent conductor, and
~-alumina is one of the best cation conductors. The importance of all those
electroceramic materials should not be overlooked. Most of the structural effects
above have been reported crucial to the operation of the electroceramic
components. But this is not always easy to be involved . In recent years special efforts
have been made in sintered electronic materials, especially regarding the synthesis of
extremely fine powders with a narrow size distribution to achieve desired properties.
In any way, all thermal, mechanical and electronical properties required for a good
performance in electronics, especially in microelectronics, demand suitable
structures obtained by corresponding technological processes.
CERAMIC CIRCUITRY
Obviously, miniaturization and integration are technological goals in virtually

all electronic materials. In present, several kinds of electroceramic materials are
most useful, as shown in Fig.3. /3/. Circuitry in ceramic materials can used in
electronic packages, integrated optics, cooling systems, electromechanical
transducers, magnetic recording, multilayer actuators, ionic batteries and chemical
sensors .
MINIATURIZATION "INTEGRATION
I JL_-crl -- ~:
ELECTRONIC OPTiCAl (IR. UV....)
I
C1
I(
THERMAL MECHANICAL
I "~ rnxJ
k
c
v a
MAGNETIC FLUX ELECTRIC FLUX
I I
~ \11111111111111 K
11111111111111 \
C1 a
IONIC CHEMICAL
I~I
0
c E<f[J 0
r
Fig.3. Ceramic circuitry for use in electronic packages, integrated optics, cooling systems,
electromechanical transducers, magnetic recording , multilayer actuators,
ionic batteries and chemical sensors /1/
370
Electronic circuitry is the most advanced, especially in thick film and multilayer
packaging technology, where the control of electrical conductivity and dielectric
constant are the key parameters /1/ . Integrated optic systems, for example utilizing
LiNb0 3, make use of small changes in refractive index to guide and control light
waves. Low absorption coefficients are also important properties. Thermal
conductivity and convective fluid flow velocities are important for the thermal
circuitry, especially as it is used in circuit packaging technology where heat must be
removed as efficiently as possible.
For magnetic circuitry the essential properties are high conductivity. So, the
ceramic materials have to concentrate and manipulate regions of high magnetic flux.
Electronic flux concentration is used in ceramic actuators to produce large
displacements with small voltages. Multilayer capacitors /6/ operate on flux
concentration principle accomplished with multilayer systems made up of internal
electrodes with high conductivity and high permittivity dielectric layers . Ionic
movement in battery systems constitutes another type of circuitry in ceramic
materials /7/ . The crucial properties are the ionic conductivity and diffusion
coefficients.
It was mentioned that the porous ceramics with high surface areas were used in
manufacturing chemical sensors. Th e movement of molecules and dissociation
products constitutes a type of chemical circuitry controlled by diffusion coefficients
and surface electrical resistance.
VARISTORS, THERMISTORS, CAPACITORS
Varistors and thermistors are special ized resistors whose electrical resistance
varies with applied voltage and ambient temperature. Most varistors and thermistors
are made of ceramic mat erials. /8/.
Varistors are categorized by their primary component material:ZnO or SrTi0 3,
or newer one as SiC. Varistors can be used in surge absorbers, arrestors and
micromotors. In fact, ZnO varistors are mounted in surge absorbers and arrestors
and SrTi03 varistors in micromotors. Keeping in mind that the varistors have been
developed for use in suppressing the electrostatic discharge pulse in de power
circuits, at present, oxide varistors are used extensively to protect electro nic circuits
against sudden surges of voltage that can seriously damage equipment.
The behavior of varistors has to be addressed in both the pre-breakdown and
breakdown regions. ZnO varistors consist of grains of electrically insulating barriers
at grain boundaries. These barriers are formed by the addition of an oth er oxide
such as bismuth oxide or barium oxide . Other oxides are added to improve the
device performance.
The NTC and PTC thermistors can be also categorized by their primary
component material /9/ . Transition-metal oxide s are typically used. The largest share
of thermistors is used in automobiles and consumer constituent in all PTC devices is
roughly divided into heaters, especially in self-regulated heaters , TV degaussers,
thermal sensors, current-surge protectors, etc .
Having in mind that BaTi03 is normally an insulator, the thermistor behavior is
in consequence of doped effects when BaTi0 3 becomes semiconductor. It has been
established that the PTCR effect is a grain boundary resistance effect, even at
temperatures well below Curie point. Grain-boundary model given by Heywang /20/
treats the grain boundary as an-type Shottky barrier with the deep acceptor states at
the grain boundaries. The resistance anomaly behavior of doped BaTi0 3 is shown in
Fig.4. /10/
37 1
insulatig
106 - region
Acceptor-shell
0/0 replaced by h'
during oxidative
cooling)
(range)
10
2
- n-type
region
I Donor-eore
10 - Tc - Curie temp. (electron compensation
I I I I I within the bulk)
-100 o 100 200 300
Temperature (0C)
Fig.4. Electrical resistivity for typical PTCR device and shematic presentation of defect chemistry
responsible for PTCR effect
Dielectric ceramics for capacitors present an important segment of electronic

ceramics. A key technology for these advanced dielectric materials is a unique
appropriate powder process and precise stoichiometry control to obtain dielectric
with a fined-grained microstructure.
The parameters for a high quality ceramic capacitors are as follows: high
dielectric constant, low loss factor, low variation of dielectric constant in the
temperature range, high insulating resistance temperature dependence. Multilay er
ceramic capacitors (MLC) devices have become more important in man y
applications /11/. They have small change of capacitance with temperature and
extremely good capacitance to volume ratio. MLC capacitors can be used in surfac e
mounting technology for circuits of higher electrical performances. The common
ferroelectric materials, whether based on barium titanates or lead manganase
niobate, in the high field limit , exhibit an energy storage which maximum storage is
not obtained in high dielectric materials which have an intermediate dielectric
constant and the highest ultimate breakdown voltag es .
SMART ELECTROCERAMICS
"Smart" material have the ability to perform both sensing and actuating
functions. Passively smart materials respond to external change in a useful manner
without assistance, whereas actively smart materials have a feed-back loop which
allows them to both recognize the change and appropriate response through an
actuator circuit /12/. Many smart materials are analogous to biological systems , as
piezoelectric hydrophones or chemical sensors( act as human nose). But, "very
smart" materials, in addition to sensing and actuating, have the ability to "learn" by
altering their property coefficients in response to the environment.
As previously discussed , smart materials are capable of sensing a change in the
environment and responding in a useful way /4,12/. Many types of sensing and
actuating functions can be envisaged, as shown in Fig.5. In many cases, it may be
impossible to incorporate the desired actuation mechanism directly into sensor , or a
controllable response may be preferred. Materials with external feed-back loops ,
such as the electromechanical transducers used in tunable elastic compliance
systems , are actively smart. Basically, two multilayer piezoelectric actuators have to
be together. In fact , one of the piezoelectric transducers is excited to vibration with
372
an applied electric field, and the result ing pressure wave is trans ferred to the other
piezoelectric sensor, where it is detected . The signal can be processed through an
external circuit.
Environmental
Impact Economy Intelligence
Resource from the
Conservation Reliability human
standpoint
User-
Friendliness Others
Human efforts Manifestation

and research
If of intelligence
self-assembly self-repair
Intelligence
self-diagnosis Autolysis inherent in
Learning Others materials
Basic atomistic Buill-in software
and molecular systems in materials
behavior
11
Intelligence at
the most
primitive levels
in materials
FigS. Shematic present ation of smart materials concept /14/
Obviously, research in the field of sensors and sensing mechani sms in ceramic
materials has enclose a variety of phenomena that can be incorp orated into actively
and passively smart systems. Most of the useful sensor materials generate an
electrical signal, such as a current of voltage, resistance, capacitance, or reman ent
polarization which can be calibrate with respect to the change in the environment.
Temperature sensors can be prepared from semiconducting doped BaTi0 3 cerami cs
with large negative or positive temperature coefficient of resistance (NTCR or
PTCR ). Most of the current piezoresistive sensors based on dop ed BaTi0 3 PTC
ceramics can press much larger uniaxial and show higher hydrostatic piezoresistance
coefficients than silicon or germanium single crystals. Thus, these material s are
useful as pressure, vibration and acceleration sensors for automotive applications.
Electroceramic materials with electronic or ionic conducti on properties can be
used as oxygen sensors. The combination of porous and dense TrO, ceramics can be
oxygen-sensitive and operated stable over a wide temperature rang e. Many different
ceramic compos ition have been investigated as humidity sensors including porou s
Al z0 3 , MgCr0 4-TiOz and CoAlP4 spinels, Si0 2-ZnO , ZnCr20 4-LiZnV0 4, doped
ZrO z and aluminum and zinc pho sph ates. In general , the essential characteristic for
humidity sensors is the changes in surface properties, especially the electrical
resistance, as moisture absorbed from the air, contrary to the polymeric systems
373
which utilize a change in bulk dielectric constant or electrical resistance as measure
of relative humidity.
Ferroelectric ceramics such as Pb(ZrTi)03 (PZT ) can be used to either sense
or generate ultrasonic waves related to the direct and converse piezoelectric effect,
respectively. Sensors for this application have been prepared also from BaTi03
ceramics.
Actuators is the material or system in which there is a large, controllable
response to an applied stimulus. In general, externally controllable strain is fairly
difficult to achieve, except in the family of ferric materials where both domain walls
and domains are strongly coupled to applied fields /13/. Ferroelectric and
ferromagnetic materials contain spontaneous electric and magnetic dipoles below
the Curie temperature. Applied magnetic or electric fields affect the spontaneous
dipoles or the alignment of domains indirectly resulted in materials stain. Such
materials form the basis for many piezoelectric, electrostrictive and magnetostrictive
transducers /14/.
Finally, the development of "smart" or "intelligent" materials is a result of
understanding the relation between intelligence from the human standpoint,
intelligence at the most primitive levels in materials and intelligence inherent in
materials /12/. The primitive functions of intelligence in materials are elementary
function of sensing, processing and affecting (actuating), all of which must work
systematically together to create an intelligent material. In any way, future trends in
the field of smart materials will be directed toward combining several types of active
functions within a single package. One way that this is being certainly approached is
via multifunctional multilayer materials. Thin layers of the active materials, screen-
printed and laminated before sintering, can be prepared in desired geometry.
Multilayer piezoelectric and electrostrictive transducers are already well known and
are used in a wide variety of devices, including adaptive optic, active damping and
light-beam deflection systems /15/
INTEGRATED CERAMICS
One can easily conclude that the age of ceramic application is upon us.
Recently, it was known that multilayer ceramic packages consisted of dielectric
material strata with metallic circuitry printed on each layer and interconnected
through mettalized via holes between layers . Latter, new additional circuit elements
were added. Finally, in the past ten years buried capacitors and resistors have been
added to the three-dimensional packages /17/.
In near future it can be expected development in the field of integrated
ceramics, illustrated by following tree in Fig.6.11,3/. Smart sensors, ad active
actuators, ceramic packages with display panels, enclosed pointed units, and voice
modules are on horizon. Thus, to conduct these different functions it will be
necessary to incorporate a wide variety of sensors, transducers and actuators,
together with thermistors and varistors.
To process such electroceramic materials it will be necessary to prepare co-
sintered multicomponent ceramic packages involves a marriage of tape casting and
thick film technologies, augmented by photolithography, etching, sol-gel films. In
these multilayer packages, thick film conductors, resistors and dielectric have to be
screen-printed on green low-firing ceramic tapes to produce patterned circuitry in
single layers /16/. However, to process integrated electroceramics, it will be
necessary to develop paste layers, in fact photoinitiators compatible with each type
of ceramic component, especially for the ferroelectric materials as titanates and
niobates.
374
FERRITE
INDUCTORS
Fig 6. Shematic presentation of integrated ceramic" tree" /1/
SUMMARY
The Golden Age of electroceramic materials is in consequence of rapid progress

in the integration and miniaturization of ceramic components which led to the
development of multipurpose electronic packages containing complex thre e
dimensional circuit. At the same time, a wide variety of smart sensors, transducers,
actuators, varistors, thermistors, were constructed utilizing most frequent oxides
ceramics. At present, the processing methods make use of tope casting the thick film
technologies but new technologies loom is on the horizon . The age of integration
followed by the age of miniaturization has to lead to new ideas and new systems. So,
having in mind that integrated ceramic systems will reach limits, especially caused by
grain size, it will be necessary to make new optoelectronic systems with extremely
small feature size. To replace integrated ceramic packages with patterned thin film
systems is probably possible in near future , but in present, obviously it is the golden
age of sintered electronic materials.
ACKNOWLEDGMENT
This work was performed as part of project "Prognosis of Materials Properties

from the Viewpoint of the Triad SSP (Synthesis-Structure- Properties)" financed by
the Ministry for Science and Technology of Serbia . and the project "Investigation of
the consolidation process of materials" financed by the Serbian Academy of Science
and Arts.
375
REFERENCES
1. RE. Newnham, Th e golden age of electroceramics, Adv.Cersm.Soc., 3(1) :12 (1988).
2. R Stevens, Advanced ceramics-an overview, Ceram. Tech.Intem., 1:51 (1992).
3. S. Dos , R Curlee, Advanced materials needs: Survey Report, Ceram.Bull., 70(11):234(1991) .
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5. K. Utsumi.,Y. Shimada,T. Ikeda,H.Takanizava, Monolithic mult icomponent ceramics (MMC),
Ferroelectrics, 68:157,(1986)
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28 :21 (1996) .
8. H. Okinata, T. Hata, Varistor, thermistor manufacturing in Japan , Ceram .Soc.Bull., 74(2) :94
(1993) .
9. J. Fukuyama,T.Kubota , Multilayer chip NTC thermnistors, Sen s. Tech., 13: 12 (1993)
10. L.M. Levinson, Advanced in varistor technology, Ceram .Bull,68(4):866(1989)
11. Y. Sakabe, Dielectric material for based-metal multilayer capacitors , Cersm Soc.Bull., 66(9) :1 518
(1987).
12. RE. Newhnam,GC. Xu, S. Kumar, L.E . Cross , Smart cermics,Ferroelectrics ,102:1( 1990)
13. RE. Newnham, S.T.Mc-Kinstry, J.ApplCrystallogr.,23,447: (1990)
14. RE. Newnham, G .R Ruchau, Smart electroceramics, J.A.mer.Ceram.Soc.,74(3):463(1991)
15. H Yanagida,Intelligent materials, a new frontier,Angew.Chem. , 100:1443(1988)
16. HJ .H uijsing, Sens.Act.,A 30,167: (1992)
17. RE. Newnham, Composite electroceramics, J.Mater.Educ,7 :605(1992)
376
SINTERING OF ZoO DOPED S002
l
L. Perazolli' , R.S. Biscaro' , T.R. Giraldi l , E. Longo? and l .A . Varela
I Chemistry Institute, UNESP, P.O.Box 355,14801-970 Araraquara/SP, Brazil

E-mailleinig@iq.unesp.brandvarela@iq.unesp.br
Z Chemistry Dept., UFSCar, P.O.Box 676, 13565-905 Sao Carlos/SP, Brazil
ABSTRACT
Dense SnOz ceramics were obtained by doping with ZnO concentrations varies from
0.5 to 5.0 mol. The obtained powder was isostaticaly pressed to 210MPa in cylindrical
shape and sintered from ambient to 1.500C using constant heating rate of 10C/min.
Densities above 97% were obtained depending on the ZnO doping concentration. A
maximum density was reached with the addition of 2 mol%. It can be concluded from
shrinkage data and the observed microstructure obtained by SEM that the solid solution
limit for ZnO in SnOz is about 1.0 mol%. Above this concentration the formation of a
second ceramic phase is observed .
INTRODUCTION
SnOz ceramic is an n type semiconductor with tetragonal structure similar to the

rutile (TiO z). Due to its physical chemistry characteristics the SnOz can be used in the
production of gas sensors!", electric-chemical devices" , as well as electrodes for the glass
fusiorr'" and others uses. Excluding the gas sensor , the other applications for SnOz requires
good thermal and electric conductivity, and mechanical resistance , therefore, the ceramic
should be dense . Pure SnOz have little shrinkage when sintered. Because its high vapor
partial pressure at elevated temperatures evaporation-condensation mechanism should
dominate during sintering of pure SnOz. This mechanism does not promote densification
and can be represented by:
(1)
Aiming to obtain dense ceramics and to reach certain physical-chemistry pro~erties,

several additives such as Co07, MnOz7, Sb z038, Cu09 , Nb10SIO, CrZ031O, and Zn0 9 0 have
already been used as sintering aid. Compo sitions from 0,05 up to 5mol% have been tested.
Advan ced Science and Technology ofSintering, edited by Stojanovic et al.

The sintering kinetics of ceramic oxides has been studied by many authors and
Frenkel 11, firstly proposed a model for the sintering of materials by viscous flow. Ever
since, many approaches have been proposed basing on one or two sintering stages l2-20 and,
more recently, the sintering have been considered as a whole 21-22. The flow of the material
has origin in the surface, inside the particle or in the grain boundary , however, the destiny is
always to the neck and only diffusion paths through the crystalline lattice or by the grain
boundaries leads to the shrinkage .
The sintering kinetic studies can be accomplished by considering isotherms or by
using constant heating rate. For the second case the sintering process can be divided in
several stages, such as: heating stage; pre-initial stage; initial stage; intermediate stage and
final stage.
In the heating stage the vaporization of the volatile occurs and sintering promotes
oxidation and physical-chemical transformations without, however, the formation of necks .
In the pre-initial stage the formation of the necks occurs and shrinkage starts with a
structural rearran~ement mechanism of the particles due to the high capillary forces applied
on the necks I5-23- 4-25. The neck growth and densification characterize the initial stage. The
intermediary stage characterized by the rain growth and shrinkage as a coarsening process
and the final stage by the grain growthi" 7.
Woolfrey and Bannister!" developed a method for obtaining the sintering kinetics in
the initial stage by using constant heating rate and is given by the following equations :
T 2 dY = Q Y (2)
dT (n+I)R
Q == R1;1; In(~ I (3)

1;-1; ~)
being T the absolute temperature in Kelvin, Y the linear shrinkage (~lIlo), Q the activation
energy in l/mol and R the constant of the ideal gases in l/mol K.
Grigoryan et al9 and Paria et altO considered ZnO, as well as other oxides as sintering
additive for Sn02 ceramic s without making any indication of technological applications for
the studied oxides systems . Studies considering ZnO as sintering additive for Sn02 is rare
and practically nonexistent in the literature . This fact motivated this work that has as main
objective to obtain Sn02 ceramics in its dense form as well as to study the influence of the
ZnO concentration on the densification and grain growth.
For the accomplishment of this study 99% pure Sn02 (Merck) with surface area of
9.22 m2/g was used as well as 99,9% pure ZnO (Royalox Unimaua) with surface area of 5.0
m2/g. The powders were mixed and homogenized using zircon oxide ball mill in isopropilic
alcohol medium for 4 hours. The following compositions were adopted: 0.5, 1.0, 2.0, 3.0
and 5.0 mol% of ZnO . The powders were characterized by nitrogen adsorption/desorption
(BET method), termogravimetric and differential thermal analysis (TGIDTA). Then the
powders with different ZnO compositions were conformed in cylindrical shape by uniaxial
pressing at 15MPa and isostatic pressing at 2IOMPa. The obtained pellets were sintered in a
dilatometer furnace up to 1500C, using 10C/min as heating rate, in synthetic air
atmosphere. Archimedes method was used to determine the sintered densiti es. After
sintering the pellets were fractured and the microstructure were analyzed by SEM (scanning
electron microscope) and by EDS (energy disperse spectroscopy). Bannister method, as
378
o,02 "'T"T"T""T'"-e-r-,.......,........ "'"T""T"T"T..............-I"""T""'l"'"T""T"T"T ..............-......."'"T""T.,....,.."T""T'".......,.......,.........-.-....
0,00 J-----1IIIIIIIl1!!! ~-~--
-0,02
rft -0,04
Q) -0,06
Cl
l
~ -0,08
c
.>:
:E -0,10
en
~ -0,12
Q)
-0- - Sn0 2+O.5%ZnO
.s
....J
-0,14 --<>- -Sn0 2+ 1%ZnO
-~ - Sn0 2+ 2%ZnO
-0 ,16
- - - Sn0 2+ 3%ZnO
- 0 - - Sn0 5%ZnO
-0,18 2+
600 700 800 900 1000 1100 1200 1300 1400 1500
Temperature rc
(a)
__
0.0000-r----1II!Il!lI_~1!IIIllII~
-0.0002
~
o
__ -0.0004
Q)
a: .
(U -00006
~-0 .0008
l
~ -0.0010
s: -00012
en . -0- - Sn0 2+O .5%ZnO
.... --<>- - Sn0 2+ 1%ZnO
~ -0 .0014
c -~ - Sn0 2+ 2%ZnO
::J -0.0016 - - - Sn0 2+ 3%ZnO
-0- - Sn0 5%ZnO
-0.00 18 2+
600 800 1000 1200 1400

Temperature rc
(b)
Figure 1. Linear shrinkage (a) and linear shrinkage rate (b) obtained for the constant heating rate sintering of
SnOz ceramics, with different ZnO concentration in atmosphere of synthetic air .
379
described in equations 2 and 3, was adopted to determine kinetic parameters of sintered
SnOz based ceramics.
Figure I shows the linear shrinkage and the linear shrinkage rate results obtained in
SnOz pellets, doped with different ZnO concentrations, and sintered in a dilatometer furnace
using a constant heating rate sintering of IO C/min. Addition of ZnO up to 2 mol%
promotes densification of SnOz, whereas higher ZnO concentration inhibit the densification
as shown in Figure I a. Otherwise the linear shrinkage rate curves show a single maximum
only for 0.5 mol % of ZnO whereas for higher concentrations two maximums occurs,
indicating differential shrinkage probably due to precipitation of a second phase .
Table I summarizes the shrinkage data obtained from the dilatometric curves. It is
observed in this table that the temperature where shrinkage starts decreases with the ZnO
concentration, except for 5.0 mol% . However, the temperature for the maximum shrinkage
rate decrease with ZnO concentration up to 1.0 mol% and then increase for higher ZnO
concentration, in agreement with solid solution saturation. The maximum relative density is
achieved when 2.0 mol% of ZnO is added to the SnOz (98.3 %).
TABLE 1. Sintering results obtained by using constant heating rate of IO C/min in a dilatometer furnace by
adding different ZnO concentration in 5n02. Tinitial is the temperature for startin g densifi cation, T rna. is the
temper atur e for the maximum shrinkage rate, Q is the apparent activati on energy, G is the grain size and p is
the relative den sity .
Composition C
TiniliaJ / Tmax.l oC GIllm Q/kJ/mol pI %
0.5% 875 1270 4.6 525 95.0%
1.0% 790 1135 6.1 457 97.1%
2.0% 770 1190 6.8 125 98.3 %
3.0% 740 1205 6.0 135 97.0%
5.0% 755 1220 5.4 116 96.5%
4000 - - - . Sn0 2+O.5%ZnO

- - 0- Sn0 1.0%ZnO
2+
~ . Sn0
2+2.0%ZnO
- +- . Sn0 2+3 .0%ZnO
3000
--<>--. Sn0 .O%ZnO
2+S
i='
>: 2000
"C
:s.
N
I-
1000
0,00 0,02 0,04 0,06 0,08 0,10 0,12 0,14 0,16 0,18
Linear Shrinkage / %
Figure 2. Bannister plot for shrinkage data obta ined during const ant heating rate sintering (10 C/min) up to
l500C ofZnO doped 5n02 ceramics in synthetic air.
380
(a) (b)
(c) (d)
Figure 3. SEM micrographs for ZnO doped SnOz ceramic s sintered at constant heating rate up to 1500C:
(a) 0.5 mol% ZnO; (b) 1.0 mol% ZnO ; (c) 2.0 mol% ZnO; (c) 5.0 mol% ZnO.
Typical Bannister" plots are observed in Figure 2 for ZnO concentrations of 0.5 and 1.0
mol%. For 0.5 mol% ZnO doped SnOz the Bannister curve has only one maximum at about
6% of linear shrinkage, corresponding to the limit for the initial stage of sintering . For
higher shrinkage grain growth dominate the sintering . The addition of 1.0 mol% of ZnO to
the SnOz, however, leads to two peaks in the Bannister's curve due, probably, to the
formation of agglomerates or precipitation of second phase at the grain boundary.
Activation energies determined by using Bannister" approach in the initial stage of sintering
are also listed in Table 1. These values decrease with increasing amount of ZnO up to 2.0
mol%. This behavior is an indicative that more than one mechanism is dominating in the
initial stage of sintering. The addition of ZnO up to the solid solution limit (around 1.0
mol%) lead to formation of oxygen vacancy that would promote mass transport in SnOz
ceramics and densification. However, for higher ZnO concentration, a second phase is
precipitated to the grain boundary that inhibits densification and grain growth .
The evolution of the SnOz microstructure doped with ZnO after sintering by constant
heating rate up to 1500C is shown in Figure 3. As observed in Figure 3a, the addition of
0.5 mol% of ZnO leads to quite dense sintered sample (95% of theoretical density) with
intergranular and intragranular pores . Increasing the doping concentration up to 2 mol%,
denser SnOz ceramics is obtained with increasing mean grain size. For concentration higher
than 2.0 mol% the mean grain size decrease (Table I). This is due to the precipitation of a
second phase at the grain boundary that inhibits grain growth. This second phase,
determined by XRD as ZnSn03, is observed for samples with ZnO concentration higher
than 1.0 mol% and inhibit grain growth . Similar phase was also observed by Varela et al30
during sintering of CoO doped SnOz ceramics , where CoSn03 phase was characterized by
electron diffraction and EDS using TEM observations.
381
CONCLUSIONS
The addition of ZnO up to 2.0 mol% enhances the densification and grain growth of
the Sn02 ceramics due probably to extrinsic oxygen vacancy formation. Shrinkage data and
the microstructure indicate that solid solution limit for ZnO in Sn02 is near 1.0 mol%. ZnO
concentrations above 2.0 mol% inhibit grain growth due to precipitation of the second phase
ZnSn03, to the grain boundary.
Acknowledgement
The authors acknowledge CNPq, FAPESP, and FINEP for the financial support.
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804, 1996.
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20. B.Wong and J.A. Pasko J. Am. Ceram. Soc., 62 [3-4] 138-141 (1979).
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1217-1225 (1991).
22. J.D Hansen, RP. Rusin, M-H. Teng and D.L. Johnson. J. Am. Ceram. Soc., 75 [5]
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23. J.A. Varela and OJ. Whittemore. J. Am. Ceram. Soc. 66 [I] 77-82 (1983).
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25. Y.M. Chiang, D.B. Birnie III, and W.D. Kingery. John Willey & Sons, 2nd ed. New
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382
26. W.D. Kingery, H.K. Bowen, and D.R. Uhlmann. John Willey & Sons, l" ed. New
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27. P.A. Cox, R.G. Egdell, C. Harding, W.R. Patterson, PJ. Tavener. Surf.Sci, v.123,
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28. D.F. Cox, T.E. Fryberger and S. Semancik. Phys, Ver. B, 38 (3) 2072-2083, 1988.
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Ceramics Intern. (1998).
383
FAR INFRARED PROPERTIES OF BaTiO J CERAMICS
P.M.NikolW, B.D.Stojanovic l , SDuric', K.Radulovic l ,

D.Vasiljevic-Radovic!, VBlagojevic', D.I.Siapkas2, T.T .Zorba2
'Joint Laboratory for Advanced Materials of SASA, P.Box 745,

2Department of Physics, Aristotle University of Thessaloniki, Greece
ABSTRACT
Far infrared and mid infrared reflectivity measurements have been made at Ba'Iit),
ceramics at room temperature in the range between 10 um and 200 um. The Kramers-
Kronig analysis and a fitting procedure. based on a four parameter model ofthe spectrum,
determined the infrared active transverse and longitudinal optical modes. their damping
factors and the values of dielectric permittivity. Group theory analysis has been done and
the number of experimentally observed infrared active modes was compared with the
theoretical prediction . The calculated values ofthe parameters were comp ared for samples
produced with different technology treatment. The highfrequency dielectric permittivity (at
10/3 Hz) decreases from 5.13 to 1.88. for the BaTiO j samples sintered at 1320 OC for ten
and two hours, respectively. Similarly. the change of other parameters provides some
information about densification of BaTi0 3 ceramics. It was also concluded that infrared
optical reflectivity measurements could give reliable results at the boundary cases. when it
is difficult to distinguish if a material has either cubic or tetragonal structure.
INTRODUCTION
BaTiO) based ceramics are widely used ferroelectric materials for capacitors and
piezoelectric transducer devices .
The technology for producing these ceramics with optimal characteristics must be
very carefully conducted':'. The sintering temperature must be rather high (above 1300C)
and the samples should be kept for a long time, usually about ten or more hours at that
temperature. Recently, more attent ion is paid to doped BaTiO) single crystals where it was
confirmed that a polaronic mechanism can explain the temperature dependence of the
resistivity in BaTiO ) single crystals doped with Nb3.4.
In this paper far Infrared and mid infrared properties of BaTiO) were investigated
with the intention of showing that infrared spectroscopy work can give useful data
concerning the sintering procedure. Different infrared reflectivity and transmission spectra
Advan ced Science and Technology ofSinter ing , edited by Stojanovic et al

Kluwer Academic/Plenu m Publishers. New York. 1999 385
were observed when the sintering time or temperature were changed. Infrared reflectivity
diagrams of pure BaTiO) and BaTiO) doped with LiF have been also compared.
EXPERIMENTAL RESULTS
For the reflectivity measurements study of BaTiO) the samples were prepared by
homogenization of pure BaTiO) powders (Merck) mill for 120 minutes. The obtained
powders mixed with an organic binder (aqueous solution of 2% polyvinyl alcohol) were
dried in an infrared radiator and pressed at 400 MPa into pallets of 10 mm in diameter. The
samples were fired at 1320 C for ten hours. The sintering density was 78-83.5% of the
theoretical value.
Sintering of BaTiO) at 1320 C gave gray specimen. Fractured surfaces were glassy,
an indication of the high density and fine grain size. X-ray diffraction showed that there are
no other phases in BaTiO).
Highly polished BaTiO) samples were used for optical measurements. One sample
surface was polished with a diamond paste, whose grain size was 3 urn and a shiny
reflecting surface was obtained. Reflectivity (R) in the far infrared and infrared ranges,
versus wave number, at room temperature, was measured using a Fourier spectrometer
(Brooker 113V). The reflectivity diagram versus the wave number is given in Fig.I, where
it was easy to determine four ionic oscillators, including a very extensive one at
approximately 180 em".
1.0
BaTi0 T=13200C
3
0.8 --t=120min
-
. .. .. .. t=180 min
0.6 ~\. ~
>, "~ :! t=600 min
oS; """ .!\
:;::; -,
cQ) 0.4 <.
li=
~ 0.2
0.0
0 200 400 600 800 1000
wave number [ern"]
Figure 1. Reflectivity diagram versus the wave number for pure BaTiO) sintered on 1320 C for 600 min,
180 min and 120 minutes
For comparison, under the same sintering temperature (1320 "C), but with shorter
sintering time (two and three hours instead often) the samples of Ba'I'rO, were synthesized
and polished, The change of reflectivity diagrams versus the wave number, for these two
samples, are also given in Fig.I. Three ionic oscillators for each sample at almost the same
wave numbers, like in the case for properly sintered BaTiO) sample (at 1320 0c) were also
observed.
For further comparison we have made another BaTiO) sample which was sintered at
950C for 20 hours. The change of its reflectivity versus the wave number is given in
Fig.2 together with the BaTiO) sample sintered at 1320 C but for only 3 hours.
In Fig.2 a reflectivity versus the wave number is also given for a BaTiO) sample
doped with 5% LiF which was pressed and sintered at much lower temperature (950C)
during 20 hours.
386
,; - 8 a Ti0
3
T=1320oC 1=120min
,' :: 8aTI0 3 T=950oC 1=20"

0.8
~'-"" ': \" "- " " : 8aT103 + 5% LIF T=950oC 1=20h
0.6
C
'S;
:;::;
U
Q)
It: 0.4 ,, ,,
,,, ,,,
Q)
1
L..
,, ,,
"
I
0.2 ...."" ,
',' ,
~ : .:'." ..
~ .:
.,
", 4 , "~
0.0 +--.----,.---.---.---.-------,----;:s..:.....,....:.;:-.-~__1
o 200 400 600 800 1000
wave number [cm']

Figure 2. Reflectivity diagram versus the wave number for pure BaTiO) sintcred at 950C (20h) and 1320
C (120 min) and BaTiO) doped with 5% LiF sintercd at 950C (20\
DISCUSSION
A numerical analysis was performed by a method of four parameters, introduced by

Gervais and Piriou', The dielectric function is given as:
(1)
Experimental results were numerically fitted with the theoretically calculated curves.
The fitting program was developed in the program language Fortran (MS-Fortran v.5).
This program enables the user to choose the values of parameters in the mathematical
model. Practically all of the parameters used can be fitted. The user selects the magnitude
of the change of each parameter. If some parameter should stay unaltered then the change
of the parameter should be selected to be zero. The fitting error can be estimated using one
of the following criteria: (a) the sum of absolute differences between the experimental and
the calculated values; (b) the sum of the squares of the differences between the calculated
and the experimental values; (c) the sum of relative errors; and (d) the sum of squares of
the relative errors.
The values of parameters obtained by the fitting procedure for all mentioned samples
are given in Table 1. It is noticeable that the values of all fitted parameters for four samples
are rather similar. Only the sample of BaTiO) sintered at 1320 C for two hours was much
different, because sintering time was too short.
At first we could also notice that dielectric permittivity (1::,') for very high frequency,
compared with the range of measurements, given in Fig.3 as a function of the sintering
time, depends a lot on the technological procedure of the sample preparation. The high
frequency permittivity increases almost three times when the sintering time at 1320 C is
extended from two to ten hours.
387
Table 1. The values of parameters obtained by the fitting procedure
BaTI0 3 BaTI0 3 BaTi0 3 BaTi03 BaTI03+ 5% LiF

1320C; lOb 1320C; 3b 13200C; 2b 950C; 20b 950C; 20b
lose. WTOI 182.0 181.9 182.3 182.8 181.9
YTOI 13.4 6.2 12.8 6.35 4.8
WW! 183.9 183.8 183.2 184.5 183.8
YWI 17.7 8.0 12.5 7.7 8.2
II osc, W T01 388.0 394.5 281.1 39Q.4 398.2
YTOl 442.2 421.7 379.3 468.1 441.2
W L01 464.3 466.9 503.1 461.2 465.4
YWl 11.8 7.3 12.0 5.3 11.36
Illosc. W T03 483.9 472.5 505.8 488.7 486 .7
YT03 35.6 11.8 8.1 23.1 35.8
WL03 702.0 677.8 516.0 695.1 671.3
YL03 109.2 422.7 516.4 445.3 104.0
Ivosc, w TOO 689.0 687.9 687.9 687.9 671.6
YTOO 78.8 104.6 63.47 169.6 76.3
WW4 702.6 700.7 700.7 700.5 713.7
YW4 49.1 84.6 66.1 61.7 47.5
&.., 5.13 2.867 1.88 2.87 4.74
i?:'
.>
E 4]
E
...
Q)
o,
o
5
3
I
; "
/
BaTi0 + 5%LiF
3
B~Ti0 3
.-=:
..... /
J
U
Q) 2 j 0 T=1320 oC
~ T=950 oC
"0
1
0 200 400 600 800 1000 1200 1400
sintering time [min]
Figure 3. Dielectric permittivity diagram versus sintering time for pure BaTiO] and BaTiO] doped with 5%
LiF
This diagram shows that the reflectivity diagram could be an indicator of the sintering
procedure for BaTiO] ceramics. At the same diagram with asterisks are given the
permittivity values for the BaTiO] sample which was sintered at only 950C for 20 hours
and also for a BaTiO] doped with 5 wt % ofLiF , with a cross, which was sintered together
with the mentioned BaTiO] sample at 950C.
While the BaTiO] sample doped with 5 wt% of LiF has got almost the same
permittivity value as a pure BaTiO] sample sintered at 1320 C, the pure BaTiO] sample
sintered at 950C for 20 hours had practically the identical value of permittivity as a
BaTiO] sample sintered at 1320 C for three hours. This is in good agreement with the
change of reflectivity diagrams, versus the wave number, for these two samples, shown in
Fig.2.
388
In Fig.4 the experimental reflectivity curves (with dots) and the calculated curves
obtained with the fitting procedure are given for BaTi03 samples sintered at 1320 DC, for
ten, three and two hours.
10 I
0.8
~
.;; 0.6
:;J
o
Q)
t+= 0.4
Q)
L..
0.2
0.0
Figure 4. The experimental reflectivity diagrams and theoretical curve versus thc wave number
Using the fitted value of the parameters we calculated transmission diagrams versus
wave number, for all our samples. In Fig.5 transmission, versus wave number, is given for
BaTi0 3 samples sintered at 1320 "C. It is very obvious that the sample sintered for only 2
hours has got the ionic oscillator at about 460 ern", slightly moved towards the higher
frequency and also it is split into two peaks. This could be a very good indicator about the
degree of sintering processes.
1.0
0.8
c:
0 0.6
"00
en
'Een 0.4
BaTi0 3 T=1320 oC
c:
co 0.2 - - t=120 min
Z
....... t=180 min
0.0
t=600 min
0 200 400 600 800 1000
wave number [cm- 1j

Figure 5. Transmission spectra vs. thc wave number for pure BaTi03 sintcrcd at 1320 DC for 600 min, 180
min and 120 minutes
In Fig.6 the calculated transmission diagrams are shown for the BaTi0 3 sample
sintered for 3 hours at 1320 C (with dots) and for the BaTi0 3 sample sintered at 950C
for 20 hours (with full line). This diagrams (for the sample sintered at 950C) is split and,
in our opinion, indicates probably the presence of another phase which does not exist when
the sintering temperature was higher. We are going to do some further investigations to
clear this problem.
389
1.0
0.8
c
0
'(ij
0.6
en
'E
en
0.4
c
BaTi0
.=co 0.2 3
T=1320oC t=3h
0.0 - - T=950oC t=20h
0 200 400 600 800 1000
wave number [crn-t]

Figure 6. Transmission spectra vs. the wave number for pure BaTiO] sintered at 950 C(20h) and 1320 (120
min) and BaTiO] doped with 5% LiP sintered at 950C.
Here it is worthwhile to mention that long time ago (1969) Mazdiyasni et al.' and
more recently Ghoneim et a1. (1990)6 had observed the differences in the shape of the
transmission peak for BaTIO] at about 468 ern" which were much sharper when the
samples were longer calcined' at 700C or at higher temperature 6(1000 "C).
In addition to this discussion we would like to mention that infrared reflectivity
analysis could help in solving some structural problem which appears with the studied
ceramics.
It is well known that BaTiO] ceramic changes from a cubic (with space group Pm3m)
to a tetragonal structure (with space group P4mm) when the temperature drops below 120
C. It means that BaTiO] has a tetragonal structure at room temperature. The number of
infrared active modes for both crystal unit cells was calculated using Group Theory
Analysis and Adams Newton Tables1 For tetragonal cells and the space group P4mm there
are 8 active modes: 4A.+4E (parallel to the c - axis (A) or normal to it (E), respectively)
while for the cubic cell and space group Pm4m there are only 3Fu active vibration modes.
If 4 active infrared modes at room temperature, for BaTiO] + 5wt% LiF, were observed
(Fig.2), that material surely had a tetragonal lattice structure. This could be very important
for a material with a perovskite lattice, in the situation when it is very difficult to solve this
problem using only x-ray work.
CONCLUSION
In this work we have investigated and confirmed that infrared reflectivity
measurements and numerical analysis can provide interesting information about their
structure and the degree of sintering processes including their density.
REFERENCES
1. K.S. Mazdiyasmi, R.T.Dolloff and J.S.Smith, Preparation of High-Purity Submicron Barium Titanate
Powders , J.Am.Cer.Soc, 52(10):523 (1969).
2. W.Herth, Kinetics of Barium Titanate Synthesis, J.Am.Cer.Soc, 71:879 (1988).
3. C.Gillo~ J.P.Michenand, M.Maglione and BJannot, SoI.St.Comm., 84(11):1033 (1992).
4. C.Gillot and J.P.Michenand, Electrical Conductivity of Similarly Doped BaTiO, Single Crystals and
Ceramics in the Rhombohedral Phase, SoI.St.Comm., 90(1):23 (1994).
5. F.Gervais and B.Piriou, Temperature Dependence of Transverse- and Long itudinal-Optic Modes in Ti02
(Rutile), Phys.Rev., 10:1642 (1974).
6. N.M.Ghoneim, S.Hanafi and T.H.Salem, Effect of Calcination on Characteristics, Surface Texture and
Sinterability of Chemically Prepared Barium Titanate, J.Mat.Sci., 25:3241 (1990).
7. D.M.Adams and D.C.Newton, Tables for Factor Group and Point Group Analysis, Beckman - RIIC,
England (1970).
390
CHARACTERIZATION OF DOMAIN STRUCTURE IN BaTi03 BASED
CERAMICS BY SCANNING ELECTRON MICROSCOPY
Ljiljana M. Zivkovic, I Biljana D. Stojanovic' and Zoran S. Nikolic!
I Faculty of Electronic Engineering, University of Nis, Nis, Yugoslavia

2 Center for Multidisciplinary Studies University of Belgrade,
Joint Laboratory for Advanced Materials of SASA, Knez Viseslava 1A,
ABSTRACT
The domain structure and domain configuration in pure and modified BaTi03
ceramics compacts sintered at various temperatures have been investigated using SEM
technique . According to the topographical contrast at domain boundaries it has been
shown that the single domain and the banded domain structure, depending on the type of
BaTi03 and on the grain size, are present only in grains greater than 111m. The single
domain structure is the main characteristic of modified barium titanate, while the banded
domain structure prevails in pure barium titanate. The number of bands per grain depends
on the grain size, but their size, shape and orientation vary from grain to grain . Mainly
0
90 domains walls are present in both types of ceramics and the herringbone and square
net pattern are the most common configurations in unmodified BaTi03 . The wall
thickness ranged from 0 ,0511m to 0,1511m , while the domain width is in the range of
0,211m to 1,211m, indicating the decrease of domain width in ceramics with additives
compared to that one in pure BaTi03
INTRODUCTION
The ferroelectric behaviour of BaTi03 and related ceramics composites based on

BaTi03 has been investigated by many authors'". It has been shown that their electrical
properties are mainly controlled by barrier structure at grain boundaries and by the
motion of domain boundaries'". The knowledge of domain structure and domain motion
is of great interest particularly for properties tailoring of electronic components based on
BaTi03 ceramics. In sintered materials which undergo the phase transformation at Curie
temperature, from cubic to tetragonal one, the domain structures that develop, depend not
only on the processing but also on the type and distribution of additives and on the
obtained microstructure. As a rule, a fine grained microstructure is desired to achieve
Ad vanced Science and Technology ojSintering , edited by Stojano v ic et al

Kluwer Academic/ Plenum Publisher s. New Yor k, 1999 391
optimum electrical properties of BaTi03 ceramics. In polycrystalline ceramics a various
domain structures may be formed, but two types of domain structures are mainly
observed l 2 ,5,6 i.e. the simple lamellar and the banded twin structure with herringbone and
square net pattern domains. The single domain structure is usually associated with
homogeneous and small grained microstructure, while the domain banded structure
prevails in coarse microstructure. The observed configurations consist of two types of
domain walls, 90 walls which run parallel to [101] planes and are almost straight lines,
and 180 walls which can be described as " water marks" . The same types of domain
boundaries are also detected in semiconducting BaTi03 ceramics'". However, some
details of the unconventional 90 domain boundaries formed in modified barium titanate,
5
are reported by Y.H .Hu The dependence of a domain thickness and domain wall width
7
on grain size was the subject to many investigations' r'". V.S.Tiwari et a1l reported that
in modified (Ba,Ca)Ti03 , a 90 domain walls can appear even in grains smaller than
lurn and that the average domain width is nearly O,IJ,lm to 0,3J,lm. In semiconducting
lO
BaTi03 , G.Kastner et all demonstrated the existence of 90 domain boundaries down to
0,5 urn grain size.
In this paper the domain structure and domain configuration in pure and modified
(Ba,Pb,Ca)Ti03 ceramics, sintered at different temperature, are investigated by scanning
electron microscope in order to correlate the domain structure with obtained
microstructure.
EXPERIMENTAL
BaTi03 and (Ba,Pb ,Ca)Ti03 samples were prepared by conventional sintering

procedure. High purity oxide powders BaC03 , CaC03 , Ti0 2 and PbO and small
quantities of AST (AI203 , Si02 and Ti0 2) were used as row materials. The nominal
compos ition of modified BaTi03 ceramics was Ba, 84,Pb o 06 Ca, 10 Ti03 with 5 mol % of
AST. Before the calcination at 1050C the powders a~e milled for 30 hours. After
granulation the green pellets of pure BaTi03 and modified (Ba,Pb,Ca)Ti03 were sintered
at temperatures ranged from between 1240C and 1370C for two hours.
The microstructure was investigated by scanning electron microscope, JEOL, SEM 5300 .
For the exam ination of domain structure the samples were etched in 10% HCI with few
drops of concentrated HF.
During sintering of BaTi03 without additives, the discontinuous grain growth is

observed Fig .1 and the grain size ranged from 10J,lm to 20 urn at sintering temperature of
1240C. At higher temperature 1370C, the average grain size is from between 20J,lm and
50J,lm, although some larger grains up to 100J,lm are also presented. The polygonization
of grains together with the coalescence of pore define the microstructure of these
samples. Planar defects are also present due to the release of stresses induced into a
crystal during phase transformation.
After chemical etching, a typical configurations of ferroelectric domains observed in
pure BaTi03 by SEM are shown in Fig.2. As can be seen in Fig .2 a banded domain
structure is formed and the grains are subdivided by a set of parallel lines, some of them
consist of 90 boundary walls and others of 180 walls. It could be pointed out that most
of the grains remained in ferroelectric state with domain lines extended to the grain
392
boundaries. The herringbone and
square net pattern are clearly
visible in Fig .2a. From Fig .2b it
can be deduced that the domain
width varies within a single grain
having a constant value only
within a band domain. The
obtained configuration in pure
BaTi03 confirms that the domains
are formed under inhomogeneous
stresses due to the different
number of neighbouring grains.
The domain pattern Fig .3a can be
interpreted as ex -type domains of
Figure 1. SEM micrograph of BaTi03 sintered at 1240C, 90 walls, since they have the one
scale bar = lO~m . to one correspondence on both
sides of the long line. For this
type of domain is known to be a
3
most mobile and that may change its size under the influence of external forces .4.
The domain structure in BaTi03 sintered at higher temperature Fig.3b is similar, in
respect of domain configuration, to that ones obtained in specimens sintered at lower
temperature. The domain width in the specimens sintered at 1240C and 1370 C ranged
from between 0,50/lm to lum depending only on grain size and not on sintering
temperature.
(a) (b)
Figure 2. SEM images of domains in BaTi03 (a) herringbone structure, (b) square net pattern .
The quite different characteristics in microstructure Fig.4a and domain structure

Fig.4b are noticed in (Ba,Pb ,Ca)Ti03 ceramics . Firstly, the small grained microstructure
was observed, mainly due to the role of Ca as grain growth inhibitor. The average grain
size is in the range of lum to 3/lm although some larger grains up to Sum are also
present. One of the characteristics of the revealed microstructure in modified BaTi03 is a
presence of the needle shape grains randomly distributed in the matrix . The aspect ratio
of needle shape grains is approximately 5. The elongated grains together with some larger
regions in microstructure are free of domain structure. Secondly, according to the
topographic contrast the single domain structure is the predominant one. As it could be
seen from Fig.4b, the observed domain patterns reveal mainly the straight lines with 90
393
(a) (b)
Figure 3. SEM images ofbanded domain structure in BaTi03 sintered at 1240C (a) and at 1370C (b).
domain walls. The domain width in (Ba,Pb,Ca)Ti03 is in the range of 0, I urn to 0,31lm
and the domain walls thickness ranged from 0,051lm to 0,15Ilm .
In modified BaTi03 ceramics it was difficult to reveal a domain structure and the
absence of domains in grains lower than lum size is obvious. Apart from the chemical
etching inconveniences, it could be pointed out that the possible reason for domain
missing in a very small grains is the existence of cubic phase, which is paraelectric.
According to Takeuchi et aliI I the cubic phase is stable at room temperature if the grain
size in ceramics is lower then 0,8Ilm . Ohara l 2 stated that a long fibrous BaTi03 , obtained
by a hydrothermal reaction was composed of fine crystallites, average size about 270nm
of cubic phase .
In order to illustrate the correlation of a domain structure with grain size, the
dependence of a band domain size and domain width on grain size in BaTi03 without
additives is investigated . The band domains may have irregular shape with a tendency to
an almost random domain structure, therefore it is rather difficult to determine the right
size of them . The band domain is characterized by a band domain thickness and domain
length. The variation of domain band thickness with grain size is very small as compared
with variation of domain band length with grain size. Since the domain band width has an
average value of 51lm independent of grain size, in the present work the length of band
domain is taken as a major characteristics of band domain size. The results of the
observation of a large number of grains and their corresponding domain configurations
are given in Fig .5.
w ~
Figure 4. SEM images of (Ba,Pb,Ca)Ti03 sintered at 1340C (a) microstructure, (b) domain structure .
394
20 40 60 80 100
grain size titm]
(a)
1.2
1.1
.....
E
.....:1. 1.0
=
'C
'j 0.9
c
ns
E
0
0.8
'C
0.7
0.6
20 40 60 80 100
grain size fltm]
(b)
Figure 5. The band domain size vs grain size (a) and the domain width vs grain size (b).
From Fig.5a it can be seen that the band domain size can be separated into two
regions depending on the grain size, increasing linearly with grain size at different rate.
In a lower part of the curve, up to the grain size of 60jlm the band domain size is not to
sensitive to the variation in grain size. In larger grains the band domain size can be
compared with a grain size. The number of bands per grain depends with grain size, as
an example, in 100jlm grain size it can be 10 band domains having a domain boundary
lines extended to the grain boundaries. It is also observed that there is no a great increase
of a number of bands in grains whose size is in the range of 60-I00jlm. In Fig.5b the
dependence of the domain width on grain size for pure barium titanate pointed out that
395
two regions are also clearly separated. For grain size greater than 40llm the domain width
is nearly constant. The effect of grain size on domain thickness in investigated specimens
may be understood in terms of inhomogeneous mechanical stresses by adjacent grains.
For grain size greater than 40llm the effect of grain boundaries on domain width is less
pronounced. However, this analysis produces structure average information that reflects
changes in overall behaviour of materials. A more selective method is required to analyse
the behaviour of specific region in structure.
CONCLUSION
The investigation of domain structure, observed in pure and modified BaTi03

ceramics, pointed out that the domain configuration varies from grain to grain depending
mainly on the grain size. The single domain pattern is the main characteristic of the small
grained microstructure obtained in modified ceramics while the banded domain structure
is associated with a coarse microstructure such as obtained in pure barium titanate. The
domain width in (Ba,Pb,Ca)Ti03 is in the range of 0,1-0,3Ilm, decreasing with the
decrease of grain size. In (Ba,Pb,Ca)Ti03 needle shape grains randomly distributed
within the structure, are free of domain structure. Some regions in modified BaTi03
independent from grain size are also free of domains. In pure BaTi03 the dependence of a
band domain size and domain thickness on grain size can be separated into two regions.
Up to the grain size of 60llm the band size is not to sensitive to the variations in grain
size. In larger grains most of the domain boundary lines are extended from one to other
side of grain therefore a band domain size may be compared with grain size.
REFERENCES
1. G .Arlt and P.Sasko , "Domain configuration and equilibrium of domains in BaTiO) ceramics",
.LAppt.Phys., 51 [9] 4956-60 (1980).
2. G.Arlt. "Twinning in ferroelectric and ferroelastic ceramics: stress relief'. J ournal ojMat erials Science ,
252655-2666 (1990).
3. Z.Surowiak. E.G. Fesenko and J.Dudek, "Peculiarities of the domain structure of the perovskite-type
ceramic ferroelectric materials", Key Engineering Materials Vols. 132-136 (1997)pp. 1048- 105 1.
4. V.V.Aristov, L.S .Kokhanchik, K.P.Meyer and H.Blumtritt, "Scaning electron microscopic investigations
of peculiarities of the BaTiO) ferroelectric doma in contr ast", Phys. Stat. Sol. (a) 78, 229 (1983).
5. Y.H.Hu, H.M.Chan, Z.X.Wen, and M.P.Hanner, "Scanning electron microscopy and transmission
electron microscopy study of ferroelectric domains in doped BaTiO]" . J Am. Ceram. Soc., 69 [8] 594-
602 (1986).
6. B.M.Park and SJ.Chung, "Optical, electron microscopic , and X-ray topographic studies of ferroic
domains in barium titanate crystals grown from high-temperature solution", JAm. Ceram. Soc., 77
[12] 3193-201 (1994).
7. V.S.Tiwari, N.Singh and D.Pandey . "Structure and properties of (Ba,Ca)TiO) ceramics prepared using
(Ba ,Ca)CO) precursors: I, crystallographic and microstructural studies" , JAm. Ceram. Soc., 77 [ 7]
1813- 18-(1994).
8. J.D .Russell. C.Leach and RlFreer , "Grain boundary structures in electronic ceramics", Key Engineering
Materials Vols. 132-136 (1997)pp. 1155-1158.
9. C.H.Lai and T .Y.Tseng, "Investigation of resistivity and permittivity for (Ba,Pb)TiO ) PTCR Ceramics".
JAm. Ceram . Soc.. 77 [9J 2419-24 (1994).
10. G.Kastner, V.Hilarius, R.Wagner . W.BOrger, "Configuration of ferroelectric domains in semiconducting
BaTiO) ceramics", Journal ofMaterials Science Letters, 8 959-960 (1989),
11. T.Takeuchi, K.Ado, T .Asai, H.Kageyama, Y.Saito, C.Masqueiler and O.Nakamura, "Thickness of
cubic surface phase on barium titanates single-crystalline grains", J.Am. Ceram. Soc.,
77 [6] 1665-68 (1994).
12. Y.Ohara, M .Miyayama, T . Shimizu and H. Yanagida , "Barium titanate fabricated from fur-fibres" ,
Journal ofmaterials science: Materials in electronics 727-33 (1996).
396
FRACTALS IN CERAMIC STRUCTURE
Vojislav V. Mitic, Ljubisa M. Kocic, Ivona Z. Mitrovic
Faculty of Electronic Engineering, Beogradska 14, 18000 Nis, Yugoslavia
INTRODUCTION
Using combination of Euclidean and fractal geometry, the new structural configuration
model of BaTi03-ceramic grains is presented . The stereological configuration of the position
of Ba'I'rOe-ceramic grains and the influence of grain's displacement on contact surfaces is
studied . The model of structural pattern, containing a pair of grains is used . The contact area
size is of distinguished importance in grains structure. The intergrain contact area is a basis of
electronic processes in BaTi03-ceramics material':". Any contact area, between any two
grains can be seen as a geometry of a microcapacitor. Its microimpedance contains
capacitive, inductive and passive resistance components. On the other hand, any contact
surface, apart of the method being used can be represented as a function of mutual position
of grains and parameters of sintering process (pressure, temperature and sintering time).
Therefore, experiments were made by using the electronic microscopy method, with the
ceramic samples prepared under pressing pressure up to 150 MPa and sintering temperature
up to 1370e.
Classical (Euclidean) geometry is used for rough estimation of the spacial configuration
of grains, while the fractal method is applied on determination the finer details in the
intergrain contacts. The grain's shape is approximated by ellipsoid. In this way we can
generalize the Coble's two sphere model. The results can be applied on the real BaTi03-
ceramic grain contacts.
Starting by Akima method of piecewise polynomial interpolant we can represent any
part of the real grain surface by a smooth spline function. Using a subdivision method this
smooth surface patch can be converted into a fractal surface with the prescribed fractal
dimension. For the BaTi03-ceramic samples it was found' D:::2.08744 . In the last part of this
paper we examine enlargement of an Euclidean figure area affected by its fractal extension.
EXPERIMENTAL
The specimens for this study were prepared from "Murata" barium-titanate powder of
the following compos ition: 65.24% BaO and 34.70% Ti0 2 . The powder consists of
Advanced Scienee and Technology ofSintering , edited by Stojanov ic et al.

Kluwer Academic /Plen um Publishers. New York , 1999 397
agglomerates range from 10 to 120 J1.m. To investigate the influence of the grain growth on
the dielectric characteristics, the following pressures have been used: 86, and 105 MPa
(Figure 1). The specimens were sintered in a tunnel furnace type "CT-I0 MURATA" at
1240, and 1370C for two hours in air.
~ ~ K
Figure 1. SEM micrographs ofsintered BaTi03-ceramic samples: a, p=86 MPa , T,int=1240C, T,int = 2h;
b. P = 105 MPa , T,int=1370C, T,Urt = 2h (x5000).
DISTRIBUTION OF INTERGRAIN CONTACTS
The grainy structure of BaTi03-ceramics is so fairly complicated that any method of

classical geometry fails to describe it. In tum, the classical Euclidean geometry can be used to
approximate each grain globally. The object from this geometry that can approximate a grain
in a rough but still satisfactory way is ellipsoid. Two grains in contact, approximated by
ellipsoids, are shown in Figure 2. In this way, a BaTiOrceramic sample can be thought of as
a huge heap of"randomly" scattered ellipsoids throughout the sample's volume (Figure 3).
Figure 2. Contact of two grains in ellipsoidal approximation.
The word "randomly" is put under citation marks because we are not quite sure if the
distributions ofBaTi03-grains are totally random or not. In fact, we believe that it is not fully
398
Figure 3. Spacial configuration of grains ' distribution in R).
random . So, the function that describes the position of grains in the ceramic sample
(distribution function) contains some amount of information that can be considered as a
slightly controlled chaos . By making use of the characteristic function of some set A
I, x E A
XA(X) = {
0, otherwise
the distribution function will be given by the product F(1) =;LE! Xo (1), where
I
1 =[x y z] E R
3
is the space variable and {Gi: i E I} is the set of all contact zones in a prescribed volume V.
The function F: R 3 ~ R is a discontinuous at the points of surface of these zones . If we
extend the definition of gradient of such function by +00 at discontinuity points, it can be
used in definition of the surface that is the union of all surfaces of intergrain contact areas in
V. This surface is given by S = {r: [vF(f)! > I}, so that the volume of all contact zones in V
is given by
A = JF(f)dV. (1)
v
In fact, the distribution function F has also a fractal structure, but it is an open problem
to examine its properties. What is important is that F plays the crucial role in the study of
BaTi03-ceramic electric properties. This function expresses another distribution: location of
intergrain contacts in BaTi03-ceramic sample. In fact, the "unit level" of F is a superset that
contains the unit level of the function XS. The distribution function F and XS can be used for
reconstruction of the whole sample or the contact zones in it. Formula (1) can be an
important tool in electrodinamical evaluations of different phenomena in the sample.
FROM AKIMA TO FRACTAL INTERPOLAnON
In our previous works'" we have established an approximate fractal dimension of a

surface of BaTi03-ceramic grain . Typically, D ~ 2.08744 is the value with the error of the
method of about 0 = 0.4% . In further examination of intergrain geometry it is extremely
important to know how to generate and describe the surface of such a fractal dimension . One
method we offer can be based on some classical kind of approximation that will result with a
smooth surface, and then apply some perturbation in order to introduce irregularity. This
399
irregularity should be kept under control, moreover it should be limited between two fractal
dimensions D - 0 and D + o.
Akima method offractal interpolat ion is based on a two-variable polynomial of the form
3
P(x,y)= L apq xp .yq, (X,y)ED. ij (2)
p .q =O
where ~ij is the subsquare of the unit square ~ = [0,1]2, subdivided by the net [Xi, Yj]i.j = O,n
while the sixteen unknown coefficients llpq are to be determined by the values Z (Xa, YfJ), z,
(x.; YfJ), Zy (Xa, YfJ), Zxy (Xa, YfJ), a = i, i+1, f3 = j, j+ 1. Only the data Z (x.; YfJ) are known
(interpolating data) while Zx, Zy and Zxy are partial derivatives that should be estimated by the
method given by Akima 5,6. In fact, if we denote the divided differences of first and second
order by
i,j = 1'00 .,9

In the case that WI = W2 = and/or W 3 = W4 = 0, the singularity will occur and it will be
avoided by putting WI = W2 = 1 and/or W3 = W4 = 1. Now, the piecewise bicubic polynomial
(2) will be fully determined over ~ with second derivative being a smooth function . Figure
4a. shows a patch of Akima interpolant for the data [(Xi, yj, sin(3.24'Xiyj): i, j = 1, .. ., 10] on
~.
Figure 4. Grain surface: a. Akima interpolant as initiator; b. and c. Two stagesof subdivision algorithm
converging to the fractal surface (D :;;: 2.08744).
400
This model of ceramics grain surface can be applied both on the outer or inner (contact)
surface patch of the grain. Its advantage is in its compactness of analytical representation,
simplicity and simplicity of manipulation. So, it is convenient for an overall visualization of
the grain and for speed graphical transformations of its image. On the other hand, it is not
precise enough to describe a high level complexity of the fractal surface.
We will describe a method for generat ing fractal surface that will have a prescribed
fractal dimension. It is based on Akima surface interpolant that will be take as initiator 7. In
fact, initiator is a set we are starting from. This set is replaced by generator - a set having
simple construction suitable for an iterative procedure. Take a cell ~ij = [(Xi, Yj), (Xi+), Yj),
(Xi+), Yj+I), (Xi, Yj+I)] from the Akima subdivision and divide it by the diagonal [(Xi, Yj), (Xi+l,
Yj+I)] to obtain two triangular subcells ~ij' and ~it . Choose a point (s, t) E ~i/ by random .
Replace the patch P(x, Y)bij' where P(x, y) is given by (2) by the pyramidal construction over
~ij' with the height hij' (generator). Repeat the procedure for ~it with the height hi/' . Let
hmax = max {hi/ , h;(}. Then, by elementary calculations, it can be found that
h
m~
2 .J3
= - . ( 3 -~
2
D 1)
__
9 '
which, for D = 2.08744 yields hmax s:: 0.096316 . If we choose O<hij', hi/'<h max for each cell
and iterate this procedure, we will create a fractal surface with fractal dimension less or equal
to D. Increasing of hmax increases fractal dimension of the resulting surface. In each step,
algorithm will produce a piecewise linear surface that will converge (in Hausdorff metric) to
this surface . Two successive stages of this subdivision algorithm, starting by the Akima
surface is shown in Fig. 4b. and c.
AREA OF THE CONTACT ZONE
In previous section, it was pointed out that intergrain contact surfaces in a unit volume
are supposed to be scattered throughout the volume in the manner that may look random at
the first sight. We believe that it is not totally random. Our argument is the fractal dimension
of the grain surface D s:: 2.08744 that must appear in more or less changed value also in
other aspects of ceramic's structure.
Let us consider how the fractal nature of a surface increases its area. Exactly speaking,
the area of a bounded surface having fractal dimension D>2 is +00. But it is not the case in
the reality. Any physical surface has finite area . It is the same with the area of the intergra in
zone or outer surface of the grain. Suppose that the rough approximation of the contact area
is given by two coaxial ellipsoids' intersection . The resulting curve of intersection is an
ellipse, with the semiaxes a and b with the area abzr. By the analogy with the Coble's model 8
we expect an enlargement of this area by the area of the neck formed in the initial stage of
the sintering process . The spherical model can be transfo rmed into ellipsoidal by a
nonhomogenous scaling (x, y, z)-.(ax, {3y, yz) , a , {3, y E R, which is an affine
transformation. The main property of affine transformation is that it preserves ratio . This
means that the elliptical area with the semi-axes a, b will be enlarged for the same ratio as the
circle in Coble's model. So, the contact surface area will be (Y2 a)(V2b)7T = 2ab7T.
From Mandelbrot 's book', it is known that the relation between length and the area of
some fractal object can be considered as L IID = K I12 .A II2 , where D is its fractal dimension and
K is a constant. Also, from the Richardson law, the length of some fractal object (of
dimension D) depends on the measure unit E, and it claims that L = EI.D.Together, above
formulas give
40 1
2{I-D)
A(D) = K c- D- , 2 <D<3,
where K can be determined by the boundary condition A(2) = 2ab7l' which yields K=2ab7l" e .
Therefore,
2-D
A(D) = 2ab7l'cD , 2 <D< 3,
is the formula that gives approximate area of an elliptical "disk" having fractal dimension D.
Obviously, if the disk is flat (D=2) and has no fractal structure, it will be A=2ab7l' which is
correct, since the area linearly depends on the scale used. But, in the case 2<D<3, it depends
on the precision e that we want to use in representing this fractal set. So, for D=3,
A=2ab7l'c- 1I3 , and if e -) 0 A-)+oo. Practically, this means that a very irregular surface may
have very large area if it is measured precisely enough.
CONCLUSION
In this paper we review authors' recent results concerning the stereology of BaTi03-
ceramic structure and add some new. The new results include the conjecture of the twofold
appearance of the fractal geometry in this structure. One is concerning with the grains' shape,
which is experimentally proven to have the fractal (or Hausdorff) dimension of the grain's
surface D "" 2.08744. Here we introduce an initiator-generator algorithm that gives a fractal
surface using the Akima interpolant as an initiator. Further, we conjectured that the function
describing spacial distribution of the intergrain contact zones is not a totally random function
(in which case D=3) but a function that contains an unknown amount of "order" which is
also reflected in fractal dimension D<3. Up to this time we do not know the value ofD, but
at least we give its global description using characteristic functions.
Also, we give formulas for fractal correction of the area of the surface having fractal
dimension D. This correction makes the amount of area bigger which can explain some
microelectric properties ofBaTi03-ceramics.
REFERENCES
1. V.V. Mitic. The optimization ofinterrelations ofmicrostructure and electrical properties ofBaTiO r
ceram ics, Ph. D. Thesis, University of Nis, Nis, (1995).
2. V.V. Mitic, l .S. Nikolic, Lj.M. Kocic , M.M. Ristic , Dielectric Properties ofBarium-Titanate Ceramics
as a Function ofGrain Size , Advancesin Dielectric CeramicMaterials, Ceramic Transactions,
Volume 88,215-223, (1998).
3. V.V. Mitic, Lj.M. Kocic, M. Miljkovic, I. Petkovic. Fractals and BaTiOrCeramic Microstructure
Analysis, Mikrochim. Acta 15, Springer-Verlag (1998).
4. V.V. Mitic, Lj. M. Kocic, I.Z. Mitrovic, M.M. Ristic, BaTiOj-Ceramics Microstructure Controlled Using
Fractal Methods, 100th Annual Meeting and Expositionof the American Ceramic Society, Advanced
Ceramic Materials, ElectronicDivision, Cincinnati, Ohio, USA, May 3-6, (1998).
5. H. Akima. A new method ofinterpolation ofsmooth curve jitting based on local procedures, 1. ACM 17,
589-602, (1970).
6. H. Akima. Algorithm 474. Bivariate interpolat ion and smooth surface jitting based on local procedures,
Comm. ACM 17,26-31 , (1974).
7. B. Mandelbrot. The Fractal Geometry ofNature, W. H. Freeman and Co., New York, (1983).
8. J.H. Chen. P.F. Johnson. Computer Simulation ofInitial Stage Sintering in Two-Dimensional Particulate
Systems, P.E. Russell, Ed., Microbeam Analysis, 405-409, (1989).
402
THE INFLUENCE OF HEATING RATE ON
SINTERING PROCESS OF BaTi0 3 CERAMICS
V.P .Pavlovic 1 ,V.B .Pavlovic2 , B.D .Stojanovic 3 , T .Sreckovic 3 ,

BvMarinkovic'' , M.M.Ristic 4
1) Faculty of Mechanical Engineering, D epartment of Physics,

2) Faculty of Agriculture , Dep artment of Physics , University of
Belgrade
3 ) Center for the Multidisciplinary Stud ies , University of
Belgrade
4) Serbian Academy of Sciences and Arts , Belgrade
ABSTRACT
Ceramic materials obtained on the basis of BaTi0 3 and its related

compounds are of great importance for their fundamental and mod el
aspects . In order to investigate the influence of he ating rate on sintering
process of BaTi0 3 ceramics, tribophisicaly activated powders of 50mol %
BaC0 3 and 50mol % Ti0 2 , were pressed , calcinated and sintered with
different heating rates (4C/min., lOoC/min . and 30C/min.) up to 1300 0 e
for 2h . Heating process was studied using dilatometer. The samples were
analyzed by X-ray diffraction. Changes of dielectric properties were
correlated with changes at different structural level s.
INTRODUCTION
Materials fabricated on the basis of barium-titanate and its related

compounds hav e found many applications such as multilayer capacitors,
piezoelectric ceramic transducers devices , PTC resistors , mak ing it one of
the most important ferroelectric ceramics. Progress in the processing of
these materials, both at the powder synthesis stage and subsequent
densification to solid components , is caused by increasing demands on the
quality of electronic ceramics . Sintering process is generally improved by
Ad vanced Science and Technology ofSintering, ed ited by Stojan ovi c et al.

Kluwer Academic/Plenum PUblishers, Ne w York, 1999 403
liquid phase sintering at temperatures above 1320C for titanium rich
BaTiO) or at lower temperatures with sintering aids!" . Also, tribophysical
activation of initial powders BaC0 3 and Ti0 2 has influence on structure and
properties of BaTi0 3 cerarnicsv". The objective of this paper is to
investigate the influence of heating rate on sintering process of BaTi0 3
ceramics.
The BaTi0 3 ceramics were prepared using the mixture of 50mol%

BaC0 3 (Merck p .a. 99%) and 50mol% Ti0 2 (Ventron p.a . 99,8%) . Powders
were homogenized in planetary ball mill (l20min), activated in high energy
vibromill (90min) and pressed at 400MPa . After calcination at 800C for lh ,
samples were sintered with different heating rates (4C/min, lOC/min and
30C/min) up to 1300C for 2h. The samples were analyzed by X-ray
diffraction . Sintering process was studied using dilatometer. The dielectric
constant and dielectric losses were determined as a function of temperature
from 20C to 1300 C.
As shown in Fig 1. the shrinkage rate shows some general features for
all heating rates . On the base on our previous results!" obtained from the
-2
-4
-6
':!( -8
"'"
0
.....l
'<, -10 . . ' ~.
d "
f.:
-12
!:'
-14
-16
-18
-Xl
400 600 800 1000 1200 1400
']( OC)
Figure 1. Dilatometric curves for different heating rates
404
DT A measurements, it can be concluded that for all heating rates at
temperature of 850C starts decarbonization process of BaCO). It can be
also observed that for all heating rates process of the solid state reaction
between BaO and Ti O, starts at the same temperature (970C). This process
is followed by another shrinkage rate and it depends on heating rate .
The minimum of the dilatometric curve correspond to the end of the
solid state reaction and it occurs at higher temperatures as the heating rate
increase . These conclusions are in accordance with XPRD analyze (Fig.2.)
which indicates that the solid state reaction between BaO and Ti O, ends by
formation of tetragonal BaTiO) form . Further decreasing of densities of the
samples at temperatures above the temperature of solid state reaction
(Fig.I) is probably caused by the change of the volume of unit cell lattice,
which is also observed by XPRD analyze . It can be also noticed that there is
a significant influence of heating rate in temperature range above
temperature of solid state reaction (Singed by dashed lines in Fig . 1.), but
further investigations should be led to explain the nature of these type of
process .
Dielectric measurements that dielectric properties of the samples arc
influenced by heating rate . As a result of increasing of heating rate Curie
temperature increase from 106C for the samples heated with the heating
rate of l O'<Cmiin to 121C for the samples heated with the heating rate of
30C/min. Taking into consideration the fact that the higher the heating
rate the more internal stress survive to higher temperatures, increasing of
(101) (110)
(111) (211)
I
(200)
r
(002) ! (202)
~") I
(001) (100) I I
[ (310) (312)
J
(lOZ)
f!\
03
'fr..113(31.1)(2.2 nIi
'I. ~~.~ L;
............ "-',4.. A I )1
( 2B)
fI . i",
1 I.2)(203)
I: _,, :\ JJ .
o 20 40 60 80 100
2S
Figure 2. Diffraction pattern of the tetragonal BaTiO} sample sintered with

heating rate of 30C/min.
405
1800
I--
.
E 1600
r - . -100 /min
1400 . -- 300/mi n I ...,
-ill
I
/ "
1200
1000
.----
....
800
600
. --.--.---.---.----
.e
ee
.#.'.
e---e- ----e- -e---e--- .----
400
20 40 60 80 100 120 140
Fig ure 3. The temper a ture d e pend en ce of E, sin te re d with different he at in g r at es at

1300C fo r 2h
th e Curie temperature with in cr e asing o f he atin g rat e is not o nly caused by

different cia rati o but al so wit h different qu ant it y of the remain ed
microstress. At t he sa me time , fo r a ll he atin g rat es t he values of E, rema in
rath er low. The lo w val ues of E, a re ob tai ne d owi ng to th e lo w
den sif icat ion , whi ch is the con se quen ce of th e rel at ive ly hi gh he a tin g ra tes
a nd sho r t sinter ing tim e .
CONCLUSION
The shrinkage evolu tio n and diel ectric prop erties are stron gly
dep enden t on th e he ating rat e . For a ll o bse rve d heating rat es sintering
occ urs in se ve ra l ste ps; decarb on izat ion proc ess of Ba CO) , so lid sta te
re acti on betwe en BaO and Ti O , and den sificat ion proc ess owing th e ch an ge
of cI a ratio. In cr e asing of the Curie temp erature with increasing of he ating
rat e is not probably caused o nly by different cI a rat io, but a lso with
different q uantit y of th e remained microst ress.
REFERENCES
1. V .Pav lovic,B .S to janov ic, Lj .Zivkovic , G .Bra nkovic , M.M .Ris tic , " G rain growt h during
sinte ri ng of BaT iO) wit h LiF" , Ferroe lectrics 186:165-168 , (1996 ) .
2. B.D .St oj an ovic, VPav lovic , S.Du ric, B.Mari nk o vic , M.M. Ris tic, " Die lec tric properti e s
o f bari um-titana te sinte red fr om triboph ysicaly acti va ted pow ders " ,
Electroceramics VI ' 98 ( 124) Abs trac t book , Mo ntreux , Switze rla nd ( 1998) .
3. B.D.S toj a novic, VPav lo vlc , B.Ma rink ovic, M.M .Ris tic , " Infl ue nce o f tribophysical
activation on structure and p ro pe r tie s of BaTiO) ceramics" CIMTEC '98 (40 ) Book
of abstrac ts , F lore nce, It al y ( 1998) .
406
MICROSTRUCTURAL CHARACTERIZAnON
BaTi0 3 - COMPOSITE CERAMICS
Vesna Paunovic, Dimitrije Stefanovic.Ljubomir Vulicevic and Violeta Dimic
Faculty of Electronic Engineering

Nis 18000 , Yugoslavia
INTRODUCTION
Composite materials constitute , at present, the object of extensive researsh and

development. Ceramic composite s a variety of ceramics which seem to be very promising
for specific applications .
Phenol based composite materials can provide the following key properties : high-
temperature resistance , flame and arc resistance, resistance to chemicals, high surface
hardness, moduls retention at elevated temperature , good electrical properties and
relatively low unit costs.
Piezoelectric composites of ceramic and polymers represent a new family of materials
which now are attracting a groving interest.
In this study, the composite based on bariumtitanate and novolac is synthesised . This
composition could not be designed as a commonly produced molding compound of novolac
matrix with ceramic powder as disperse phase because in this case the disper se phase play
an active role.
Composites of piezoelectric ceramics and polymers are two-phase materials in which
the ceramic produces the piezoelectric effect while the polymer phase reduces density and
permittivity of the material and increases loss factor. The first phase, active phase, is a
ceramic powder , and the second phase is polymer. In a composite the resulting properties
depend on the volume fraction and characteri stics of the components and on the way in
which they are interconnected. The connectivity of a composite is defined as the number of
dimensions in which each component phase is continuous .
The properties of composites depend on the way of connectivity of their phases. It
points to the particular physical or chemical properties are used to illustrate a sum, product
properties or combination of properties for particular constitutive phases.
Advan ced Science and Technology ofSintering, edited by Stojanovic et al.

Kluwer Academic/Plenum Publishers , New York, 1999 407
EXPERIMENTAL WORK
BaTi03 powder is synthesised by the high-temperature reaction in the solid phase

starting from precursors BaC03 and Ti0 2 (BaO:Ti0 2 = 1.(05). Precursors are homogenised
as a water suspension in a ball mill (A1 203 99.9%). Calcination has been carried out in the
tunnel furnace at I320C/min. The powder pressed in a steel die in the form of round
tablets and than isothermally sintered under various conditions. On this way the sintered
samples with 90-96% theoretical densites were obtained, as shown by Upadhyaya I . BaTi03
ceramic, sintered at the temperature 1380C and in the continuous time 240 min, are
characterised by constant value of dielectric constant E,= 1800 and tg8=O.610-4 in the
working temperature region 2510C.
A phenol novolac is prepared by polycondesation process from resin with appropriate
molar ration of phenol, and aqueus solution of formaldehyde . The po1ycondesation has
been carried out in vacuum.The starting components a waning up with appropriate acid
who is added as a catalyst. Novolac sample (0% BaTi0 3) is obtained in the form of
cylinder with diameter D = 14.94mm and thickness of d = 1.05 because of determining the
electrical characteristics: C =6.9pF, E, = 4.5 and tg 8 = 0.04.
BaTi03 powder with particle size below 100flm is used as inorganic phase. Powder
mixture of ceramic and novolac powders are mixed together and hot pressed at 162C /
15MPa. Various hot-pressed composite samples are polarised at 25C and 6V by silver
electrodes . Composite samples in the form of cylinders with diameter D = 15mm and
thickness of d "" 3.5 mm, as showen by Hi-Hisiano 2 . Dielectric properties were measured
on a 4262 LCR meter and HP 9194A device and similar results are obtained .
Chemical etching is most comonly applied technique for producing microstructural
contrast. Etching proceeds by selective dissolution according to the electrochemical
characteristic of the component areas. The silver electrode of electronical component were
chemical etched by the solution of HN0 3:H2S04= 1:9.
Only features which exhibit a significant diference in reflectivity ( 10% or greater) can
be viewed without etching. The surfaces of BaTiOrnovolac were etched chemically by the
solution of 90% HCl : 10% HF. Preventing the charge-up on the specimen under
observation by covering the nonconductive material. Increasing secondary electron
emission by covering the specimen surface with little secondary electron emission by
covering it with a metal Au coating. Composite samples are examined by scanning electron
microscopy with JEOL - ISM-T20.
The dielectric constant of BaTi03 multilayer capacitors decreases substantially under

high voltage fields, often by 100% or more. Selecting appropriate can exceeded mentioned
shortage second (matrix) phase so that at as obtained composite values for permitivity are
field-independent.
Various sintered BaTi03 ceramic samples are polarized at 110C and 1.5 kV/mm.
Values for dielectric constants (s.) and tangens of angles of dielectric losses (tg8) before
and after polarization are also measured. At polarised ceramics is noted raise of dielectric
constant and capacities in the vicinity of Curie temperature and decreasing of tg8 because of
increasing of resistance (figure I) what resulted from defect anihilation in the vicinity of
grains boundaries and pores, as shown by Tanaka 3 . Formation of defects during ceramic
polarisation follow to creating of interior fields whose prevent "hoping" effect of current
conducting. Loss factor tg8 of polarised samples is lower than at nonpolarized ones.
Ceramics are often porous and contain cracks and therefore should be impregnated with a
resin to preserve the speciement.
408
12000 - 1000 140
120
10000 800
C- 100-0
C- 8000 ..I<i
80----
~ 600
..I<i
"""' ~
;:; 6000 ~
4000
't 400 - ~
- 60'-'
~
'-' 40
2000
a. 200
20
0 0 0
70 80 85 90 95 70 80 85 90 95
BaTiO J (OJo] BaTiO J (OJo]
(a) (b)
Figure 1. Dependenc (a) R and (b) p vs BaTiO) content of hot pressed ceramic samples before and after
polarisatino
Novolac isn't polarised and all changes connected with polarisation are the same as in
the case of pure BaTiO J , as shown by Stefanovic 4, i.e. the dielectric constant E, has been
changed insignificantly because the ferroelectric fields, in the arrays of used fields of
polarisation, have the same slope. Otherwise, e, has been changed as the logarithm function
In Er = 0.0450013 (%BaTi0 3 ) + 0.8884.
Microstructural changes in samples hot-pressed are examined by scanning electron
5
microscopy of untreated, chemically etched and fracture surfaces, as shown by Miljkovic .
In the observed chemically etched surfaces of specimens BaTi03-novolac composites,
presented grains are small sizes in order to be clearly observed ones uunder low
magnifications (here, magnifications up to 7500 are used). From the observed specimens
are noticed particle grains of irregular form which dive into the dark-gray substance of
novolac. The fracture surfaces were observed which are yielded by the fracture of sample
by axis being normal to the basis. The fracture surface reveals that the grain size bulk is in
the range between 1 urn to 100 urn and those grains have so-called terrace structure. The
large difference in grain size was observed at hot-pressed (162C) samples, although the
smaller grains prevail. Also several features of the observed microstructure in BaTiO J -
novolac specimen should be noticed. On the photomicrographies permeating of grain
boundaries are noticed as and appearance of increasing pores what is the consequence of
their coalescence (figure 2 - the photomicrostructure 95% BaTi0 3) .
By observing specimens micrographs it can be concluded that the dark-gray substance
of novolac "wet" the grains and the most part of sample the grains are separable (fig.2b-
thephotomicrographs 70% BaTi03). Nonhomogeniety in composition point to differences in
hardness of particular regions. Larger and smaller irregular regions of solid matter like
agglomerates can be also observed (figure 2a). With increasing percents of the BaTi0 3
content in composite it's noticed the pores which round, nearly regular form.
In recent time, the consolidation of ceramic powders on the base of BaTi0 3 has a great
importance, especially from the point of view of electrical characteristic of BaTiO r
novolac. The purpose of the present investigation was to correlate the effects of the
percentage of BaTi03 in novolac with the dielectric characteristics of as obtained
composites (figure 2).
409
250
;~~~ ',' ~~,~ .f(

experimental
200
....~ ~ ., "" '.t
~:,~ -"..:,1:. :; .,.~.,
150
100
50
o
70 80 85 90 95
BaTiO,I%1
(a)
20
15
5
"-:":"':~
')._") .
. 'It .
' ./ . after before
1_.. ."' .... ~ I . "_.
O-+-------r----.,.-----,--- - - , - - -
70 80 85 90 95
BaTiO,I %1
(b)
Figure 2. Depedance (a) E, and tg I) vs BaTiO) content of hot pressed ceramic samples before and
afterpo larisa tion
410
CONCLUSION
The dielectric properties of BaTi03-novolac composite are determined by ferroelectric

properties of polycrystalline BaTi03 and microstructural characteristics such as grain size,
porosity, BaTi03 particle distribution, internal defect and stresses. Since BaTi0 3 has a wide
region of application, the understanding of relation between microstructural features and
electrical characteristics, as the dielectric constant, loss factor and specific resistivity , are a
very important.
REFERENCES
1. G. S. Upadhy aya, Sintering ofreal systems, Science of Sintering, 27 pp. 45-152 . (1995),
2. Hi-Hisiano, Dielectric properties and ferroele ctric domain of BaTi0 3 powders, l ap. J ofApp/. Phy .
Part 1,32:5029 (1993) ,
3. I.Tanaka and G.Pezzotti , Evulation of slow crack growth resistance in ceramic for high-temperature
applications, JAm. Ccrsm. Soc, 75: 772 (1992),
4. D.Stefanovic, V.Dimic , M.Radmanov ic, D.Mancic , L.Lukic and Lj.Vulicevic, BaTi03 Ceramics-
synthe sis for piezoelectric transducers, Science ofSintering, 28 : 51 (1996).
5. M. Miljkovic, V. Mitic , and Lj. Zivkovic, Characterisation of BaTi0 3 microstructure by SEM and EDS
analys is, EMAS '96, Balatonfued, Hungary, (1996) ,
411
SEMICONDUCTING PROPERTIES OF
DOPED BARIUM-LEAD-TITANATE CERAMICS
B. D. Stojanovic,' T. V. Sreckovic,' V. B Pavlovic ,'

3
B. A. Marinkovic,' Z. Preradovic
lCenter for Multidisciplinary Studies University of Belgrade,

Joint Laboratory for Advanced Materials of SASA, Yugoslavia
2Faculty of Agriculture , Department of Physics,
University of Belgrade, Yugoslavia
3IRITEL , Belgrade , Yugoslavia
ABSTRACT
Donor-doped barium titanate based systems are widely used semi-conducting

materials. It is well known that different tehnological processes distinctly influence the
microstructure and electrical parameters governing the characteristic increase of resistivity
above Curie temperature - PTCR effect. Having this in mind, in the present investigation
the identical mixed-oxides route for powder preparation and two-steps firing for various
systems was used. High purity BaC03 , TiO z, PbO, Al z0 3 , SiOz oxide powders as raw
materials and Sbz0 3, MnS04HzO, and ZnO as dopants, were homogenized in three steps to
obtain a mixture with the desired composition. After calcination, milling and pressing, the
samples were sintered at various temperature for two hours . Studies of phase compositions
and crystallographic data, after calcination and sintering, using X-ray powder diffraction
were done. Possible variation of stoichiometry, caused due to volatilization of lead during
firing processes and influence of stoichiometry on PTCR effect was examined. Th e
resistivity temperature profile with characteristic values of resistiv ity, Curie temperature
and temp erature coefficient were shown .
INTRODUCTION
Barium titanate has attracted much attention in the field of electronic ceramics.
Donor doped barium titanate systems have been widely used semiconducting
materials in the last three decades . The characteristic rise of resistivity near the
Curie temperature the so - called positive temperature coefficient of resistivity
(PTCR effect) has resulted in the wide use of semiconducting ceramics in electronic
devices, especially for temperature controlling, temperature sensing and energy
. 1
convertmg systems .
Adva nced Science and Technology ofSintering , edited by Stoj anovic et al.
This anomaly of resistivity was first explained in terms of a temperature
dependent Schottky grain-boundary potential barrier originating from a charge
accumulation due to grain surface acceptor states' compensated below the Curie
point by the spontaneous bulk polarization' . Meanwhile, this model has often been
questioned because many experimental observations indicate deviations from the
simple predictions of this theory". In particular, the results of different authors can
difficulty to draw a consistent view of PTCR effect because different technological
processes distinctly influence the microstructure and electrical properties.
In this paper, the problem of semiconducting properties has been discussed in
terms of interpretations of the experimental results, but not only on the basis of
observations of the grain boundaries effects. These investigations have to provid e
further information about semiconducting properties of barium-lead-titanate
systems.
EXPERIMENTAL
High-purity BaC03, CaC03, Ti0 2, PbO, A120 3, Si02 oxide powders as raw
materials and Sb203, MnS04H20, ZnO as dopant were homogenized in three steps
to obtain mixture of general composition Bao.84Pbo.16Ti03 + a(AI 203) + b(Ti02) +
+c(Si0 2) + d(Sb 203) + e(MnS04H20) + f(ZnO), where a, b, c, d, e and f represent
the molar contents as follows: a = 0.02; b = 0.015; c = 0.0015;d = 0.006; e = 0.0008 and
f = 0.001.
Powders of proper compositions were weighed and mixed using a plastic jar and
alumina balls in deionized water for 30 hour. The powders were formed by pressing
in briquettes and calcined at 1050 C for 1 hour in air and then remilled with
deionized water containing 1.5 wt % polyvinyl alcohol. After drying the calcinated
powders were granulated by sieving. The green pellets were formed by pressing the
granulated powders with initial density of pellets Pi =3.5 g/cm3. The samples were
sintered for 2 hour at 1320 C and 1380 C in air (sintered density was in the range
5.1 g/cm3 to 5.8 g/crrr' ), in one case covering with calcinated powder, and in another
uncovering.
The phase and microstructural analysis by X-ray powder diffractometry
(Phylips Analytical - PWl710) was done.
Electrical properties were determined on the two type of samples (covered with
calcinated powder of mixture and uncovered) as a function of temperature in the
range from 20 C to 220 "C, in two series of measurement. The Curie point was
determined using differential scanning calorimetry - DSC analyzer (DSC-50
Shimadzu)
The preparation of semiconductive barium titanate ceramics through the use of

controlled - valence substitution and the occurrence of a large positive temperature
coefficient anomaly (PTC anomaly) in the electric resistivity of such materials were
first reported by Haaijman et al.s. Subsequent extensive studies were carried out by
Saburi et al." who ascertained that the onset of the resistivity anomaly with the Curie
point of the doped (Ba,Pb )Ti03 ceramics occurred at higher temperatures than for
BaTi03 alone .
Among the modified BaTi03 compositions, the Bao.84Pbo.16Ti03 system has
attracted considerable attention. The partial replacement of barium by lead is
414
reported to improve the electromechanical behavior, increase the temperature range
of stability of the tetragonal phase, and inhibit the formation of the unwanted
hexagonal phase of BaTi03. Hence, shifts the semiconducting region of doped
BaTi03 based ceramics to higher values of electrical resistivity are caused by the
compensation effect of acceptors over donor ions'.
Taking into account such literature data, the formation of doped Bal _xPbxTi03
solid solutions was verified. The figure 1 depicts the X-ray diffraction patterns for
calcinated and sintered samples. In our previous investi~ation8, it was observed that
during the solid state reaction, the replacement of Ba + (with ionic radius 1.35 A)
with Pb2+ ions (with ionic radius 1.20 A) occurred. Accordingly to literature data'"
values of unit-cell parameters for BaTi03 are a = 3.994 A and c = 4.038 A, and our
experimental results for calcinated doped BaTi03 are a = 3.982 A and c = 4.032 A
which confirmed previous conclusion . On the same time it can be noticed that the
values of unit-cell parameter for sintered doped BaTi03 samples are a = 3.988 A and
c = 4.029 A. A neglect increase of unit-cell parameters for calcinated related to
sintered samples can be explained by the change amount of Pb 2+ ions, essentially
shown that volatilization of lead during firing process occurred.
500 200 (101 100)

(101j(110) calcinated sintered at 1320"C
450 *PbO 162 PbO
I I
400 128
350 98 (112)(211)
1;1
300 72
(002)(200)
250 202
50
200 32
(OOl~1001 : (102)(201
150 111
18
01
(112)(211)
100
100 8
~II~
50 210 2
101
o * : . .
0
20 40 60 20 40 60
29
Figure 1. Powder diffractometer records for calcinated and sintered samples
Based on careful consideration, it was noticed that the investigated doped -

barium-lead-titanate system was a relatively dense ceramic with 6 % (sintered at
1380 "C) to 17 % porosity (sintered at 1320 0C). Characteristic scanning electron
micrograph for Bao.84Pbo.l6Ti03 doped system is shown on figure 2. Direct
observation showed that the grains have a rounded shape with several faces, which
were in close contact with other grains. The small grain sizes (1-5 urn) were observed
in all sintered specimens. Obviously, addition of 5mol% mixture of A1 20 3, Si0 2 and
Ti0 2 and 0.001 mol % of Sb203 inhibit the grain growth of the ceramic system,
which is in accordance to the literature data'.
415
Figure 2. Scanning electron micrograph of (Ba,Pb )Ti0 3 sintered at 1320 C
It is well known that the stoichiometry has an important influence on the PTCR
effect in doped barium titanate systems. The Curie point T, of Bao.84Pbo.16Ti03
doped ceramic determined using DSC analysis was shown a significant increas e of
temperature related to pure BaTi03 system as can be seen on figure 3.
mW
1.00
pure RaTiO j
0 .00
128.5 C
-1 .00
semicond. (Ba,PbITiO j
-2.00
o 100 200 300

Temperature (C)
Figure 3. DSC analisys of pure and dopped BaTi03
The resistivity R as a function of temperature is given in figure 4 and related

characteristics electrical parameters in table l.
The ferroelectric-paraelectric phase transition at Curie point, rapid decrease of
the dielectric constant above T e, according to the Curie-Weiss law, caused an
increase in the potential barrier height, consequently a PTCR anomaly results .
416
1000 R (KObm) 120Hz,I.5V
100 I---------------:l~----------l
10 1------------f1r------------;
series I
series 2
series I
series 2
O.II- ~--~--~--~--_--_----I
o 50 100 150 200 250 300 350
Temperature CC)
Figure 4. Resistivity vs. temperature for doped BaTi03 samples sint er ed at 1380 C
Table 1. Characteristic electrical parameters for doped BaTi03 samples

Samples R min 'r, Rc a(%/K)
(KQ) (0C) (KQ) T =220C T = 200C
cov. series 1 1.03 180 2.06 5.59 10.85 10.8
cov. series 2 0.64 183 1.28 6.23 12.68 11.3
uncov . series 1 0.66 195 1.32 12.85 14.68 17.6
uncov . series 2 0.55 190 1.10 11.45 15.59 17.8
Having in mind the grain-boundary layer model that assume the existence of
intergranular insulating layers, for understanding the mechanism of the PTCR grain
boundary structure and the shape of the PTCR characteristic, using strictly single-
grain boundaries, has to be necessary. So, in this study , a much closer picture of the
PTCR mechanism could not be obtain only from the PTCR anomaly results. On the
other hand examination of many single boundaries formed between grain s, on which
various types of growth step patterns can be appeared, desires to obtain a complex
quantitative analysis not only of the microstructure than also of the 1-V
characteristics in single boundaries in barium-titanate ceramics. In any way it could
be recognize that a slightly positive temperature coefficient found for dop ed
(Ba ,Pb)Ti03 system, has been confirmed to be significantly affected by grain
structure. The presence of low temperature donor dopants like Sb 5+ (Sb 3+) which
substitutes for Ti 4+ and the presence of acceptor dopants as manganese substituting
also Ti 4+ can affect that barium vacancies are not the dominant cation vacancies. In
this context, it is probable that acceptor impurities will be located to a region close to
the surface of the barium titanate grains' , Otherwise, in donor-doped BaTi03
ceramics dopant segregation will lead to the junctions at intergranular contact.
CONCLUSION
The doped Bao.84Pbo.16Ti03 system was investigated. The resistivity temperature

3
profile of semiconducting ceramics with characteristic values of R = 1.1-2.1 .10 n,
T, = 180-190 C (Tref =160-170 0C), UR = 10.8-17.8 %/K was shown.
417
The PTCR effect characterized by an abrupt increase in resistivity, more than
three orders of magnitude, exhibited essentially for stoichiometrc BaO.84Pbo.16Ti03
system added by 5 mol % mixture of Al z0 3 , SiOz and TiO z and doped by 0.78 mol %
of Sbz0 3, MnS04 and ZnO .
REFERENCES
1. H.A.Sauer, and J.RFisher, J. Am. Cersm. Soc., 43/6:297 (1960).
2. O.Saburi and K.Wakino, IEEE Trans. Compon . Parts, CP-1O:53, (1963).
3. G. V. Lewis, C.RCatlow; J.Am.Ceram.Soc., 68/10:555 (1989)
4. W.Heywang, Solid State Electronics, 3,1:51 (1961).
5. P.W.Haaijman, RW.Dam, H.A.Klansens, Netherland Pat. 84, 015 (1987).
6. G.Goodman, J.Am.Ceram.Soc., 46,1:48 (1963).
7. B.S.Chion , I.H .Wang, J.Mat.SciMat.Elect., 9:145 (1998).
8. B.D.Stojanovic, T.Sreckovic, V.R.Pavlovic, B.A .Marinkovic, Z .Preradovic, EUROMAT'97,
Proceedings ofthe jh ECAMPA, VoI.3, 3:483 (1997).
418
SYNTHESIS AND DIELECTRIC PROPERTIES OF
BaTi03-NOVOLAC COMPOSITE
Ljubomir Vulicevic,' Dimitrije Stefanovic.' Lazar Lukic;'

Zagorka Preradovic;' and Dragan Mancic/
ITechnical Faculty, Svetog Save 65, Cacak, Yugoslavia

2Faculty of Electronic Engineering, Beogradska 14, Nis, Yugoslavia
3EI IRITEL, Batajnicki put, Belgrade, Yugoslavia
ABSTRACT
Composite materials have found a number of structural applications. Here, BaTi03

phase in the form of the particle size less than IOO/lm is dispersed in a homogenous organic
matrix material. Variation of some composite properties by change in volume ratio ceramic
powder: novolac as an organic matrix is examined. It is assumed that sum properties of
composite depend on the corresponding coefficients of its component phases. Dielectric
constant is used to illustrate a simple sum property. The mixing rules involve only the
relative dielectric constants (relative permittivity) of BaTi03 (EST) and novolac (EN) and
their volume fractions. When plotted as function of composition, dielectric constant of
composites (Ec) decrease smoothly from EST to its minimum value for EN. The series and
parallel models represent extremes for the mixing rules. Maximum values are obtained with
parallel mixing and minimum for series case. In this study, mixing rule lies between these
extremes. Some other characteristics of a new composite dielectric material composed of a
barium titanate and novolac are also investigated.
Keywords: composites, organic matrix, barium titanate, novolac
INTRODUCTION
In most cases pure materials (metals, oxides, and resins) may satisfy only one or two of
the necessary requirements for particular application . However, composite may satisfy all
(or most) of those requirements. The traditional approach to making composite materials
usually result in materials with microstructures consisting of discrete, dispersed, and
isolated phases embedded in an otherwise homogeneous matrix materials. Here, it is of
interest to determine critical volume concentration of the second (disperse) phase. By
Advanced Science and Technol ogy 0/ Sinterin g, ed ited by Stojanovic et al.

Kluwer Academ ic/Plenum Publishers , New York, 1999 419
increasing the volume fraction of second (disperse) phase(s) raises the possibility of
deliberately making composite material in which each phase is continuos and
interpenetrating through microstructure. Connecting with mentioned are the basic ideas
underlying sum and produce properties. For a sum property, the composite property
coefficient depends on the corresponding coefficients of its constituent phases. Product
properties are more complex involving different properties in its constituent phases with the
interaction between the phases causing unexpected results.
On the other hand, barium titanate, used as a disperse phase, is well known due to its
high capacitance value averaging relative permittivity of 1500 and higher. However, there is
a wide variation in dielectric properties due to deviation from BaO:Ti0 2 ratio as well as due
to the presence of other phase(s).
Here, composites based on novolac as a matrix and barium titanate as a disperse phase,
using different BaO/Ti0 2 volume ratio, are synthesised. For this purpose, classic
compression moulding process is applied.
EXPERIMENTAL
A phenol novolac resin is prepared via standard procedure for producing of the resin
on laboratory scale' . A 0.5dm 3 resin kettle is equipped with a reflux condenser, stirrer,
thermometer, and siphoning tube leading to a collecting trap for the removal of samples
for testing . The obtained resin, brittle at room temperature, is easily powdered and
powder mixture with particle size below 100J..lm is used. On the other hand, powdered
commercial grade BaTi0 3 sample, with particle size also below 100J..lm was used as an
inorganic phase . Both, ceramic powder and novolac powder mixtures are mixed together
with curing agent and lubricant. As obtained mixtures with various mass ratio BaTi0 3 :
novolac in the range from approximately 95:5 to 70:30 mass percents (volume ratio from
80:20 to 30:70, in percent, respectivel y) are exposed separately , under the same
conditions to the further treatment. After milling and premixing by using laboratory hot
two-roller apparatus, granulated premix is moulded by commonly used compre ssion
moulding process. Physical and dielectric properties of synthesised composite are
examined by using samples in the form of discs with diameter of -15mm with thickness
of-2mm.
Relative permittivity of composites are calculated from capacitance measured by using
HP 4194A Impedance Gain Phase Analyser and HP4262A LCR-meter at 1kHz and 1,5V.
By measuring on the both mentioned instruments, nearly the same values are obtained for
the relative permittivity of the composite samples.
Phenolic resins are, most commonly, the reaction product of phenol and formaldehyde,
although substituted phenols and higher aldehydes are used for special applications.
Phenolic are thermosetting resins, typically hard, stiff (high-modulus), and notch sensitive
or brittle. Phenol is made from cumene, which comes from benzene and propylene.
Formaldehyde is made from methanol. Methanol and ammonia are based on natural gas.
Phenolic resins are excellent glues and are used for laminating various materials. The terms
"one-step", "one-stage" and "resole" refer to resin made by adding more than a one-to-one
mole ratio of formaldehyde. The phenol-formaldehyde ratio, type of catalyst, and reaction
conditions determine the properties of the resin.
Two-stage or two-step resins or novolacs, are made by reacting less than one moll of
formaldehyde with phenol. About 90% of all phenol moulding compounds use novolacs.
420
Phenolic moulding compounds are made from phenolic resin plus fillers, colorants,
lubricants, and catalyst. Typical moulding materials are 40-50% resin by volume and may
be either one-stage or two-stage. One stage materials are used for odour-free applications
such as closures, refrigerator controls, hermetically sealed electrical devices, and products
that are wet on one side and dry on the other, like pumps and vaporisers. Novolacs are used
on most other applications. Moulded phenolic parts have good thermal and mechanical
properties plus retention of properties at elevated temperature. Retention of physical
properties at elevated temperature sets phenolics apart from other plastic materials. They
retain a high percentage of their room-temperature properties at elevated temperatures,
some of them up to 455K. Dielectric strength of phenolics varies from 11 to I8MV1m.
Phenolics are very easy to mould ; compression, transfer, and injection moulding techniques
are used . Materials are formulated for the moulding method to be employed in terms of
granulation, plasticity or flow, speed of cure , and lubricant system. Also, shrinkage may
vary between methods of moulding with the same material and gate mould design .
Phenolics may be compounded with almost any filler. Usually a mix of filler is used to
provide a balance of properties. Cellulose as wood flour, paper flock , and cotton flock are
used for impact and lower density. Mica, wollastonite, and glass are used for heat resistance
and dimensional stability. Fibrous glass is used to reduce and control shrinkage, and
improve physical and electrical properties.
In this study BaTi03 powder is used as an active disperse phase . The ferroelectric and
dielectric properties of these materials are largely determined by heterogeneity in the
microstructure and chemical composition. Even today most of the dielectric materials in use
are based on barium titanate. Careful control of the impurity level , the grain size and the
distribution of the additives in the material can only meet its high performance according to
insulation resistance, lifetime and permittivity'. The high performance of these materials
owes much to new non-conventional techniques such as coprecipitation, sol-gel and others .
At so-called Curie point (T, = 403K) the ferroelectric , tetragonal distorted perovscite unit
cell of BaTi0 3 transforms into the cubic paraelectric one. Pure BaTi0 3 ceramics are not
qualified for dielectric use. In high-capacitance BaTi0 3 based ceramics the Curie maximum
is broadened and shifted to room temperature. By incorporating of so-called 'shifters' like
Sn or Yr for Ti or Sr for Ba, the Curie point can be reduced to room temperature. On the
other hand , the broadening of the peak (the dielectric maximum) is strongly dependent on
the microstructure.
In the case of composite synthesised here, relative permitivities of BaTi0 3 and novolac
will be used to illustrate a simple sum property). The mixing rules involve only the relative
permitivities of BaTi03 (ES T) and novolac (EN) and their volume fractions, VST and VN,
respectively. When plotted as a function of composition, relative permittivity of the
composite (Ed, decreases smoothly from ES T =1790 to its minimum value, EN = 4.6. The
senes
(1)
And parallel models
(2)
Represent extremes for the mixing rules as it is shown in Fig.I . Maximum values are
obtained with parallel mixing, and minimum for the series case.
Having in mind that VST+ VN =1, mentioned rules can be described as:
1
EC = 8234(1790 - I785.4vsTr (3)
421
for series and:
ec = 4.6 VN + 1785.4vsT (4)
parallel model, respectively.
____ 2000
co
'-'
.2
.:::.... 1500 1- e - 81
C Parallel
Measured
.'::
-.6.-D Series
E
v
0.. 1000
v
>
.... //
/
~
Q) 500
0::
0 I
0,0 0,2 0,4 0,6 0,8 I,D

BaTi0 3 volume content (V
BT)
Fig. 1. Dependence relative permittivity (er) of composite vs. BaTi03 volume content (VBT)calculated
according to parallel (B) and serial model (D) and measured values (C).
There are, of course, other rmxmg rules, which lie between these extremes .
Experimental values for permittivities lie also between values calculated by using two
mentioned mixing rules . All values for permittivities, calculated from both mixing rules
and experimentally measured on compound samples , had have the same BaTi03 volume
contents: 0.322, 0.450, 0.537, 0.648 and 0.795. Permittivities of both hardened novolac
and sintered BaTi03 pure samples are measured by using mentioned instruments.
Experimental values for permittivity lies between ones calculated by using both extreme
models . On the other hand, the known "Lichtenecker formula" developed for the two-
phase systems":
lnec = VST IneST + v N IneN (5)
Can be successfully applied for the two-phase systems where the permittivities do
not differ much one from another (less than factor 10). According to our preliminary
consideration, for the more precisely calculation of the relative permittivity for numerous
composites with inorganic powders dispersed in the organic matrix , it is necessary to
respect the fact that the sum VST+ VN <1 because the pore phase fraction vp>O (cpzl). The
mentioned can't be neglected because the first member on the right side from the equation
(5) in the great extent determines the permittivity of three-phase composite.
Unfortunately, at the composites examined in this study, the permittivities of the present
phases differ mutually very much (CS T =1790, cN=4.6 and cp z1) and mentioned
Lichtenecker formula can't be here applied . As it can be seen, solid dielectric phases
present in the synthesised composite have relative permittivities that differ from one
another by more than factor of 10 (tenj'. For the preliminary calculation are used values
422
for densities of BaTi0 3 (measured by picknometer method by using powdered materials)
and novolac of6120 and 1200 kg/rrr', respectively.
According to the experimental data, volume content of the disperse BaTi0 3 phase of
- 80% by volume or nearly 95% calcu lated on mass in as synthesised composite, can be
designed as critical. At first , volume content of disperse phase above critical one in the
great extent makes possible direct contact between BaTi0 3 powder particles in
synthesised composite sample. On the other hand, significant presence of the air closed in
the pores and direct contact between BaTi0 3 particles requires more differently model for
the calculation the relative permittivity of the composite with BaTi0 3 content above ones
designed as critical. Previous examinations are showed that relative permittivity of the
BaTi0 3 ceramics greatly depends on the grain size and grain size distribution in the
sintered BaTi0 3 samples.v" Mentioned needs keep in mind at the more precisely defining
of the Ba'FrOj-phenolic resin composites. On the other hand , further examinations will be
also conducted in the sense of the synthesis of phenolic resin s with optimal
characteristics from the standpoint of its dielectric characteristics and compatibility by the
disperse active BaTi0 3 phase . Some examinations pointed that resole types of phenolic
resins have some advantages at synthesis this type of composites."
CONCLUSION
Synthesised composites based on the phenolic resins as an organic matrix and

powdered BaTi03 as a disperse phase has significantly high values of relative permittivity .
By raising volume ratio of disperse BaTi03 phase up to -80% it is possible to synthesise the
samples via conventional press moulding process with relative permittivity of nearly 200.
Characteristic of starting BaTi0 3 ceramics, particle size distribution and type of phenolic
resin used can play an important role in producing composites with high relative
permittiv ity and good results reproducibility.
REFERENCES
I. H.Mandler, Du roplaste, Veb Carl Marhold Verlag, Halle (1959).

2. K. E. Nelson and R. L. Cook, Effects of contamination introduced during wet milling on the electrical
properties of BaTi0 3 , . Ceram . Bull . 38 :499 (1959).
3. C. Jovalekic, Lj. Vulicevic, and M. M. Ristic , Electrical properties of the epoxy resin- BaTi0 3
composites, Mat. Engineering I : 521 (1990).
4. H. Lichtenecker, und K. Rother, Die Herleitung des Logaritmischen Mischungsgesetzes aus Allgeme inen
Principien der Stationaren Stromung.. Phys, Z. XXXII: 255 (1931).
5. K. Kinosh ita, A. Yamaji , Grain-size effect on dielectric properties in BaTi0 3 ceramics, J. Appl. Phys.
47 : 37\ (1976).
6. R. C. De Vrie s, and J. E. Burke, Microstructure of BaTi0 3 ceramics, J. Am . Ceram. Soc . 40 : 200
(1957).
7. N. E. Hill, W. E. Vaughan, A. E. Price , and M. Davies , Dielectric Properties and Molecular Behaviour ,
Van Nostrand Reinhold Ed., London (1969).
423
RESISTIVITY VERSUS GEOMETRY RELATION IN BULK - SINTERED
AND THICK FILM MnCoFe - OXIDE THERMISTORS
Obrad S. Aleksic, Pantelija M. Nikolic, Mirjana N. Sirnic,

Verica Z. Pejovic, Dana G. Vasiljevic-Radovic
Joint Laboratory for Advanced Materials, SASA

P. Box . 745, 11000 Belgrade, Yugoslavia
ABSTRACT
A relation between the electrical resistivity and geometry in bulk (pressed and
sintered) and thick film NrC thermistors was determined A powder mixture consisting of
MnO, Coo and Fe]03 called NrC-3K3 (EI Ferrites) was used for the realization of
classical NrC disc shape thermistors sintered at 12000C 130 min. After that, a thick film
NrC thermistor paste was composed using the same powder (0.9 um particle size on
average), 4% of Bi]03 and an organic vehicle (NTC-3K3-95 12 EI Iritel). Different thick
film thermistorgeometry 's wereprinted ofNTC paste on alumina and sintered at 850oCII0
min. PdAg paste was printed on both sintered-bulk and thick film thermistors. Their
resistivity vs. geometry was compared. NTC coefficient B was determined on NTC - R (T)
curves as B=4200 K. The range of the resistivity values obtained variedfor planar shapes
from 100 Q to 10 M[4 andfor classical disc typesfrom 2-200 kil
INTRODUCTION
NTC therm istors based on Mn,Co,Cu and Fe oxides have been known for several
decades'r'. They come in a variety of sizes. The forming methods employed include: powder
pressing, tape casting, screen printing and sputtering. The thermistors obtained are usually
called: disc, small chip, thick film and thin film thermistors. They can be applied in
temperature measurement, control and compensation, time delay, voltage regulation and
surge suppression.
Focusing our attention on sensor application of thermistors a question was asked : what
are the advantages and disadvantages of these four differently formed thermistors: disc, chip,
thick and thin film. Using a high coefficient B NTC thermistor powder needed for measuring
applications we started experiments to define a relation resistivity vs. geometry between
the three sintered thermistors: pressed, cast and printed types . As the cast and printed types
Advan ced Science and Technology ofSintering , edited by Stojanovic et al.

have a similar microstructure the problem was reduced to differences between powder
pressed and screen printed types.
POWDER PREPARATION AND CHARACTERIZAnON
The NTC thermistor powder (called NTC2 grade 3K3) used in the following
experiments was prepared using a classical powder preparing procedure applied in EI
FERRITES since 1975 3. A dry powder mixture ofNTC formulations (nearly 60 % MnO,
32% CoO and 8 % Fe203 wt) was formed and then the fluid suspension was consolidated,
dried and granulated . The resulting oxide powder mixture was calcined at 900C 1 2 hours in
the air.
After vibratory, ball and ultra fast milling the average powder particle size of 0.9 urn
was achieved. That initial NTC powder was used for disc shape thermistor forming and NTC
thick film thermistor paste composing . The NTC thermistor paste (called 3K3 95 12 was
composed in EI IRITEL (paste producer) adding 4 % of'Bi-O, and an organic vehicle to the
initial NTC powder. The pressed NTC disc samples were sintered at 1200 CI 30 min in air.
The NTC paste was screen printed on alumina substrata and sintered at 850C 1 10 min in a
hybrid conveyor furnace. Both types of samples were analyzed using a X-ray diffractometer
to check the chemical changes. They were then observed under optical and SEM
microscopes. After powder characterization, electrical resistivity was measured on the same
samples (plated with PdAg for electrodes) in the range from -30C to 120 c (fig.1).
::::::::::::::::: :::::::R1;~I ~E :::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: ::::::::: :::::::::::::: ::::::::
100 ":'::::;"";~";~;"~::~ ~ ~~;":::::""~"";";"";~:~""":;~;:~;"~~;~;~:;~"~~~""~;~;~;~""""";";~"""; """;~~"~~;~; ;
0,01
0,001 - ' - - - - - - - - - - - - - - - - - - - - - - -- ----'
Figure 1. Resistivity vs. temperature of Nl'C thermistor samples : Rl disc type (pressed and sintered), R2 and
R3 thick film small rectangular and sandwich types (screen-printed and sintered).
The main thermistor constant B was calculated from NTC diagrams as B=4200 K,
Tmax about 130C. The results obtained were quite successful, compared to the literature
data", so the NTC powder obtained as can be treated as high quality powder for further
experiments. After that several different disc and thick film thermistor shapes were realized
and analyzed. The results obtained on cubic and planar geometries represent a relation
between bulk and sheet resistivity and geometry .
426
SINTERED NTC THERMISTORS
Cross-sections of the thermistor geometries realized and measured are given in fig. 2,
together with a list of their possible geometrical variables.
2 < 1
'1
2
3 /' / 1
\
f I
disc rectangular
2 1
~ 2 1
I I
sandwich multilayer
1
3 1
~ EfSIt'I DI
~
ED .. ~ ..
3 2
segmented
interdigitated
1- PdAg electrodes, 2- NTC thermistor layer, 3- alumina substrate
SHAPE: GEOMETRY VARIABLES

Disc S-electrode surface value, h-NTC layer thickness
Rectangular I-thermistor length, w- thermistor width, d- NTC layer thickness
Sandwich S-e1ectrode surface value, d-NTC layer thickness
Multilayer S-electrode surface value, d-NTC layer thickness, n- number of cells
Segmented S-e1ectrode surface value, d-NTC layer thickness, n- number of cells
Interdigitated I-interelectrode length, w-electrode spacing, d-NTC layer thickness
Figure 2. Cross- sections of the NTC thermistors realized and measured and a list of their
geometrical variables that can be varied.
Resistivity change vs. geometry at room temperatures (25C) for 6 different shapes are
given in figures 3-8. Disc samples were sintered at 12000C / 30 min and thick films at 850
c /10 min.
DISCUSSION
The NTC thermistor powder was first synthesized and characterized. X-ray powder
pattern showed that spinel (Mn'oxCox)30. is dominant, although small quantities of other
oxides may exist, which is well known in literature s. A submicronic NTC thermistor powder
(0.9 urn particle size on average) was used for pressing and sintering disc samples and thick
film forming. After PdAg was platted as an electrode, resistivity of the same samples was
measured in a climate chamber in the range of -30 to 130C. The thermistor main
427
300 , -- - - .,-- - - - - - ----,
R[kQ] 100 ,-----..,--------,---~
~ ~R(r~ril]_=j===I=~I=-=--=-~
250 ~ ----..::..---- .--------
200
~ 60 -----=j=-~---I=--=-:=--
150
100
~ 50
40
- .--
30
h [rnn] 20
50
O ~~~~
10
o + - - -- -,-- - - --,-- ---''-==.:.&1
0,8 1,2 2 2,5 2 4 6 8
Figure 3. Disc thermistor resistivity vs disc Figure 4. Rectangular thermistor resistivity vs.
thickness h, electrode surface values SI=12 mm", thermistor length I, w=2 mm -thermistor width,
S2=50 mm', S3=120 mnr' . d=60 um NTC layer thickness.
700
[S
~-------,---------,
am 600 ____ R[ q ] S1
5CXll ~ S2
500
4CO) 53
400
~ S4
:D)) 300 ---------..---.
2OCO 200
n
lCXXl 100
0
0 -+-- - - - - - ,- - - - - --1
3) EO 9') 150 270 39':l 1 2 3
Figure 5. Sandwich thermistor resistivity vs. Figure 6. Multilayer thermistor resistivity vs.
NTC layer thickness d, SI=25 , S2=16, S3=9, number of cells n, SI=25 , S2=16, S3=9, S4=4
S4=4 mm! -electrode surface value. mm2 - electrode surface value, d=90 urn - NTC
layer thickness.
12000 . -- ,-----:--
I I
--,-- -,--
I
-,---,--,---,--
I I
-,
Rlpl i , - - r- .----
' i. . [ ~ S1 1
I I
10000 - -.----. -+- .- 250 . - -- - - -,-- - - - - , - - ----,.
!
8000 - - - - -j- -- .-- - .-- -
I - 52
~ 53
200
R[kO]
---I-------_.._-~--__-- . -
I
---1--/- -
6000 -- - 1-.--
I 150
I
4000 100 1
2000 50
n
O +----,- - ,- -,-- ,---,-- -,-- ,---{ o +--'= - - ---,- - - - ....,- - - - 4
1 3 5 7 9 11 13 15 17 100 500 1000 2000
Figure 7. Segmented thermistor resistivity vs. Figure 8. Interdigitated thermistor resistivity vs.
number of segments n, SI =1.2, S2=2, S3=4 mnr' , electrode spacing wand interelectrode length I:
w=0.3 mm -spacing, d= 60~m - NTC layer w=0.2, 0.5, I, 2 mm vs. 1=60, 40, 20, 10 em.
thickness. d=60~m-NTC layer thickness.
428
coefficient B was calculated as B=4200 K using a well known equation B=( 11 TrT 1) In
(R2/Rl) and curves given in figure 1. The results obtained are not the best, but are adequate.
They enable the realization of various geometries such as: disc, rectangular, sandwich,
multilayer, segmented and interdigit (their cross-sections and geometrical variables are given
in fig 2) . The resistivity behavior obtained by variation of main geometry parameters (given
in fig.3-8) could be compared mutually in Table 1.
Table 1. NTC thermistors comparison
NTC THERMISTORS COMPARISON

Shape/val Disc Rectangle Sandwich Multilayer Segmented Interdigitated
R [knl 5-250 500-7500 0.1-5 .5 0.01-1 1-20 3-300
S [mm'] 10-120 4-16 36-9 36-9 24-120 100
U rVl Middle High Low Low middle high
P rw: High Low Middle Middle middle low
R -resistivity at 25 C, S- occupied area on substrate, U - compared to 100 V de,
Other comparisons could be made such as: resistors vs. occupied area , total power,
maximum voltage applied, or speed of thermal change (sensitivity). According to theory
resistivity R is dependent on the specific bulk resistivity of a material p and geometrical
variables such as l-length and S- normal surface (s=wd, w-width, d-high or thickness). It
gives the well known equation R = pl/S = pl/wd. Using this equation and the results obtained
on various geometries a specific bulk resistivity at 25C could be calculated as shown in table
2. It is evident from the table that disc, rectangular and interdigit types have the bulk specific
resistivity p of375-750 nm, and sandwich, multilayer and segmented geometries give ten to
twenty times smaller values such as 25-35 nm.
Differences in specific bulk resistivity
between disc and rectangular or interdigit types could be explained as follows : thick films do
not exceed 85% dens ity of disc sintered types, and due to higher porosity the diffusion
effects ofPdAg printed as electrode metal affect the resistivity (lower it tw ice). But the very
high drop of sandwich, multilayer and, segmented resistivity was expected. Sandwich
thermistors of less than 30 urn in thickness could have short circuit junctions between
electrodes. Diffusion of PdAg is very high, due to low thickness and a high electrode surface
value . Yet , they could be applied as low value, low voltage, high power, small volume, but
planar thermistors.
Table 2. Specific bulk resistivity
SPECIFIC BULK RESISTIVITY

Shape/values Main thermistor values obtained (examp.) p - equation o rQml
Disc R=12 K, S=50.4 mrrr', h=0 .8 mm RS/h 750
Rectangular R= 6.4 M, w=2 mm, 1=2 mm, d= 60 urn Rwd/l 384
Sandwich R=1.2 K, S=4 mrrr', d=150 urn RS/d 32
Multilayer R=0 .3 K, S=4 mm', d= 90 urn, n=3 RnS I d28
Segmented R=5 .5 K, S=4 mrrr', d=60J.lm, n=15 RS Ind 25
Interdigitated R=250 K, 1=100 mm, w=2 mm, d=60um Rld/w 375
R-resistivity, S- electrode surface, d, h- thickness, I-length, w-width or spacing for interdigitated shape .
429
Sheet resistivity could be calculated for the rectangular type in the way it is usually done
with thick film resistors : ifl=w=2mm for a fixed thickness d (see table 2) sheet resistivity has
a value of 6.4 MQ I[] which is in the range of 10M BIROX (Du Pont) resistor paste for
hybrid technology and ESL NTC thermistor paste 6.
CONCLUSION
Six different cubic and planar types of NTC thermistors were realized, measured and
analyzed. Their specific bulk resistivities were calculated from electrical resistivity and
geometrical variables and compared mutually. The main advantages obtained with thick films
were faster response to heat change. Two quite different groups of thermistors were
obtained : high resistivity geometries such as disc, rectangle and interdigit vs. low resistivity
geometries such as sandwich, multilayer and segmented. Moreover, multilayer thermistor
types save the occupied area on the substrate . The segmented type is a parallel combination
of the sandwich and interdigit type. All the thick film geometries realized and analyzed are
suitable for hybrid integration .
REFERENCES
1. Maclean E.D., Thermistors, Electrochem. Pub. , Glasgow, (1979).

2. Sache B.H., Semiconducting Temperatyre Sensors, Wiley, New York ,(I975).
3. EI Ferrites, Thermistors 75, Catalogue, Belgrade (1975) .
4. Ketema-Rodan, Thermistor Product Guide, R 07/92 -5K, (\ 992).
5. Buchanan C.R., Ceramic Materials/or Electronics, Marcel Dekker, New York and Basel, (1986).
6. ESL (Elect. Sci.Labs., N.J.,USA) Thick Film and Optoelectronic Materials, Catalog 5-73-74, (\975).
430
BaTiOJ STRUCTURE PROGNOSIS
Vojislav V. Mitic, Ivona Z. Mitrovic
Faculty of Electronic Engineering, University of'Nis, Beogradska 14,

18000 Nis, Yugoslavia
ABSTRACT
The level of microstructure in BaTi03-ceramics structural hierarchy can be considered

to a certain extent in the scope of adequate and logically consistent apparatus . Such
apparatus for the microstructure is the theory of grain boundaries. Research of processes
acting on boundaries and on contacts between two or more grains of sintered BaTi03-
ceramic material is possible from the viewpoint of sintering theory, by studying the main
kinetic mechanisms acting on grain boundaries, and during the neck is being formed, or from
the viewpoint of mathematical modelling and simulation methods establishing so called
model-experiment with different shapes and sizes of grains in corresponding structure of
BaTi03-ceramics constituents. In this paper those two approaches are united. Thus, a new
structural model of BaTi03-ceramics is developed for given geometry of grains' model
system, on the basis of SEM micrographs, using the basic sintering kinetic mechanisms.
Connection of model and proper mathematical relations leads towards further prognosis
upon structural and electronic properties of the sintered BaTi03 material.
INTRODUCTION
Sintering process of ceramic materials is characterized by an exceptional complexity', as

a result of simultaneous and successive influence of elementary transport mechanisms that
can not be, or can hardly be experimentally followed, and qualitatively and quantitatively
described. In that case, the application of modelling and simulation method presents a
possible method of investigation. Generally speaking, defining model, as a research method,
means the introduction of some assumptions and simplifications, and because of that they
represent only the approximation of real systems and processes. However, in the first stages
of investigation, the model application is necessary and justified, because it makes possible
the formation of subset of the most probable ways from sets possible for discovering laws
and for formulating the process theory in the very physical base.
Advanced Science and Technology of Sintering , ed ited by Stojanovic et al.

Kluwer AcademiclPlenum Publishers , New York, 1999 431
In that sense, in this paper a new structural model of ceramic grains is given making
possible further structure prognosis of ceramics. Starting from the sintering kinetics of two
spheres - Coble's two-sphere model'', by applying mathematical relations, sphere-shaped
grains are transformed into ellipsoidal grains. Then, the volume conservation law of two
spherical grains is applied on ellipsoidal grains. The main emphasis in the model is put on
estimation of the grain's neck material value in order to establish the valid relations
connecting geometrical and kinetics parameters of the ceramic consolidation process.
It is known that barium-titanate ceramics dielectric properties depend on values and
distribution of grains' contacts':'. In that way, the developed model can be applied as a
structural model of BaTi03-ceramics being useful in electric properties prognosis of this
ceramic electronic material. Also, it should be mentioned that the model can be applied on
any ceramic structure that has a structural model being in agreement with the model
presented in this paper.
EXPERIMENTAL
Different stereo logical constituents of BaTi03-ceramics, such as the grains and pores,
are responsible for the distribution of areas in grain boundary intergranular phases. The
intergranular and integral surfaces are the basis for the different electric properties, specially
for the capacity'. The geometry of grains and grain boundary surfaces are very important for
the space charges and the processes on the electric level near to grain boundaries. The grain
contact patches are small in size, but highly complicated in form. So, in order to be as close
as possible to the real structure of BaTi03-ceramics, the grains are approximated by
ellipsoids of different sizes and orientations . Experimental study in this paper included the
scanning electronic microscopy analysis (type of microscope JOEL-JSM- T20) of BaTi03-
ceramic samples.
The samples were prepared from "Murata" barium-titanate powder of the composition
65.24% BaO and 34.70% Ti02 To investigate the influence of the grain growth on the
electrical characteristics the following pressures have been used: 86-150 MPa. The specimens
were sintered in a tunnel furnace type "CT-lO MURATA" from 1240-1370C for 2 hours.
Micrographs obtained by SEM method are shown in Figures 1a. and b. Both
micrographs are referred to sintered samples of BaTi03-ceramics and represent an
experimental base for developing a new structural model.
a. b.
Figure 1. SEM micrographs of sintered BaTi03-ceramics (T.irlt=2h): a. Tsint=1370C, p=3.6xl03 kg/m'

(x5000) ; b. Tsint=1180C, p=3 .2x10 3 kg/m" (xlOOOO).
432
TOWARDS COBLE'S MODEL GENERALIZAnON
J
Let C I = (XI, yI, ZI) and C2= (X2, Y2, Z2) be two points in R . Consider two ellipsoids E I
and E 2 having parallel semi-axes ai, b., Ci (i=l, 2) provided that ai>bj>ci, and
a2/al=b2/b I=c2/cI=k (k>O), and having C I and C2 as centers. Suppose that E I and E2
approximate two neighbor grains in sintered BaTi03-ceramics (Figure 2), such that E I n E 2
= (xp, yp, Zp). In the local coordinate system, the parametric equation of a half-line emanating
from C I is
xp=cosat, yp=cosf3t, Zp=cosyt,
where a, {3, yare angles of the segment C IC2 towards (x, y, z) - coordinate system.
Straightforward calculation gives that the distance between C I and C2 at the beginning of
sintering process (sintering time r-=O) is given by
l+k
(1)
cos' a cos' fJ cos' y
- 2- + -2- + -2-
a b c
Note that (1+k)CISOE(r=O)s(1+k)al. Suppose that for r>O two grains penetrate each other
due to the sintering process (Tsinh Psint). In order to find geometric parameters of contact area
we will transform two-ellipsoids model into two-sphere model by the transformation
(2)
By (2), ellipsoids transform into the spheres
s; (x -:: r (Y - ~I r (z - ~r
+ + = p2 = R}2
S2: (x- ::r +(y-y;r +(z- z:r =p e =R22.

2
Now, we can use known relations 3
x 2
2
P2=4.R'
2
where RI, R 2 are radii of the spheres; PI, P2 - are heights of spherical caps (forming the
common volume S lnS2); XI - is the radius of the common circle; X 2 - is the radius of the
neck formed by diffusion in initial stage of sintering .
Let the centers of two spheres be (ax., by., CZj) (i=l, 2). Then, the distance between two
centers is
433
P, r
.
s"
c2 +
Figure 2. The Coble's two-sphere model and its ellipsoidal analogy.
Contacting factor between two spheres (contraction of initial distance) will be
so that 8, = A, .(RJ +R2 ) . Since the affine transform (2) preserves ratio the formula
analogous to the previous one is taking place
In this way the penetration depth is 8(T) = 8E(T = 0) - 8E(T) = ~J + ~2 8E(T = 0) and by
J + 2
the volume conservation law we have
434
It follows by (1) that
(1 +k)
cos' a cos' f3 cos' r
- -2 + -2 - + - -
a b c'
The value of 8(T) expresses the difference between grain center distances at the
beginning and at the end of sintering process during the ellapsed time T . It contains
information about dynamics of the intergrain's neck formation . From this formula we can
express the neck radius via the proportionality factor k. This relationship is given by
(3)
The diagram of this function is given on Figure 3.
The presented model is tested for the case of two grains displayed in Fig1b. According
to the given micrograph's ratio, the dimensions of grains are as follows : a=3.5 J.lm, b=2.8 J.lm
and c=1.2 J.lm. Furthermore, coordinate axes can be chosen parallely to the main axes of
ellipsoids. In this case, the angles of the segment C,C 2 are: a=90, /3=90, y=0. This
simplifies the starting grains' distance (formula (1)) to 8/
=(1 + k) c .
1.5
0.5
Figure 3. diagrams of gra ins' necks radius as a
k function of gra ins' proportionality factor for
different 0: 15% - upper , 12.5% - middle and 10%
0.2 0.4 0.6 0.8 the lowest curve.
Following the procedure explained above on those two grains the reduced form of
equation (3) is obtained :
X2 =2'Rl~-kk . 8( ..) -k.

+I c
435
where R 1 is the radius of spherical grain corresponding to given ellipsoidal grain. Knowing
that the penetration depth of BaTi03-ceramic grains does not exceed the value of 10-15 % of
grain size s, the diagrams of'X, = f{k) are obtained for three constant values of o(r): 10, 12.5
and 15 % (Figure 3). This parameter o(r) in geometrical aspect of the problem represents the
measure of contraction of grains' center distance arbitrarily positioned in the specimen.
What we want to obtain is how the grains' neck radius changes its values when the
grains proportionality factor k varies. Figure 3 shows that when k increases, X2 increases
too, which is expected situation, but certainly there are limits on the values of k in the
sintering process. The importance of obtained curves is in possibility of reading the exact
value of the neck radius for k obtained from the data based on other physical calculations of
sintering process, e.g. the spacial grains' distribution. Research aimed to this direction is in
progress.
CONCLUSION
Up to now, studying of sintering process is basically realized through two-sphere

models. In this paper, the developed model is a step further because it offers a possibility for
transition from spherical to ellipsoidal ceramic grain geometry. Starting from the Coble's
two-sphere model the equation of ceramic grains' neck radius as a function of both
geometrical and kinetics parameters is derived. Observing of'Ba'Tifh-ceramic morphology by
SEM method confirmed the fact that BaTi03 grains can be approximated by ellipsoids of
different sizes and orientations. So, the neck radius equation is applied on BaTi03-ceramic
grains.
Obtained curves represent a good correlation between structural/geometrical and
kinetics/physical parameters making possible control under structural properties of BaTi03-
ceramics. The given structural model can be an effective tool not only in BaTi03-ceramic
materials prognosis, but in ceramic study and prognosis in general.
Acknowledgement
This research has been supported by the projects : "Prognosis of material

characteristics" financed by the Ministry of Science and Technology of Republic of Serbia
and "Physical chemistry processes of technology of modern materials" financed by Serbian
Academy of Sciences and Arts.
REFERENCES
1. V.V. Mitic, The optimization ofinterrelations ofmicrostructure and electrical properties of

BaTiOrceramics, Ph. D. Thesis, University of Nis, Nis, (1995).
2. V.V. Mitic, 2 .S. Nikolic, Lj.M. Kocic, M.M. Ristic. Dielectric Properties ofBarium-Titanate
Ceramics as a Function ofGrain Size , Advances in Dielectric CeramicMaterials, Ceramic
Transactions, Volume 88,215-223, (1998).
3. J.H. Chen, P.F. Johnson. Computer Simulation ofInitial Stage Sintering in Two-Dimensional
Particulate Systems , P.E. Russel1, Ed., Microbeam Analysis, 405-409, (1989).
4. V.V. Mitic, Lj.M. Kocic , I. Mitrovic, M.M. Ristic , Models ofBaTi03-Ceramics Grains Contact
Surfaces, The Journalof MaterialsSynthesis and Processing (1998).
5. V.V. Mitic, I. Mitrovic, B. Jordovic, V. Brankov. The application ofStereology Method for Estimating
the Number of3D BaTiO rCeramics Grains Contact Surfaces, 7tl> European Congress for Stereology,
Bookof Abstracts, Amsterdam, The Netherlands, April 20-23, P47, pp. 131, (1998).
436
SYNTHESIS AND SINTERING OF MANGANESE
DOPED S002 IN SEVERAL ATMOSPHERES
(Chemistry Departament, UEPG, Ponta Grossa/PR, 84.010-330

2Chemistry Institute, Unesp, AraraquaralSP, P.O.BOX 355,.14.801-970
3Chemistry Departament, UFSCar, Sao Carlos/SP, P.O.BOX 676, 13.565-905
E-mail: sergiot@iq.unesp.br
ABSTRACT
Manganese doped (up to 1.0 mol%) Sn02 ceramics were synthesized by polymeric
precursor method. The powder was compacted and isostatically pressed at 210 MPa given a
green density of 60% . Sintering of pellets was performed in synthetic air, argon and C02,
using a dilatometer with constant heating rate of 5.0 DC/min up to 1350C. XRD analysis
indicated the formation of cassiterite structure of Sn02 and FT-IR spectra displayed the
metal-oxygen stretching bands. Sintered pellets were characterized by SEM and the
micrographs indicated the segregation of a second phase for the 1.0 mol% manganese doped
Sn02. The larger the amount of dopants the higher is the sintering rate and oxygen
atmosphere retards the densification.
INTRODUCTION
In the search for new technological materials, tin oxide has been stud ied as a single
crystal' or as polycrystals' in dense ceramics due to its electronic mobility for the use as
varistors':', and in porous ceramics in which the fundamental application is as gas sensors'",
Sn02 crystallizes in the tetragonal structure similar to the Rutile, (Ti02)1 in which the
most stable faces correspond to planes (110) , (101) and (100) in the proportion of 60, 20
and 20% respectively. For single crystals, faces {I10} and {101} contribute to the decrease
ofthe excess in the surface free energy",
Sn02 powder is frequently prepared by the French process of evaporation and
oxidation of metal tin, by the sol-gel process or by the polymeric precursor process9-12.
Among the major advantages of the Pechini method" :", when compared to other methods
are : a) the homogeneous distribution of dopant cations in the Sn02 structure, since these
ions are directly introduced in the lattice, whereas in the mixture of oxides, the doping
Advanc ed Science and Technology ofSintering , edited by Stojanovic et al.

Kluwe r Academ ic/Plenum Publishers, New York, 1999 437
process occurs by means of solid state reaction; b) the possibility of homogeneous
introduction ofvery small quantities of dopant cations in the lattice .
To obtain Sn02 based devices the sintering process is used. This is a thermal process
that causes the reduction of the surface area by the formation of grain contour between
particles", grain neck growth and normally densification". Because this process is diffusion
on the oxides can affect the kinetics of the sintering. As to the thermodynamic strength
responsible for the process, it can be said that compacts with higher surface area density
faster than those with lower surface area",
It is well known that non doped Sn02 ceramics do not density during sintering. In the
attempt to explain such behavior, QUADIR and READEyl8 observed that the sintering of
Sn02 atmosphere, causes an expansion of the compact, decreasing the apparent density, and
that this behavior of excessive growth of the particles, is not isotropic, since the oxide
crystalline structure is tetragonal. As a result, the particles become elongated, leading to
expansion. The authors propose the following reaction for the vapor transport:
(1)
Similar studies have been performed employing argon, oxygen or humid argon
atmospheres". Also, several dopants have been used to promote densification and to favor
the microstructure control. Among the dopants, manganese is especially effective in the
absence of liquid phase formation during the sintering, and in the oxygen vacancy formation
process, according the reaction".
(2)
A variation of the Pechini method enables the preparation of Sn02 with controlled
and low amount of manganese. The product is extremely homogeneous and the specific
surface area can be controlled with appropriate calcination, forming weak agglomerate
powders that lead to a high efficiency during the sintering process'", Moreover, the presence
3
of Mn + ions in relatively small quantities does not change the specific surface area or the
average size ofthe Sn~ crystallite",
The atmosphere, in which the material is sintered, can greatly influence in the kinetics
of the process. This importance has been demonstrated in previous works in the sintering of
non doped Sn02 in several atmospheres", However, no studies have been performed to
investigate the effect of different atmospheres when Sn~ doped with transition metals is
sintered. Therefore, the main goal of this work is to study the effect of oxidizing and neutral
atmospheres on the sintering ofmanganese doped Sn02 based ceramics.
Samples ofSn02 powder doped with 0.2,0.3,0.4,0.5 and 1.0 mol% ofMn02 were
obtained via Pechini method. This method consists in adding tin ions (from SnCh.2H20) and
manganese ions (from manganese acetate) to citric acid dissolved in ethylene glycol to form
a polymeric precursor in the citrate form after heating at 140C until complete elimination of
water. The cr was eliminated after successive washing of the tin citrate. The negative test
for chlorine ions was determined by using an analytical PbS04-0.4 M solution.
The polymeric organic solution was heated to 170C to complete poliesterification
and then burned in a furnace at 400C for 4 hours followed by calcination at 500C for
15 hours. The powders were characterized by nitrogen adsorption-desorption and surface
438
Thennogravirnetric and differential thermal analysis (Netzsch STAY09) were used to
characterize the calcined powder. Infrared spectroscopy (Nicolet-Fl') was used to determine
the presence of carbon and water species as well as the metal-oxygen stretch. X-ray
diffi:actionpatterns was used to study the crystallization ofthe SnO;z based powder.
The oxide powder was uniaxially (15 MFa), and then isostatically pressed
(210 MFa), in the form of cylindrical compacts of approximately 0.6 em diameter by 0.7 em
height, up to an average green density of 60%.
Once obtained, the compacts were sintered in a horizontal Dilatometer from
environmental temperature to 1350C with heating rates of 5.0 DC/min in of synthetic
air (S.A.), argon (Ar) and C02. Ff-IR and XRD were also used to characterize the sintered
compacts. The microstructure developed were analyzed by scanning electron microscopy
(Topcom 300)
Spectroscopic results of the Sn02 powder in the infrared region are presented in
Figure 1. Bands around 521 and 620 em" correspond to the metal-oxygen bond stretching
and bands around 1629 and 3429 indicate the presence of water (O-H stretching). To verify
the form, in which the water is incorporated in the compound, the powder was kept at 80C
for 24 hours and after it was observed that these bands had reduced to an average of 50% in
intensity as shown in Figure Ib, indicating water loss.
1629.671
-_ (a)
.. ""- -
3429.574
~ .
3424.110
(b)
4000 3000 2000 1000
Figure 1. IR spectroscopy in the 0.5 mol% MnO:z doped Sn02 powder calcined at 500C during 15 h: a) for
powder kept in ambient atmosphere; b) after drying at 80C during 24 h.
439
t
o
-SDO: - 0.4mo1% MaO:

1600 ~
1400
I
1200
ell
0..
U 1000
-...
ell 100
~
.-C=
600
-=
400
200
25 30 35 40 45 50 55 60 65 70 75 80 85 90 9' 100 105 110 115 120

28
Figure 2. X-ray diffraction pattern s on 0.4 mol% Mn02 doped Sn02 calcined at 5000C durin g 15 hours.
.(l.10
o
...J
:::J
<] .(l.U

... 1.0'a(Ar)
0.5%(SA)
1.O'a (SA)
1000 1050 1100 1150 1200 1250 1300 1400
Temperature / C
0.001-----1IIIt~ ....~~L.
.(l,05

.(l.10
o
S
<] .(l.15
1000 1050 1100 1150 1200 1250 1300 1350 1400

Temperature / C
Figure 3. Linear shrinkage curves of Sn~ ceramics, with different manganese concentrations, sintered
in (a) atmospheres of argon (Ar) and synthetic air (AS) and, (b) atmospheres of C~ and synthetic air
(AS)
441
(b) (a)
(d) (c)
Figure 4. SEM micrographs of Sn02 compacts sintered in (a) synthetic air with 0.2 mol% manganese; (b)
synthetic air with 0.5 mol% manganese; in (c) synthetic air with 1.0 mol% Mn~ and (d) argon with
1.0 mol% Mn~.
Thermogravimetric and Differential Thennoanalysis were performed from

environmental temperature to 1550C and no weight loss was observed under synthetic air,
argon and CO2 gas fluxing and therefore the oxide was kept in its original Sn02 form.
From the X-ray diffraction patterns on 0.4 mol% manganese doped Sn02 calcined at 500C
during 15 h only the cassiterite phase could be identified in the powders (Figure 2). Similar
results were observedfor other manganese concentrations on Sn02.
Dilatometer furnace was used to obtain linear shrinkage curves of Sn02 ceramics,
with different manganese concentrations, sintered in atmospheres of argon, synthetic air and
C02 as depicted in Figure 3. Several features can be observed in those curves. Increasing
amount of manganese lead to decrease in the sintering temperature (on set of shrinkage
curves). This behaviorcan be explained if one considersthat the amount of extrinsic oxygen
vacancies is increasing with the amount ofMn02.
Argon and CO2 have similar effect on the sintering curves as observed in Figure 3.
Considering the same manganese concentration, the shrinkage starts in the same temperature
as compared with synthetic air atmosphere. However, in argon or CO2 atmospheres the
shrinkage rate is higher for lower temperatures, indicating that those atmospheres increase
surface diffusion. However, for higher temperatures, the shrinkage is inhibited as compared
with synthetic air atmosphere due probablyto the effect of adsorption of CO2 or Ar on Sn02
surfaces,whichdecrease masstransport.
442
Figure 4 shows the SEM back scattering micrographs obtained from Sn02
samples with different concentrations of Mn02 and sintered at constant heating rate
(5C/min) up to 1350C at different atmospheres. As observed in these micrographs the
amount of 0.2 mol% of manganese was not sufficient for densification of the Sn02
ceramic in synthetic air (Figure 4a). Average grain size of 0.5 um is observed with high
porosity, in agreement with low shrinkage observed in Figure 3. However, for 0.5 mol%
Mn~ doped Sn~ sintered in the same conditions, 95% dense samples are observed
with average grain size of 10.9 um (Figure 4b) . The highest density (98%) was observed
for 1.0 mol% Mn02 doped Sn02 samples sintered in the same conditions with average
grain size of9.3 um (Figure 4c) . Sintering in argon, however, for same composition lead
to 92% ofthe theoretical density with average grain size of 2.5 um as observed in Figure
4d. Then, argon inhibit both, densification and grain growth of Sn02 ceramics. This
behavior is opposite of that for sintering of pure Sn02 where the argon atmosphere
enhance grain growth by evaporation-condensarion". The argon atmosphere probably
enhances the Sn02 reduction to SnO and more Mn02 is segregated at the Sn02 grain
boundary that would inhibit grain growth. Mn02 segregation at the grain boundary was
also observed for 1.0 mol% Mn02 doped Sn02 samples sintered at 1350C and inhibited
grain growth (comparing Figures 4b and 4c where average grain size is higher for
samples sintered with 0.5 mol% Mn02).
CONCLUSIONS
As results ofthis study it can be concluded that both, sintering atmosphere and Mn~
concentration, significantly affect the grain growth and densification of Sn~. Higher Mn02
concentration lead to lower sintering temperatures. Sintering in argon or C~ atmospheres
allow higher densification rates for lower temperatures as compared with sintering in
synthetic air. This behavior is probably related to the increase in surfuce diffusion due to
interaction ofthese species with Sn02 surface,
Acknowledgments
The authors gratefully acknowledge CNPq, FINEP, FAPESP and CAPES for the financial
support.
REFERENCES
1. P. Jones and J. A Hockey. Trans. Faraday Soc. , 67, p. 2679 (1971).

2. Z.M. Zarzebski and J.P . Marton , 1. Electrochem. Soc ., 123:(10), C333-C346 (1976).
3. L.M. Levinson and H.R Philipp, Am. Cer. Soc. Bull, 65:(4), 639-646 (1986).
4. P.H. Duvigneaud andD. Reighardderie, In: Science ofsintering, Vol. 12, Edited by
Vicenzini. Ceramurgia Srl, Faenza, Italy, 287-92 (1980).
5. N. Yamazoe, T. Fughigami, N. Kishikama and T. Seiyama, Surface Sci., 86, 335-344
(1979).
6. C.G. Fonstad and RH. Reiker, 1. Appl. Phys., 42(7), 2911-2918 (1971).
7. J.G. Fagan and V.RW. Amarakoon, Am. Ceram. Soc. Bull, 72(3), 119-30 (1993).
8. J.A Marley and T.C. Macavoy, J. Appl. Phys., 32(12), 2504 (1961).
9. J.C. Giuntini, W.Granier, sv. Zanchetta and A Taha, 1. Mater. Sci. Lett., 9:(12), 1383-
1388 (1990).
10. M. Ocana and E. Matijevic, 1. Mater Res. 5(5), 1083 (1990).
443
11. G. Pfuft:J.P. Bonnet, M. Onillonand P. Hagenmuller, Eur. 1 Solid State Inorg., 27:(3),
367 (1990).
12. P.A Lessing, Ceramic Bull, 68(5), 1002-1007(1989).
13. R Katiyar,P. Dawsonb,M.M. Hargreave and G.R Wilkinson, 1 Phys. C. Solid St.
Phys, 4, 2421 (1971).
14. J. Nowotny and L.C. Defour, Mater. Sci. Monographs, 47, Amsterdam, p.194, (1988).
15. C.F. Hoge and J.A Pask; CeramurgiaInt., 3(3), 95-99 (1977).
16. lA Varela, E.Longo, N. Barelli,AS. Tanaka and W.A Mariano, Ceramica, 31(191),
241-246 (1985).
17. lA Varela and E. Longo, Ceramica30, 103-110 (1984).
18. T. Quadir and D.W. Readey, in Sinteringand heterogeneouscatalysis 00. By G.C.
Kuczinski, AE. Miller, E. Albert, G.A Sargent and A Gordon, New York: Plenun,
159-169:(12) 1984.
19. P.A Cox, RG. Egdell, C. Harding, W.R Patterson and P.l Tavener, Surf Sci., 123,
179-203 (1982).
20. M.K. Paria, S. Basu and A Paul, Trans. Indian Ceram. Soc. 42, 90 (1983).
21. D. Gouvea, lA Varela, E. Longo, A Smith and J.P. Bonnet, Eur. 1 Solid State Inor.,
30:(9) 915-927 (1993).
22.J.A Varela, O.J. Whittemore, and M.J. Ball, in Sintering85, Ed. G.C.Kuczinski, D.P.
Uskokovic, H. Palmourand M.M. Ristic, PlenumPress, New York. p. 259 (1987).
444
SINTERING OF MnZn FERRITE IN THE PRESENCE OF Biz03 PHASE
Marcel Feder', Virgil M. Vilceanu', Nicolae Teoharie',

Eugen Segal', Ovidiu Caltun'iand Georgeta Cosmeleata"
IAFERRO S.A., P.O. Box 30-30, Bucharest, Romania

2University of Bucharest, Faculty of Chemistry, 13 Republicii Blvd.,
7003 I-Bucharest, Romania
3"AI. I. Cuza" University, Faculty of Physics, 11 Copou Blvd., 6600-Iasi,
Romania
4"Politehnica" University, Faculty of Science and Engineering of Materials,
313 Spl. Independentei , 77206-Bucharest, Romania
INTRODUCTION
An outstanding importance is given to the high initial permeability ferrites among the
other sorts of the MnZn ferrites family, due to the widespread application (filters, pulse
transformers etc.).
The initial permeability (Ili) offerrites depends on the mobility of the Bloch's domains
walls. In order to achieve high Ili it is mostly important to lower the anisotropy and the
magnetostriction of the lattice. Hence, the adequate selection of the composition is of first
importance. In the same time, coarse and uniform grain distribution is required for
achieving high Ili.
lt is well known '< that the addition of Biz03 enhances the sintering of Li ferrites by
generating a liquid phase around the grains during sintering. This way, Li ferrites with Ti
and Zn substitutions can be sintered at relatively low temperatures (~ IOSOC), avoiding
the Li-O evaporation and the depreciation of the microwave behavior offerrite.
lt has been recently' reported that Bi203 has positive influence on Ili of the MnZn
ferrites . As shown by Ohial , it is assumed that Bi promotes diffusion mobility of O2
through grain boundaries.
The present study aims at calibrating the effect of the Biz03 quantity upon the
sintering and properties ofa MnZn ferrite having Ili = 4000.
EXPERIMENTAL
We chose the MnZn ferrite with the formula : MIlo,54 ZIlo,37 Fe2,o6 0 4. Samples were
obtained using the conventional technique.
Advanced Science and Technology ofSintering, edited by Stoj anovic et al.

t
0\
250
E
~ 1 50
z
o
....
VJ
z
rt. 100
x
UJ
50
100 200 300 l,Q0 500 ~OO ...... 700 800 900 \ 1000
./""\
HEATING TEMPERAl1JRE, DC
50
30mm
imi
Vi 150
EJ
20mm
Figure 1. Typicall linear dimensional change during heating of compacts: curve I - samples 0,1, or 4; curve II - sample 7.
The oxides used as raw materials (aFe203, Mn304 and ZnO) were suitable for the
high performance MnZn ferrites considered. The oxide mixture in the ratio corresponding
to the above chemical formula was presintered for 1 hour at 800C in air.
The presintered powder, containing ascending Bi203 additional quantities as shown
below, was wet milled to BET specific surface values of 4.3 +/- 0.3 m2g- 1 in a steel ball-
mill :
Sample o I 2 3 4 5 6 7
Bh03 content [% weight] o 0.01 0.03 0.05 0.07 0.1 0.3 0.5
This green powder was pressed into toroidal shape compacts with outer diameter,
inner diameter and height of 25, 12, and II mm respectively. The green density of the
specimens was 2.9+/- 0.1 g ern" .
Successive sets of specimens were sintered in an electrically heated oven with
protective nitrogen atmosphere under various temperature, time and atmosphere
conditions . The optimal electrical and magnetic properties were obtained for the compacts
sintered at 1370C for 2 hours in an atmosphere with O2 > 15% vol. at the maximal
temperature and O2 < 0.1% at temperatures below 1100 C. These conditions will be
hereafter refered to as "optimal sintering conditions" .
The dilatometric curves of the corresponding 20 mm diameter cylinder compacts were
drawn for the temperature domain between 20 - 1000 "C. A Leitz dilatometer was used
and heating was conducted at a rate of 2Cmin-I.
Microstructure images were obtained from an optical reflection microscope.
Electrical and magnetic properties ( resistivity, initial permeability, relative loss factor
tg8/).li, B = f(H) magnetization curve) were measured as described hereafter'.
RESULTS AND DISCUTION
DILATATION CURVES
The dilatation of the disks is shown in Figure 1.

The compacts with less than 0,5 % wt. Bh03 display a typical linear temperature
dependency of the dimensional changes at relatively low temparatures 900C, curve I,
Figurel) as shown by Sugimoto". This remarkably linear behavior can be attributed to an
interdifusion process without new phase formation at temperatures below 800 C. The
spinelic ferrite formation occurs over this temperature accompanied by volume increase,
due to the lower density of the ferrite as compared to the density of the ferric oxide.
An abnormal linear dimensional change appears at the powder compact with relatively
high Bh03 content (curve II, Figure 1). The linear dimensional expansion ceases at
~5 00oC, followed by contraction over this temperature. An explanation for this behavior
can be offered by the relatively high Bh03 quantity : the liquid phase generated by the
Bh03 melting penetrates between the adjacent ferrite particles enabling their
rearrangement, and the neck growth as shown by Kingery?
MICROSTRUCTURES
The typical microstructures of the sintered samples are shown in Figure 2.
447
Figure 2. Optical micrographs ofthe samples 0 (a), I (b), 4 (c), and 7 (d) sintered in optimal conditions.
The samples containing < 0.03 %wt. Bb03 display a microstructure with relatively
fine grains, and a narrow dispersion. The small number of pores are mainly placed at the
grain boundaries (Figure 2, a and b).The samples containing 0.5 ... 0.1 %wt . Bb03 display
a "duplex" type microstructure including both giant and very small grains, with numerous
pores located inside the grains (Figure 2, c).The samples containing 0.3 ... 0.5 %wt. Bb03
display a microstructure composed by relatively large and uniform dimension grains
without inner pores (Figure 2, d).
ELECTRICAL PROPERTIES
As shown by Snelling', since these materials are semiconductors, their d.c . resistivity,
p, should depend on temperature according to :
p = poexp(EplKT) (1)
where: po is the resistivity extrapolated value for T = infinite;

E p is the activation energy ;
K is the Boltzman's constant ( 8.62 x \0-5 eV'K- 1) .
448
1.95-r-------------------':l7"---,
1.90
1.85
1.80 III
-175
E
o
c:
0..
1.70
1.55
1.50
2.0 2.2 2j. 2.5 2.8 3.0 3.2 3.t.

3
.!Q.(K-1)
T
Figure 3. The variation of the d.c. resistivity VS. temperature: I) sample 0; II) sample 1; III) sample 4;
IV) sample 7.
A linear behavior is observed on the samples containing > 0.07 % wt . Bb03

(Figure 3,curves I and II).Break occur in the curves for samples with <0.07 % wt. Bb03,at
temperatures corresponding closely to the observed Curie temperatures,Tc, (Figure
3,curves III and IV). This is a proof of the influence of the magnetic order in the electrical
conduction process, as shown by Luca et al.". E p values were derived from equation (1)
for each curve (Table I) .
449
MAGNETIC PROPERTIES
The characteristics of the magnetization curves (saturation induction Bs, remanent

induction Br, coercivity He, and the energy loss associated with the surface of the
hysteresis loop Ph) are shown in Figure 4
Positive effects upon the magnetic behavior are considered to be the increase of the
Br and Bs and the decrease of the He and Ph. These effects are more visible for the
sample 1 (Figure 4, b) as compared with the other considered.
The relative initial permeability (lli), and the loss factor (tgo / lli) as a function of the Bb03
content are given in Table 2.
20 9 0,6
-+-85
" 8
0,5
15 --9-Hc 7
---Q- Ph 6 0,4 "1l
zr
1= 5 f; .....
l"'
E 10 j> 0,3 -c
!l
L.
(1) 4 3- 2-
VI
(1)
0,2

3
5

2
0,1
-+-- 3r
a
0 0 0,0
0 2 4 6 8 10 12 14
Frequency (KHz)
25 5 0,35
-+-Bs
0,30
20 4
0,25
-+-Hc
15 --a--Ph 3 "1l
P :r: 0,20 zr
E
l"'
j>
.....
.Q
3-
L.
(1) 0,15 o,
10 2-
til !l.
0,10
--6- Br
5
0,05
b
0 0 0,00
0 2 4 6 8 10 12 14
Frequency ( KHz)
Figure 4. The characteristics of the magnetization curves vs. frequency for samples : 0 (a), I (b), 4 (c)
and 7 (d)
450
Table 1. E p values for some sintered samples with Bh03 sintered in opt imal
conditions.
Sample Ep(eV) Llli = E p2 - EpI

at
T<Tc T>Tc (eV)
(EpI) (p2)
o 0.022 0.043 0.021

I 0.036 0.058 0.022
4 0.028 0.031 0.003
7 0.048 0.052 0.004
20 9 0,6
--...-Bs
8
0,5
15 7
8 O,~
..... -+-Hc ~
E 10 -e--Ph
5 ~
0,3 :g:
eo ~ .!P..
Vl
eo .. .. .. * .. . 3
4
0,2
5
-+-B r 2
0, 1
C
0 0 0.0
0 2 4 6 8 10 12 14
Frequenc y (K Hz)
20 9
---+-B s 8
0,5
7
15
6 0,4
_ _ He ::y
i= 5rr
. 10 0,3
.. "i
-Q--Ph
.. .. .. .. .. .. ..Q
L-
eo C-
Vl' ~
eo 3 0,2
5 --A--Br 2
0,1
d
0 0 0.0
0 2 t; 6 8 10 12 14
Frequ en c y (KHz)
Figure 4. Continued
45 1
Table 2. /li and tgB / /l i for samples of MnZn ferrites with Bb03 addition .
Sample /li
o 4445 <8
1 5539 <8
2 4787 < 10
3 3650 < 30
4 2541 < 70
5 2487 < 90
6 3360 < 190
7 3456 < 170
CONCLUSIONS
We can conclude that the optimum level of'Bi -O, in the investigated MnZn ferrite
is achieved at relative low value of concentration 0.03 % wt. ). Intermediate
concentrations of Bb03 ( 0.05 to 0.1 % wt. ) promote coarse crystallization and results
deterioration of magnetic properties. Samples with higher Bb03 levels ( 0.3 to 0.5 %wt.)
exhibit a well microstructure, but poor magnetic properties.This may be due to a thicker ,
stiffer grain boundary phase, causing mechanical stresses within the grains.
REFERENCES
1. P.D.Baba , G.M.Argentina, W.E.Countney, G.F.Dionne, and D.H.Temme,Fabrication

and properties of microwave lithium ferrites,IEEE Trans.Magn . MAG8:83 (1972).
2. M.Feder, G.Catoiu, M.Catoiu, E .Segal ,and P.Cristea, Sintering of LiTiZn ferrite with
low saturation magnetization,J.Mater.Sci.Let .6:1201(1987)
3 .T.Nomura and T.Ochiai,Current topics in the field of materials technology of soft
ferrites, Ceram.Trans.47 :211(1995).
4..T.Ohiai, Current status of soft ferrites in Japan, J.Phys.IV France 7:CI-27(1997).
5.E.C.Snelling.Soft Ferrites, London I1iffe Books Ltd.,London (1969).
6.M : Sugimoto., Abnormal dimensional change ofMn-Zn ferrite in the initial stage of
sintering,in: Sintering and Related Phenomena,G.C.Kuczynski,N .A.Hooton,and
G.F.Gibbon cd.,Gordon and Breach Science Publ. ,New York,(1 967).
7.W.D.Kingery, Densification during sintering in the presence of a liquid phase.I.Theory,
J.A ppl.Phy s.30:30 I(195 9).
8.E.Luca,N.Rezlescu,E .Rezlescu,Research on properties of some spinel ferri tes ,
Me moriiIe Sec tii/or Stiintifice.Academia RSR,seria IV,tomul 1,1977-1978:77(1979)
452
Part VI. NON-OXIDE MATERIALS
THE INFLUENCE OF SINTERING ON THE PROPERTIES OF LITHIUM
FERRITE
Ecaterina Andronescu', Bogdan Trifanescu', Virgil Vilceanu',

Marcel Feder', Dorel Crisan 3
IPolitehnica University - Bucharest , Romania
2Aferro S.A. Bucharest , Romania
3mstitute ofPhysical Chemistry, Bucharest, Romania
INTRODUCTION
Ferromagnetic materials such as ferrites are widely used in high-frequency

devices. The importance of these materials lies in their properties and high electrical
resistivity, which allow electromagnetic wave to propagate through the medium with
characteristics that depend on its state of magnetisation.
Knowledge of chemical, physical and technological properties becomes
necessary to improve their performance in practice.
Out of the classical triangle "recipe - processing - properties" , the present paper is
focussed on the processing - properties relation, studying the properties of Mn02 added
Ti0 2 substituted lithium ferrite s versus the associated sintering conditions .
EXPERIMENTAL
Four samples were manufactured by standard ceramic techniques, having a

composition described as :
( Li2 0 ) I (F'203h563~5x ( Ti02)x
where x= 0.387; 0.735 and 1.126 respectively for samples 31, 32; 33. and
(Li 20) I (Fe20 3) 3.563.Q 5(X+Y) (Ti02)x (Mn0 2) y
where x=1.126 and y=O.204 for sample 331.
High purity iron oxide, lithium carbonate, titanium dioxide and manganese oxide
were the raw materials used. These were weighed according to the recipe and wet mixed in
a ball mill. The slurry was dried and presintered at lOOOC for 4 hours. The
Ad vanced Science and Technology ofSintering, edited by Stojanov ic et al.

presintered powder was wet grinded for 40 hours in a ball mill. The slurry was dried and
binder (trimethil- cellulose - Thyllose) was added to granulate. 20 - 30 mm diameter by 4 to
5 mm thick disks and 20 mm outer diameter by 7 to 8 mm thick toroids were pressed. With
the purpose of obtaining < 10 % porosity parts, 1050 - 1200 C temperatures were
proposed. these values being limited by oxygen dissociation, lithium volatilisation and
grain growth. Sintering was conducted in a tube oven in air for 5 hours.
The saturation magnetisation was measured with a Walker Scientific MH 10-20
hysteresisgraph and the resistivity was measured with a KeitJine bridge on parallel lapped
disks.
The X ray diffractometer TUR M-62 was used in order to identifY the solid
erista1line phase. The microstructure of the fired samples were determined on lapped
and etched specimens with a solution of 25% HCl. The porosity of the samples were
determined by means of image analyser adjusted to an optic microscope.
Ceramic structure
Microscopic analysis and X-ray determination indicated that the system

(Li20)l (F~0Jh.563 - oJlfi0J),. presents a single phase solid solution in the studied
range of composition (x=O.387 ; 0.735 ;1.126)
Cell edge measurement was used to calculate the X-ray density of the
composition investigated as shown in Figure 1
4.65
4.6
~ 4.55
e
lJ 4.5
~
4.45
......
DlI
4.4
4.35
4.3
4.25 X-Ra)' density
4.2
4.15
Bulk density
0.387
Fipre 1. Bulk density and X-ray density vs. Ti0J concentration for sintered samples
0
at 1000 C
454
High density lithiwn ferrites are widely known to be difficult to obtain' . For the
studied bodies, densities over 4g1cmc were generally obtained even in light sintering
condition.
Ti(h and Mn(h addition generally causes a decrease of density relatively to the pure
lithiwn ferrite and, consequently, some sintering difficulties , as no outstanding benefit is
brought about by rising of the sintering temperature.
The variation of two significant body features was studied versus the sintering
conditions'.
Microstructure
Optical microstructure was employed for revealing the size and shape of pores in
the specimens, provided they were monophase bodies.
The total porosity remained constant while increasing the content of Ti(h but
growth of the increasing nwnber (2.5- 7.5 urn) has been observed on behalf of the little
pores (0.5-2.5 um), (samples 31 and 33 in Figure 2).
sample31 sample33
F~ure 2 - Metallographic view
The growth of the total porosity and of the number of middle pores has been
observed while increasing the sintering temperature for sample 33 (Figure 3).
Addition of Mn02 caused the alteration of the texture (Figure 4). In the presence of
his trace the temperature increase caused the decrease of porosity accompanied by a
grown number of middle pores .
The saturation ma~netisation
The value of the ferrite saturation magnetisation is of outstanding importance for the
application. Ferrite magnetisation is given by the balance of the magnetisation of the two
opposite sublatices' Substitution of the Fe 3+ ions with other magnetic ions in the
octahedrical lattice decreases the magnetisation value.
455
70
/
1200 d e ~ C
Temperature
1000 deg.C
Dimension (urn)
Fi:ure 3- Porosity hystograms
31 .ntered at: 1000C 1200C

S_Ie3 SI hie view
Fi:ure 4- Metallograp
456
3000
2500
5'
-
- 2000 ./
-....
.~
.~ 1500
q"
C
r:)i)
(': 1000
~
500
Sample
1150
Temperature[deg.C]
Figure 5. - Saturation magnetisation as a function ofthe sintering temperature.
Increasing of both Ti02 and Mn02 contents causes the decrease of the
m~etisation (Figure 5). The explanation of this fact resides in the way the Ti 4+ and the
Mn occupy the octahedral positions , pushing the Fe ions to migrate towards the
tetrahedral sites as Fe2+
A maximum of the magnetisation is attained while increasing the sintering
temperature. This accounts for the effect of the microstructure on the magnetic
characteristi cs.
The resistivity
Lithium ferrite is considered to exhibit interesting properties; depending on the

way the sintering is conducted, values between 105... 107 Ohm. cm are obtained, which
give these materials good application in the microwaves field 4
Progressive Ti~ substitution causes the decrease of ferrite resistivity, consequent
to the enhancement of the Fe3+ to Fel + transition in the presence of Ti 4+
Addition of small Mn02 quantities considerably improves the resistivity. This is
probably the consequence of the redox kinetics competition between the Mn and Fe
ions, out of which Mn seems to be the most velocious , thus blocking the electrons.
Also lithium volatilisation at high temperature introduces supplementary punctual
defects in the lattice, which amplify the complexity of the electric conduction
mechanism. The consequent resistivity increase suggests a possible VLi<->e- interaction
which reduces the charge mobility in the lattice.
457
CONCLUSIONS
The magnetic properties of Ti substituted and Mn doped lithiwn ferrites vs.

sintering temperatures were studied.
The optical micrographs of the specimens displayed a unimodal size distribution of
the pores centred around 2.5 um,
The bulk density, the microstucture and the electromagnetic properties have been
found in a good correlation and consistent with the sintering conditions
The Ti02 substitution and the MoO] traces act upon the electromagnetic
properties both via the sintering denification of the body and the lattice
modifications.
REFERENCES
l.P.D.Baba, G.MArgentina, W.E.Cowtney, G.F.Dionne, D.H.Temme-Fabrication and

properties ofmicrowave lithiwn ferrites, IEEE Trans. Magn. MAG 8 ; 83 (1972)
2. A Yousif: M.E.Elzain, SAMazen, MH.Abdalla- X- ray diffraction and Mossbaner
investigation of Li-Ti ferrites, J. phys. conds. matter 6, 5717, (1994).
3.N.Nogues, G'Villers . J.L.Dorman, J.Teillet-Field and temperature dependence of
magnetic viscosity in randomly canted Li-Ti ferrites, IEEE Trans Magn. MAG
26; 2229 ( 1990);
4.lBarbariol, S.Roitti, N.Sparvieri,F.Ricciardiello--Electrical propreties of Li-Ti
ferrites, Interceram 45;320 (1996).
458
DEVELOPMENTS IN THE POWDER METALLURGY OF NON-OXIDE
CERMETS
H. PASTOR
CERMeP
54, Avenue Rhin et Danube
F-38 100 GRENOBLE
INTRODUCTION
We will, here after, review the latest developments in the powder metallurgy of non-
oxide cermets, viz : tungsten monocarb ide-, titanium carbonitride-, and titanium diboride-
based cermets .
TUNGSTEN MONOCARBIDE-BASED CERMETS
The latest developments in the field ofWC-Co cermets (or cemented carbides, or hard
metals) mainly concern :
the production of ultrafine (or nanometric) powders,
the production of gradient materials ,
the design of new binder phase.
Production of ultrafine (nanometric) powders.
It is well known that, for a given cobalt content, the hardness of a WC-Co cermet can
be increased by decreasing the WC mean grain size; which explains the present-day craze
of research for new production processes of ultrafine powders.
The classical ways of production of WC are presented in figure 1. In order to produce
ultrafine W powders - 0.3 to 1 urn -, starting for instance from W03 , the formation of
W l 8049 (o.i. = 2.72) should be skipped over and the two main reduction steps : W0 3 ~
W0 2 and W0 2 ~ W should take place in the lowest possible humidity environment. The
formation of ultrafine grains is favoured by :
. using a co-current hydrogen flow,
Ad vanced Science and Technology ofSintering ; edited by Stojanov ic et al.

Kluwer Academ ic/Plenu m Publishers, New York, 1999 461
decreasing the oxide layer thickness in the boats,
increasing the hydrogen flow rate,
decreasing the passing through rate of the boats,
decreasing the reduction temperature,
using hydrogen with the lowest dew point,
using a two-step reduction process,
a smooth temperature gradient in the furnace .
APTA H,O cuboids

Ammonium Tungstate evaporation) APT. 6 H20 platelets
Aqueous solution -H20 { APT. 10 H20 needles
Precipitation
H'
calcination/reduction
H,
calcination TBO reduction

WO x H2
ATB
pseudomorphs, +CO(CI4)
Figure 1 - Classical ways of production of WC powders
If ultrafine tungsten powder is carburized at less than 1500C, ultrafine WC powder

can be obtained, since at such temperatures the relation : <l>wc == 1.10 <l>w holds. But when
one has to deal with these powders for sintering, the need of special cobalt binder arise,
since the classical cobalt powders are too coarse (1-3 um). This problem can be solved in
three possible ways:
- the preparation of new submicronic cobalt powders,
- the coating ofultrafine WC particles by cobalt,
- the development of new production processes of preparation of submicronic WC-Co
mixtures.
A new process has been developed for the production of cobalt powder which is based
on the reduction (at 210C) of cobaltous hydroxide by a mixture of ethylene - and
diethylene-glycol (1). This "polyol cobalt" powder is characterized by the spherical shape
and very narrow grain size distribution of its particles, which furthermore are not
agglomerated. The powders are very pure, non pyrophoric, and can be produced with a
mean grain size ranging from 0.3 to 4 urn. The replacement of the classical "hydrogen-
reduced cobalt" by "polyol cobalt" greatly improves the microstructure (better distribution
of Co among WC crystals ; very low porosity), and furthermore allows to decrease the
milling time by half, to decrease the sintering temperature by 50-75C, and even to spare
HIPping of low-Co grades.
The polyol process can also be used to coat WC particles with a cobalt layer (2). An
even distribution of cobalt over the surface of the WC powder is obtained without any
462
formation of cobalt islands . WC grains can also be coated with a cobalt layer by spray-
drying a slurry of WC grains in a solution/suspension of cobalt salt (3) .
Composite WC-Co powders with nanometric structure can be produced (4) by a three-
step process :
preparation and mixing of an appropriate starting solution (ammonium para-or meta-
tungstate + cobalt salt) ;
spray-drying to form a chemically homogeneous precursor powder ; and
classical or fluid-bed thermochemical conversion of the precursor into the desired
nanoscale composite powder.
For instance :
((AMT.4 H 2 0 ))aq. + ((CoCI 2))aq. "pray-drying ) < AMT + CoCl 2 >

precursor
H 2 , Ar H2 , CO, CO 2 < WC > + < Co >

700C 700 - 1000C intimate mixture
fluidized bed <l>wc = 20-50 nm
Another way (5) (6) is to react APT and soluble salt of cobalt in water at temperatures
from room temperature to the boiling point of the solution keeping the solution pH at a
constant level during the chemical reactions. The powder is filtered off, dried and reduced
to a metallic powder which may be further carburized to a WC-Co powder. In both
processes the incorporation of grain growth inhibitors is possible .
The key to ultrafine-grained WC-Co attractiveness (compared to classical fine-grained
WC-Co) lies in their ability to achieve a higher hardness at identical toughness, thus
displaying a 2 to 6 times higher wear resistance. They find increasing applications in wear
parts, metal- and wood- machining, dental work and printed-circuit board drilling. For
instance, in this last application, a WC ( = 0.4 11m) - 6 % Co grade , with a hardness of
HV 30 = 2050 (94 HRA) , is used to produce drills with a particularly sharp cutting edge,
working at a rotating speed of 40000 revolutions/min .
Production of multilayer - or gradient - materials.
It is possible to create structural discontinuities such as a sharp variation of the WC

grain size and/or of the cobalt content in a cemented carbide by-co-compaction and co-
sintering of two different grades . These discontinuities are relatively stable when sintering
is performed at relatively low temperatures but they vanish at high sintering temperatures
because of the diffusion of cobalt enhanced by the gradient of capillary forces (7) .
The problem can be most efficiently solved by the technology based on the absorption
of a cobalt melt (ColW/C : 65/32.8612.14) by pore-free sintered components welded
together (i.e. C04/C020, C06/Co15, C06F/C06C, C06/ColOF, CollC/Co15, C06F/C04).
This technology ensures the obtention of high quality components with the maximum
variation of their structure and properties throughout their volume (8) .
A better knowledge of the W-C-Co phase diagram and thermodynamics has allowed
(9) (10) a multilayered material to be produced , whose composition (along a line
perpendicular to the surface and starting from it) is as follows :
. a surface zone free of eta-phase where the binder phase content in the outerpart of
said zone is lower than the nominal (and which is consequently very hard) and, in addition,
constant or near constant ;
. an intermediate zone (which is the inner part of the eta-phase free zone) where the
binder content is higher than the nominal (this zone is thus less hard but more tough) ;
463
a core of eta-phase containmg cemented carbide, a little less tough than the
intermediate zone but harder by the mere fact of a fine dispersion of eta-phase .
At the end of sintering of a slightly substoichiometric grade, a carburizing thermal
treatment is applied in an atmosphere (CO, CH4, . . .) with a carbon activity of 0.8-1.0, so
that the speed of carbon transport onto the surface of the material is higher than the speed
of diffusion of carbon towards the core. This DP (dual properties) material has applications
in the production of buttons for rock drilling bits and for mineral and asphalt cutting tips .
The design of new binder phase.
It has been for many years a concern of the cemented carbide industry to use elements
other than cobalt as the binder metal. There are many reasons for this, but the two major
ones seem to be to gain less sensitivity to current price fluctuations of cobalt and to develop
alloys with new and interesting properties (for instance for application in seal rings,
nozzles , ball valves, etc ...). However WC-Co cemented carbides offer many advantages as
compared to most other systems. Good wetting between the carbide and the binder, easy
carbon control and superior mechan ical propert ies are often referred to. Wetting is indeed
very good between WC and Co but it is also good between Fe and Ni and We. It has also
been shown than dense products are easily made by using these binders as well .
However, it might be more difficult to obtain competitive mechanical properties and
to find the optimum choice of carbon content for such alloys. A comprehensive work by
PRAKASH (11) (12) indicated that these problems can also be solved . A special attention
was given to Fe/Co/Ni binder phase because its strengthening could be achieved by phase
transformation, precipitation hardening and order - disorder transformation.
New computational tools for the description of high-order systems (phase diagrams)
have increased the possibilities of overcoming many of the problems encountered, when
using Fe and Ni as binder metals . UHRENIUS's work (12) shows how calculations can be
used in the process of selecting suitable compositions of these complex alloys . To
investigate the usefulness of the calculated Ni-Fe-Co-W-C phase diagram, a study was
undertaken where five different Ni/Fe/Co-ratios were chosen to check the agreement
between calculated and experimental phase boundaries . Each metal ratio was tested at five
different carbon levels . A number of phase diagrams corresponding to these metal ratios
were calculated. These diagrams could be used to estimate the limits within which the
carbon content should be chosen to avoid the precipitation of graphite or eta-phase. In
figure 2 these limits are plotted together with the experimentally determined carbon
contents and the results of the microscopic examination. Within the limitations of the
experiments it is found that the agreement is rather good for the quaternary Fe-Ni-W-C
alloys, but more assessement work must be done to gain the high accuracy needed for
grades based on cobalt-rich binders .
TITANIUM CARBONITRIDE-BASED CERMETS
In 1970, KIEFFER et al. (13) modified the TiC-NilMo cermet by adding TiN . They
found that optimum properties were obtained at medium TiC contents in the carbonitride
and that the 70/30 (wt. %)-NilMo binder phase gave optimum hardness and transverse
rupture strength (TRS) . Cutting performances proved to be much better than those of
nitrideless cermets because of an excellent wear resistance and a negligible cratering.
In 1974, RUDY et al. (14) claimed that by selecting the compos ition and solution
temperature, a single solid-solution phase (Ti,Mo)(C,N) will, upon cooling, undergo a
464
Legend:
n-phase 0 no precipitate
~ minor n -phase
,
graphite
Ni/Fe/Co :.....------ Stoichion:etric

ratio, w/o : ccrnposruon
7/13/0
I -la ~
%:l
~

:
/.

..
~
13,7/0
I ~ o:~
: /
I ~
5/1 0/5 {d~ ;;
.. -~
~~
10 /5/5 , ;;; 0
: ~
p.
, ~
I '

0/0/20
I ~~
4.50
CD 8 :);2;
,: ~r ,
5.00
5.5 0
weight % Carbon
Figure 2 - Comparison between calculated WC + free binder windows

and experimental results (12) on, WC-Ni-Fe-Co alloys with 20 % of binder metal
spinodal decomposition giving a Ti- and N- rich a ' -phase surrounded by a Mo- and C- rich
a "-phase . In (Ti, Mo)(C,N)-NilMo cermets, this spinodal decomposition brings about an
extremely fine microstructure, and an excellent stability towards grain growth .
Sintering.
The sintering of TiC- and Ti(C,N)-NilMo cermets has been studied by many authors
(15 to 23) . We will present here after two different approaches , one by PIRSO (23) using
X-ray phase analysis, and the other by ETTMAYER et al (21, 22) using chemical analysis
of the gas phase, both all along the sintering cycle.
The mechanism of formation of the (Ti,Mo)C rim on the surface of TiC grains during
the sintering of TiC-NilMo cermets has not yet been adequatly studied. BOGOMOLOV et
al. (20) assume solution-reprecipitation to be prevalent, while LINDAU et al. (16) regard
the diffusio n of molybdenum atoms in the TiC lattice as dominant.
According to PIRSO's studies (23) on the sintering of TiC-50 % Ni/Mo and TiC-20 %
NilMo cermets, changes begin at 500C with a narrowing of the Ni diffraction lines (200,
I ll) originating from the relaxation of milling stresses. At 750C the Ni diffraction lines
widen abruptly and shift towards smaller angles. At the same time the intensity of the Mo
lines (110) and the TiC lines (Ill , 200) is reduced.. This corresponds to the dissolution of
molybdenum in nickel and to the beginning of the dissolution of molybdenum in TiC.
A further decrease of the TiC line intensity between 750-1 150C indicates an increase
of the molybdenum dissolution in TiC. At 1280C the Ti-Mo-NiC eutectic melts. The
nickel lines narrow, shift into the molybdenum position and intensify . This shows that the
molybdenum content in nickel has decreased because part of it has dissolved in the TiC
465
lattice, forming the (Ti, Mo)C rim. Furthermore, part of the titanium atoms is driven out
from TiC into the binder. An increase in molybdenum content brings about an increase of
the Ti and Mo contents in the binder. As a consequence, the hardness (and thus the wear
resistance) of the cermet increases, while its transverse rupture strength decreases. At the
same time the molybdenum content of the rim increases.
Grain growth starts at 1280C when a liquid eutectic forms . At l3IOoC the carbide
grains have already grown but the cermet still contains porosities. At 1400C the sintered
cermet has no pores. The mechanism of a carbide grain growth is basically recrystallization
through the liquid phase. Coalescence of carbide grains only occurs in high molybdenum
and low binder content cermets. Carbide grain growth is not significatly affected by the
sintering time (up to 1 hour) while TiN addition appears a good grain growth inhibitor.
ETTMAYER et al. (21, 22) have studied the influence of various starting raw
materials on the sintering behaviour of cermets. They used mixtures of : binary
compounds TiC, TiN, M02C with Ni ; solid solutions Ti(C,N), (Ti,Mo)C with Ni ;
quaternary solid solutions (Ti,Mo)(C,N) with Ni, in such proportions as to yield identical
gross compositions. They observed that the microstructures of the sintered products were
different with respect to the distribution of Ti and Mo depending on whether alloyed or
unalloyed hard materials had been used as starting powders. However any significant
influence on the sintering behaviour could not be observed. Only the presence of free
carbon in the starting mixture influences the nitrogen evolution rate.
By chemical analysis of the gas phase during the sintering cycles, tey have observed
the following steps :
- the evolution of CO from chemisorbed or chemically bonded oxygen (TiC, M02C ,
free carbon, ...) starts at about 900C, peaks around lIOOC and fades out at about 1250C.
Nickel and/or cobalt accelerate the process.
- the evolution of nitrogen starts at about 1200C, passes through a maximum at
l300C, decreases between l300-1400C and then increases gradually above 1400C. The
nitrogen evolution is linked to the formation of localized solid solutions (Ti, Mo)(C,N) on
the surface of hard particles .
- the onset of the formation of liquid phase at approximately 1320C coincides with
the drop of nitrogen evolution et does not appear to be influenced by the starting raw
materials . The (Ti, Mo)C rim forms rapidly around the hard particles and seals the core
against attack by the liquid phase.
Microstructure and properties.
The influence of TiN upon the strength of TiC-M0 2C-Ni cermets has been extensively
studied (see for instance : 19, 24, 25, 26 to 35). Figure 3 shows the effect of the TiN
content in TiC-(0-20%)TiN - 20 % M02C - 20 % Ni (or Co) cermets on the defect size,
TRS and hardness (24, 36). It can be seen that HIPping brings a pronounced increase in the
TRS of TiN-containing cermets, and the more is this increase as the higher is the TiN
content.
The replacement of the nickel binder by cobalt significantly rises the hardness and
lowers the TRS. The average defect size increases rapidly as the TiN content increases, but
HIPping brings back the defect size to an acceptable level.
The influence of the binder content on TRS, hardness and average defect size (24, 36)
is shown in figure 4. It should be noted that the TRS of HIPped cermets reaches a
maximum of 2700 Nzmm- at a binder content of 20 %. Figure 5 allows to compare the plot
of hardness versus TRS for various cermets (24, 36) : cobalt as a binder appears to give a
better HV-TRS compromise than nickel.
466
oN 1800
>
J:
I 1600
-- -- -------------.. ...............
-
III
.......
III _-- Ni
aJ
C
"C
L..
III
J:
_ - - - - - - - H IP'ed
NI > /'
/
,/
N 2400 /'
/'
E /' Co
E /'
<,
z ./
'4
/
I 2000
./
./
Ass intered
U)
.-
/
0::
160 0
--------------
--- Ni
- -- --
Co
120
Co
100
E
::t / / Ni
I 80
/
/
aJ
N ,/
..
,/
III ,/
60 ,/
--
,/
_....- ....-
u ,/
.....C1l 40
C1l
0
HiP ' ed
- - :::-::_=-:_=---------- ,
20 K
0
0 5 10 15 20
T iN content- %
Figure 3 - Effect of TiN content of TiC-(0-20%)TiN-20% Ni(Co) - 20% MoC
cermets upon defect size, TRS and hardness, according DOl (36)
467
1800
0 1600
N
>
I
-- --- ...........................
I
III
1400 ......
NI "- ......
III <,
120~1
Ql <,
c <,
......
"0 <,
L
l\l
I 1000
Hlp'ed
///---!..'\----
2500 Ni/
/
/
/
-
......
(Il ...... "
.>:
E 2000 ......-
/ .......
E ......-
Z .> Ni
I As-sintered......-/
~co
(/)
0:: 1500
I-
,,-
1000
<,
100 <,
<,
<,
-
<,
E ......
~ 80 <,
<,
-.
I
Ql
N
60 Ni
III
.....
U 40
--o
Ql
Ql HIP' ed
20
k' Co
oL....l.-------....I--------"-'
10 20 30
Binder content-%
Figure 4 - Effect of binder content of TiC (15%), TiN (10-30%) , Ni(Co) (20%)
MojC cennets upon defect size, TRS and hardness, according DOl (36)
468
1100
o
N
>
I 1500
I
III . . . 7'i e , J}-.e,c
III
C
Ql
.....
..... .....
7- -.....
'IV,
1'tt1,
"\
, 0
'"tJ
....
lU
'e '~:' 0 <,
I
I
1300
I I
I
I
I
I
1 100 '----'- --=-~__=_-----____:~_:__------.J
1500 2000 2500
TRS-N/mm 2
Figure 5 - A comparison of Hardness-TRS relation among various kinds of cermets,
according DOl (36)
NISHIGAKI et al. (27) have found that the hardness, TRS and 0.002 % offset
compressive yield strength of a Ti(Co 7 NO.3) - ] 5Ni-8Mo cermet decrease appreciably by
adding carbon (up to 1 % wt.). NISHIGAKI et al. (28) have investigated the influence of
the N/C + N ratio on the properties of Ti(C,N)-30M0 2C-13Ni cermets. The conclusions are
that, with an increase of N/C + N ratio : the growth rate of the (Ti,Mo)(C ,N) rim, the
hardness, the plastic strain and the Young's modulus decrease ; the TRS remains unchanged
; the 0.002 % offset compressive yield stress, the thermal expansion coefficient, the thermal
conductivity and the thermal shock resistance increase.
The mechanical properties of TiCo.7 NO.3 - and TiC o.s N o.s - 19 % M02C - 23-24 % Ni
cermets, sintered in nitrogen, were studied by SUZUKI et al. (31) as a function of the
nitrogen pressure PN2 . TRS passes through a maximum at PN2 = 0.2 kPa and 3 kPa
respectively for TiCo.7 No.3 - and TiC o.s N o.s - cermets. This is explained by the fact that
pores acting as fracture sources were apt to form during sintering under nitrogen, but pore
size was always smaller in TiCo.7 No.3 -cermets, and pore size in each alloy was minimized
at the above given P N2 where each carbonitride was found to be stabilized under these
pressures . For the same reasons sintering under nitrogen partial pressure has also been
recommanded by PASTOR (19).
SUZUKI et al. (33) have studied the mechanical properties of TiC o.s No.5 -(2-18 %
vol.)M0 2C-16.4 % vol. Ni cermets in relation to the M02C content. The samples were
sintered and HIPped at 1450C and then resintered at 1550C (resintering eliminates nickel
pools often formed in nitrogen-containing cermets when HIPped) . The TRS at room
temperature of sintered cermets increased with increasing the M02C content and passed
through a maximum at about ]0 % vol. M0 2C . M02C also increased the TRS value at
lOOOe. The highest hardness is obtained (at room temperature) for 14 % vol. Mo.C .
The structure difference between TiC-TiN-M0 2C-Ni and Ti(C,N)-M0 2C-Ni cermets
has been investigated in details by TSUCHIYA et al. (34) and UEKI et al. (35), using TiC-
18.3% TiC-20 M0 2C - 20 Ni and Ti(Co.7 No.3) or Ti(C o.s No.s)-20M02C-20Ni (% wt;)
cermets . The structure became finer in both cermets with increasing the nitrogen content,
469
and the structure of (TiC + TiN)-based cermets was considered to be finer than that of
Ti(C,N)-based cermets. In the former cermets coarse and extremely fine carbides and
carbonitrides coexisted. The hardness at RT and 1l00C were higher in the (TiC + TiN)-
based cermets, although TRS and creep strength were nearly the same in the two cermets.
Applications
Most cermet grades are suitable for machining of long and short chipping work piece
materials (ferrous and non ferrous metals, and non metals) . They are able to operate over a
wide range of cutting speeds. Compared to cemented carbide grades they allow higher
cutting speeds because of their higher plastic deformation resistance, and they display a
reduced edge build-up at lower cutting speeds because of their chemical inertness. Cermets
achieve excellent surface finishes and close size control in turning, grooving, threading and
milling applicat ions. Expensive grinding operations are frequently replaced through
machining with cermet cutting tools. Coolant is applicable, except in rough machining
operations, and generally results in longer tool life (37).
Furthermore, there is undoubtedly a future for these cermets in wear parts for aircraft
and land-based gas turbines, automobile engines, oil industry and bearing industry.
TITANIUM DffiORIDE-BASED CERMETS
Transition metal borides, because of their unique bonding characteristics , display a

unique combination of high hardness, high melting point, high electrical and thermal
conductivity and very good corrosion and oxidation resistance. Hence, borides are very
promising candidates for hard material applications. However, until recently, most of the
attempts at finding a suitable binder had failed. An extensive review of the literature, up to
1976, on the sintering and properties of transition metal borides and cermets based on
them, has been made by PASTOR (38). Nowadays two new generations of boride-based
cermets are developing : those based on TiB 2 and those based on M0 2Fe(Ni)B2 and WCoB.
We will restrict our comments to TiBrbased cermets only.
Sintering and properties
Many papers have been published recently on the development of TiB2-based cermets
by German (39 to 43) and Franco-Spanish (44 to 50) research teams.
The German team has mainly focused their investigations on TiBrFe cermets . The
mixing of the powders is made in a planetary ball-mill, with steel balls, under n-heptane ,
for 12 hours (40, 41). Pressureless sintering investigations led to the following conclusions
(40) :
- Adequately specified cermets, with 15-20 % vol. binder phase, reach nearly full
density by pressureless sintering at nearly 1600C.
- Boron carbide (B4C) being a contaminant of the raw TiB2 powder, F~B and Ti203
are formed during heating at relatively low temperature (1000C) before shrinkage starts,
because of the reaction :
2 Ti0 2 + 8 Fe + B4C ~ 4 F~B + Ti 203 + CO
- Shrinkage begins after liquid phase formation at 1140C, in the range of the Fe-F~B
eutectic . After the resulting particle rearrangement, the densification rate decreases.
- Densification is reaccelerated when the Fe-TiB2 eutectic temperature is reached
(1340C) and an increasing amount ofliquid phase is formed.
470
Table 1 - Properties of various TiBrbased cermets
Ref. Composition Hardness KIC TRS E

1/2
HV10 (MPa .m ) (MPa) (GPa)
TiB 2 + 19.8 Fe + 8.6 Ni % wI. 1420 5,5 436 325
TiB 2 + 14.4 Fe + 6.1 Ni + 8 TiAI) 1780 9,2 1019 405
TiB 2 + 18 Fe + 7.7 Ni + 10 TiAI) 1490 .. 1221 396
TiB 2 + 20.8 Fe + 8.9 Ni + 6 TiAI) 1450 .. 98 5 343
92 TiB 2 + 13.6 Fe + 5.8 Ni + 1 Mo + 8 TiAI) 1792 8,1 - -
TiB 2 + 13.6 Fe + 5.8 Ni + 1 W + 8 TiAI) 1796 10,7 - -
TiB2 + 13.6 Fe + 5.8 Ni + 2.6 CI + 8 TiAI) 1496 6,4 - .
TiB 2 + 20 (316 L) + 8 TiAI) 1714 7,7 . -
TiB 2 + 21 (316 L) + 4 TiAI) + 3NiTi 1842 7,9 . -
TiB 2 + 5 (Fe + Fe2B) % vol. 2260 5,9 610 510
TiB 2 + 20 (Fe + Fe2B) 1520 7,9 720 465
87 TiB 2 + 20 (Fe/Cr/N i + Fe2B) 161 0 8,7 790 465
TiB 2 + 5 (Fe/C r/NilTi) 2040 7,3 900 515
TiB 2 + 10 (Fe/Cr/NilTi) 1800 8,1 1010 510
TiB 2 + 20 (Fe/Cr/N ilTi) 1480 12,4 950 465
* : cennets con taining an austenitic binder phase; the others have a bind er of ferriti c type
**: non cracks genera ted (pal mqvis t method non applicable)
.j>.
-.J
- Fe2B makes an important contribution to the densification behaviour but deteriorates
the toughness by consuming some iron of the binder phase while forming. Its formation
can be prevented by the addition of titanium (43). This addition probably results in the
formation of small amounts of TiC (by the reaction : 2 Ti + B4C ~ 2 TiB 2 + C) which
hinders or delays the reduction of oxygen layers on TiB 2 grains during heating. Therefore,
densities do not exceed 95 % after pressureless sintering, but full densification is possible
by a post-HIPping treatment.
The Franco-Spanish team has revised the TiBrFe phase diagram and demonstrated
that pseudo-alloys TiB2-Fe cannot exist, the equilibrium existing only between TiB 2 and
Fe-2/5 % at. Ti (88,9 1). It has also been found and demonstrated that the pollution of the
starting TiB 2 powder (by 0 , C, N but above all oxygen) is very detrimental to the
sinterability of the cermet. Wetting of TiB 2 by an equilibrated TilFelB melt is considerably
decreased by the presence of oxides (45) . The "cleaning" of the powders can be achieved
by addition of strong deoxidants like rare-earth metals (e.g. neodymium as Nd/Ni alloy) ,
aluminium or titanium . As a result :
- Nearly dense (97-98 %) samples of TiB 2-Fe/Ni /Ti cermets containing a fine
dispersion ofNd 20 3 and Ti(C ,N) (resulting from the "cleaning" action) have been obtained
by pressureless sintering at 1450C. Full densification is obtained by HIPp ing.
- By adding controlled amount of aluminium to a Fe-Ni binder, the formation of
undesi rable borides (e.g. M 2B, M 3B 2) is totally prevented. The crystallographic
characteristics of the Fe/Ni/AI binder phase can be easily changed from BCC-ferrite to
FCC-austenite by varying the amount of aluminium (46, 49) .
The liquid phase sintering conditions of TiB 2-TiF e2+x cermet has been deduced from a
thermodynamic approach (50) . Densification up to 93 % of theoretical density can be
achieved at 1400C and for a rather low solubility (1.7 %) of TiB 2 in the liquid .
Table 1 gives the properties of cermets according to JUNGLING et al. (43) and
SANCHEZ et al (48) .The hardness-toughness profile of TiBrbased cermets expands
beyond the range covered by commercial cemented carbides. These cermets are thus
potential candidates for cutting tool applications. Their high hardness and good resistance
to oxidation and corrosion open also their application as wear parts .
CONCLUSIONS
This survey has presented briefly the complexity but also the many advantages of
cermets. It is true that WC-based cermets strongly dominate and will continue to dominate
the hard material market. However, because of their high wear resistance, high corrosion
resistance and high resistance to oxidation, there is no doubt that Ti-based cermets will
develop and become indispensable in many niches in a near future . This is already achieved
by titanium carbonitride-based cermets.
REFERENCES
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474
SINTERING BEHAVIOUR AND MICROSTRUCTURE DEVELOPMENT IN
ELECTROCONDUCTIVE Si3N4-TiN COMPOSITES
Ljiljana M. Zivkovic,' Snezana M. Boskovic ,' and Miroslav S. Miljkovic 3
'Faculty of Electronic Engineering, Beogradska 14, 18000 Nis, Yugoslavia

2Institute of Nuclear Sciences "Vinca", 11000 Belgrade, Yugoslavia
3Laboratory for Electron Microscopy, University of Nis, Brace Taskovic 81,
18000 Nis, Yugoslavia
INTRODUCTION
The Si 3N4-TiN composites offer the unique combination of thermal, mechanical and
electroconductive properties making them suitable for wide range of engineering
application. The use of the appropriate amount of TiN , which is dispersed in Si 3N4 matrix,
enable s to achieve tailored electrical conductivity of composites, from high insulating to
electroconductive ceramics. The use of TiN, ranging from 35 to 50%, together with
appropriate sintering aids, resulted not only in fully dense compacts but also in compacts
with a resistivity less than 10-' Dm as well. The addition of TiN has a marked effect in
obtaining the uniform microstructure and improves also the mechanical properties such as
the fracture toughness and flexural strength of composites as compared with those of the
monol ithic Si 3N4 (Bello si et al ., 1992; Gogotsi, 1994; Boskovic et al ., 1994; Choi et al. ,
1995). The electrical resistivity of Si 3N4 - TiN composites depends primarily on the amount
of TiN content, but due to the percolation phenomenon and the probability of forming a
conductive network, the conductivity depends in a great extent on the starting powders size
and on the micro structure formed during the liquid phase sintering as stated by Martin et al .
(1989) , Bellosi et al. (1991) and Yasutomi et al . (1991) .
Since the densification of Si 3N4 - TiN based composites is promoted in the presence of
yttria or some other oxides like rare earth oxides as sintering aids, the new silicate phase
appeared. The densification degree and the corresponding microstructure depend on the
amount and viscosity of new formed liquid phase which can be amorphous on partly
crystalline and usually appears as a intergranular phase, described firstly by Gre skovich and
Clair (1978) and Hwang and Tien (1989) .
The present study was undertaken to investigate the effect of various amount of TiN
on the microstructural and electrical properties of Si 3N4- TiN composites sintered in the
presence of yttria and rare earth oxides Nd 203, Sm.O, and DY203' as sintering aids. In
addition, the special attention is given on the examination of systems with 35% TiN.
Advanced Science and Technology of Sintering, ed ited by Stoj anovic et aJ.

MATERIALS AND METHODS
Silicon nitride - based composites are made by mixing fine grained powder of a -Si3N4
and TiN (H.C.-Starck) with R Z03 (R=Y, Sm, Dy and Nd) as sintering aid. The amount of
TiN varies from 0 to 50 wt.% and that of RP3 was 10 wt.%. The particle size of a-Si3N4
powders ranged from between 0.2 11m and 0.4 11m, although some agglomeration of
particles is also noted. The size of agglomeration was between 1.5 11m and 2.5 11m. TiN
powder consisted of irregular shape particles ranged from 1 11m to 7 11m. Suspended in
isopropanol, the powders were mixed in attritor with Si3N4 balls for 2 hours. After drying at
room temperature, powder mixtures are uniaxially pressed and thereafter isostatically
pressed under 147 MPa. The pellets are sintered for 10, 60 and 120 minutes at 17800C in
nitrogen atmosphere. Densities were measured using the Archimedes method.
The microstructural investigation is performed using SEM JSM 5300 equipped with EDS
(QX 2000). The electrical resistivity is determined from V-I measurements using Keithley
instrument Mod. 237 with corresponding resistivity chamber.
Numerous properties of Si3N4- TiN composites are in function of TiN content such as
sinterability, microstructure, mechanical and electrical properties and oxidance resistance.
The role of TiN can not be discussed without taken into account the presence of sintering
aids. The function of each additive, or synergistic effect of TiN and RP3' is not always
fully understood but it is known that TiN inhibits the grain growth in Si3N4 matrix,
increases the flexural strength and toughness of Si 3N4-TiN up to 30 wt.% TiN. With content
of TiN higher than 35% the electrical resistivity of composites is decreased drastically.
Regarding the influence of the rare earth oxides and amount of TiN on the sintered
density it has been noticed (Boskovic and Zivkovic, 1995) that density firstly decreases up
to 30% TiN thereafter with the increase of TiN the density increases and fully dense
compacts have been obtained with 50% TiN after prolonged sintering time of 120 minutes.
The most pronounced drop in density is observed with samaria doped system, due to higher
viscosity of Sm-silicate phase formed during sintering process (Boskovic et al., 1994). On
the other hand, the fully dense compacts doped with yttria reached the theoretical density
within one hour of isothermal sintering even with low content of TiN such as 30 wt, % as
shown by Zivkovic and Boskovic, (1996).
TiN has also a strong influence on electroconductivity of Si3N4-TiN based composites.
According to experimental results of several authors, it was noticed that the percolation
concentration (the concentration at which the dramatically drop in resistivity occurs) is
around or higher than 35 wt.% TiN.
The material with the resistivity lower than 10-1 Om could be electrically discharge
machined described firstly by Petrofes and Godalla (1988) and bearing in mind the
influence of TiN on the mechanical properties and oxidation resistance it is of interest to
access the appropriate content of TiN to obtain the desired resistivity without deleterious
effect on the mechanical properties and oxidation resistance.
It is known that flexural strengths and fracture toughness of Si3N4-TiN composites
investigated by Choi et al., (1995) increase with the addition of TiN up to 30% of TiN
thereafter a significant decrease of these values occurs with further addition of TiN. Bearing
in mind that the electrical resistivity of composites with 40% of TiN is 10-3 Om to 10-4 Om
and that with 30% is to high _10 10 Om it is necessary to optimize a content of TiN in order
to make them suitable for electrically discharge machining process.
476
Since some interesting phenomena are observed in composites with 35% of TiN with
various sintering aids , the sintered density and resistivity of these composites in function of
isothermal heating time are given in Table 1.
Table 1. Sintered densities and electrical resistivity in function of isothermal heating time for
composites sintered at 1780 -c
Si 3N. -TiN Heating Time

35 wt % TiN 10 minutes 60 minutes 120 minute s
with RP 3
T.D. (%) o (n m) T.D. (%) o (n m) T.D.(%) p (n m)
Y,O , 87.0 1010 98.0 2 99 .4 2.210' \
NdO, 80.0 108 88.0 102 99.0 2.4 102
Sm,O 82.0 2.2 85.0 10.2 99.0 2.4 10.2
Dy,03 86.0 1010 92 .0 102 96 .0 1.6 10.1
Several important features from the data given in Table 1. should be noticed. Firstly, a
variation of the type of sintering aid influences both the density and the resistivity of
composites. The density of composites increases with heating time and it is for believed that
the spreading out of liquid phase became easier with prolonged isothermal heating. For
heating time of 120 minutes, densities seem to be independent of sintering aid used in this
investigation. Secondly, independent of sintering aids a low resistivity can be obtained for
heating time of 60 and 120 minutes. With shorter soaking time the low resisti vity remains
only in samaria doped composites and is still very high in others doped composites.
The grain growth in silicon nitride ceramics proceeds by the solution-diffusion-
precipitation proce ss and the atomic diffus ion through the intergranular liquid phase seems
to be a controlling step. Instead of growth exponent of 3 found for diffusion as the rate
controlling mech anism , Granger et at. (1997 ) pointed out that the growth exponent in
length and width direction s are 4 and 5 respectivel y for ~-S i3N. It appears that due to the
viscosity and the amount of the liquid phase , in systems with N~0 3 where is the highe st
liquid amount, compare to other composites (Boskovic and Zivkovic , 1995) the grain
growth of ~-Si3N. is remarkable one. The amount of 35% of TiN is not enough to suppres s
the exaggerated grain growth in Si 3N. matrix . The high visco sity of Sm 2Si207 phase
contributes to the finer microstructure therefore enable s the formation of conductive
network during the prolonged sintering time and the lowest resistivity in these composites
can be achieved. It should be said that a low resistivity of composites is associated with the
formation of continuous conductive network together with the elimination of liquid phase.
Some of the properties of Si 3N4-TiN composites may be explained on the basis of a
microstructure obtained during liquid stage sintering.
The microstructure of Si 3N4-TiN(15%) with samaria additive (Fig . 1.) reveals some
exceptionally large and acicular grains (5 - 10 11m) along with small columnar grains.
The aspect ratio of ~-Si3N4 grai ns is from between 3 - 5. With increasing TiN up to 35%
but after very short isothermal heat ing time of 10 minutes, a slightly lower aspect ratio is
observed only in samaria doped composite, as can be seen in Fig. 2. A broad grain size of
~-Si3N4 distribution is presented in composites with 35% of TiN in both yttria and disporsia
doped systems as illustrated in Fig . 3. Microstructural observations clear ly show that
elongated ~-Si3N4 in form of hexagonal prism grow in appropriate liquid phase
environments (Fig. 3b). It is rather difficult to determine the average grain size in these
composites , even through the aspect ratio. Bjorklund et at. (1997) suggested a computer
simulation for the determination of the three dimensional grain size distributions for
477
~- Si3N4 ceramics, which can also be applied, to other ceramic systems. With prolonged
sintering time of 2 hours and at same content of 35% TiN the abnormal grain growth is
almost suppressed and a fairly uniform microstructure is produced. SEM micrograph
(FigA.) reveals that the microstructure consists of conductive polyhedral TiN grains, which
are homogeneously distributed within Si3N4 matrix. This fact plays an important role in the
electroconductivity behavior of these composites since Si3N4- TiN composites can be treated
as a mixture of conductive TiN particles (p - 10-6 Om) dispersed in high insulating Si3N4
matrix whose electrical resistivity is greater than 1013 Om.
Figure 1. SEM of Si3N. -TiN(15 %) Figure 2. SEM of Si3N.- TiN(35 %)

with samaria, 1780 c, 2 h. with samaria, 1780 -c, 10 minutes
b
Figure 3. SEM of Si3N.-TiN(35 %), 1780 c, 10 minutes, (a) with ytrria, (b) with disporsia
478
Figure 4. SEM of Si 3N.-TiN(35 %) with samaria, 1780 -c, 2h
Figure 5. SEM of Si 3N4-TiN(35 %), 1780 -c, 2 h , (a) with yttria , (b) with disporsia
479
Figure 6. SEM of EOM treated surface of Si3N4- TiN
The function of TiN on the microstructure and electrical resistivity of composites can
be analyzed through the aspect ratio of P-Si 3N4 With low content of TiN in composites,
with 35%, independent of rare earth oxides, the aspect ratio in composites sintered for
10 minutes is similar and is lower than 3, although the smallest value is found in samaria
doped systems . With prolonged soaking time and same amount of TiN, the grain growth
critically depends on the amount and viscosity of the intergranular phase, and the extent of
these effects is greater than the grain growth inhibitor effect of TiN phase. In yttria and
neodimia doped systems the aspect ratio is ranged from 2 to 5, compare to the aspect ratio
of 2 in samaria composites.
With higher content of TiN (40-50%), the predominant effect of TiN in suppressing
the grain growth eliminates the difference in aspect ratio in composites with various R203.
In these composites a pronounced drop in resitivity from 1010 to 10-3 Om is associated with
the formation of continuous conductive chains of TiN grains as can be seen in Fig. 5.
The electrical discharge machining could be easily performed out on composites with
35% and higher content of TiN. Wire EDM tests have been done using a brass wire as the
electrode and water as dielectrics. The morphology of the treated surfaces, shown in Fig. 6.
reveals that the surfaces are covered by layers with resolidified - melt formation droplets .
The resolidified droplets are almost Ti-rich phase as proved by EDS spectra (Zivkovic and
Boskovic, 1996), since Si 3N4 should be removed by evaporation.
CONCLUSIONS
It has been shown that among various rare earth oxides used as sintering aids, Sm 203
has a most beneficial effect on the formation of small grained microstructure and on low
resistivity. With content of 35 wt.% TiN the conductivity of composites depends on the
soaking time and type of additive, being the highest in composites with samaria additive.
After 60 minutes of isothermal sintering, the low resistivity can be achieved only in
composites with samaria as sintering aids. Due to the intensive grain growth in P-Si 3N4
matrix, in composites with DY203 and NdP3 is not possible to achieve the continuos
conductive network for shorter soaking time. With prolonged sintering time of 2 hours a
low resistivity is obtained in all investigated composites independent from the sintering
aids. The electrical discharge machining could be easily performed out on composites with
35% and higher content of TiN .
480
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silicon nitride - titani um nitride and resistivity si licon nitride - al umi num ox ide composites ,
J . Am . C eram . S o c . Vol. 74 , No .5 , pp . 950-957 .
Zivkovi c, Lj., and Boskovic , S., 1996., Microstructural and electrical investigation of Si 3N.-TiN based
composites, Proc. Of Eurem- I I , Vol.2 , pp 726 -727.
481
STRUCTURAL AND MECHANICAL CHARACTERISTICS OF ZA27 7wt. % SiC
COMPOSITES
S. Covic', M. Tasic\ 1. Bobie, D. Bozie
'Scientific - research Center, Ufice

2Institute for Nuclear Science "Vinca", Belgrade
ABSTRACT
In this study the results of compression strength determination of ZA27 alloy and
ZA27-7wt.% SiC composites, obtained by ingot metallurgy (1M) and powder metallurgy
(PM) processes, are presented. Compression strength has been tested at temperature range
from 20C to 170C. Ingots were obtained by Compocasting treatment. Than the cast
samples have been hot pressed at 230C, under pressure of 100 MPa for 30 minutes in order
to reduce porosity. Consolidation of zinc alloy powder and SiC particles mixture has been
carried out by hot pressing at temperature of 230C, under the pressure of l70MPa for 60
minutes. The appropriate testing of structure and fracture has been performed on the optical
and scanning electron microscope followed by EDAX and X-ray analysis. The compression
strength of the obtained composite, microstructure as well as SiC particles distribution in the
metal matrix are strongly dependent on the applied procedure.
At all examined temperatures, the strength of sintered composites and casting alloys has
been higher than the strength of casting composites. The strength of casting alloy has been
higher than the sintered composite at the room temperature, but the value or sintered
composite strength has been superior more over 70C.
INTRODUCTION
A new family of zinc alloy with higher aluminium contents, comercially designated as
ZA27 alloys, have been applied in the last ten years, particularly in automobile industry [1].
However, a wider commercial use of these alloys is limited because of the rapid decreasing
of mechanical properties at elevated temperatures (over 100 C). One of the way to avoid
this problem is the production of the composite materials based on ZA alloys; and the
secondary phase includes SiC particles or AI20 3[2]. Previous attempts of producing these
Advanced Science and Technology ofSinteri ng, edited by Stojanovic et al.

Kluwer Academic/Plenum Publisher s, New York, 1999 483
composites are used the ingot metallurgy techniques [3]. However, these materials can be
interested for some other technology, i.e. powder metallurgy, because of the simplified
introducing and more homogeneous distribution of the reinforcement particles in the metal
matrix [4].
The aim of this work is the producing of ZA27-SiC composites by ingot and powder
metallurg y techniques ; examination and comparison their strengths with strength of matrix
alloy at the room temperature and at the elevated temperature.
The production of matrix alloy and composites by ingot metallurgy
Zn-alloy, comercially designated as ZA27 alloy, with nominal chemical composition:

Zn-25AI-3Cu (wt.%), is produced by melting in graphite crucible in electroresistant furnace;
ZA27-SiC composite is obtained by Compocasting process. The average size of SiC
particles is 50 urn, The semi-strength mixture of composites is casted into the copper mould,
preheated at 200C. Then the cast sample is pressed at 230C, under the pressure of 100MPa
in order to reduce porosity.
The composites producing by powder metallurgy techniques
The prealloy, comercially designated as ZA27, is atomized in nitrogen atmosphere at

500C. Homogenizati on of metal and ceramic powders (93 wt, % ZA27 : 7 wt . % SiC) is
carried out in the cylindrical mixer with constant rate of 70 o/min, under the following
conditions: mixing time, tm= 60 min; filling of vessel mixing, Vm= 30%. Powder mixture is
pressed at 230C, for 60 min, under the pressure of 170MPa. The average size of SiC
particles, in this case, is from 0.7Ilm.
The cast sample of ZA27 alloy and composite compacts are machined for compression
testing. The dimensions of obtained samples are: H=I Ommand D=5mm. The examination is
performed on the lnstron in the temperature range from 20C to 170C with deformation
rate of 2,4 x 1003 sol . Microstructural analysis of samples is carried out by optical and
scanning electron microscopy. The density of compacts is determined by measuring
dimensions.

Figure 1 shows the microstructure of ZA27 casting alloy. The dendrite form is a
characteristic of this microstructure , formed by slow cooling.
Dendrite nuclei , consisted of n-phase riched in aluminium, have light colour. Most of
dendrit es termin ated with gray a. +11 perimeter. The interdendrite space is represented
11- phase, riched in Zn.
The prealloy ed powder with particles size in the range from I to 75 urn is obtained by
atomization of ZA27 cast sample. Microstructure of powder is homogeneous and the
particles are nodular in the shape (Fig. 2a-c).
Nodular shape of particles ( the presence of ligaments is noticable, Fig. 2b) and
presence of agglomerates, consisted of small particles (Fig.2a and 2b), are the consequence
of applied technological and constructive parameters of atomization process [5]. The
presence of smaller dendrites in the powders particles structure (Fig. 2c), in this case, is
caused by higher solidification rate.
484
Fig. 1. Structure of ZA27 casting alloy
Fig. 2. The size, shape (a,b) and microstrucmre (c) of atomized powder particles
ZA27 alloy
485
a
Fig. 3. Microstructure ofZA27-7 wt.% SiC composite obtained by (a) ingot and (b) powder metallurgy
Microstructures of ZA27-7 wt.% SiC composites, obtained by two different

technologies are shown in Fig. 3a and 3b.
Microstructure of ZA27-7wt. % SiC composite, obtained by ingot metallurgy, is the
result of introducing reinforcement particles in the metal matrix by Compocasting process
[6]. The distribution of SiC particles is not homogeneous; particles tend to form smaller or
bigger groups of these particles, depending on their dimensions.. The transformation of
dendrites shape is also evident in the composite structure. Namely, the dendrites structure is
decomposed during the Compocasting process and the most of primary nuclei agglomerate
in a relatively great elliptic surface, without dendrites (Fig 3a). Although the structure of
sintered composite is more homogeneous than the structure of casting composite, it is
noticed the presence of SiC particle agglomerates at the certain places. These agglomerates,
in this case, do not generate as the consequence of introducing method of reinforcement
particles in the metal matrix, but the agglomerates are presented in the starting ceramic
powder. Since the bond between agglomerates and matrix is weaker than in the case of
individual particles, the agglomerates represente most frequently reason for arising porosity
of sintered composite.
Figure 4 shows the dependence of yield strength, 0"02' at the temperature range from
20C to 170C for casting alloy and composite obtained by various techniques, during the
compression testing.
At the room temperature, matrix alloy shows the higher strength value than the
composite . The main reason is absence of remaining porosity. As the temperature increases
(above 70C), the value of strength rapidly decreases. It is one of the negative feature of this
alloy, as mentioned in the introduction.
At the room temperature, the casting composite strength (curve 2) is lower than the
strength of matrix alloy. It is caused by high percentage of remaining porosity and
486
500 I=~I
~ 3
I-The alloy obtained by ingot metaIlurgy;
density value. P = 5.oog/cm3 i.e. 100% of
~'" 400
theoretical
density (Plh = 5.oog/cm3)
.&! 2-The composite obtained by ingot metallurgy;
~300 density value. P = 4.20g/cm 3 i.e. 84.85% of
!J theoretical density (P'h = 4.95g/cm3)
'"
~ 200 3-The composite obtained by powder metallurgy;
;;: "- - " ' --' density vale. P = 4.70g/cm 3 i.e. 94.95% of
100.J....---,----,...-------,--- theoretical density (Plh= 4,95g/cm3 )
50 100 150
Temperature, DC
Fig.4. The dependence of yield strength of ZA27 casting alloy and ZA27-7wt.% SiC composite on the
temperature
inhomogeneous distribution of SiC particles. However, decreasing of yield strength with

temperature is not so intensive as it is in the casting alloy, besides the lower strength value at
room temperature. It is the consequence of hard SiC particles presence in the metal matrix,
because SiC particles presente barrier for dislocations movement in material. At the room
temperature, the composite obtained by powder metallurgy (curve 3) shows the lower
strength than the strength of casting alloy, as the consequence of little porosity degree.
However, the aim of this work is achieved; it can be detected from Figure 4. As the
temperature increases, the composite (obtained by powder metallurgy) strength decreases
less than the strength of ZA27 alloy (curve 1) ; also, the values of yield strength are better
(especially at l200C and l70C).
Figure 4 shows identical change of yield strength with temperature for both composites
(curves 2 and 3) and superior strength values of sintered composite. The presence of SiC
particles has an influence on the character of curves, while the distribution of reinforcement
particles has a main effect on the composite strength at room temperature as well as at
elevated temperature.
CONCLUSION
1. ZA27-7 wt. % SiC composites were obtained by ingot and powder metallurgy under
the laboratory conditions
2. Comparing with nonporous structure of ZA27 casting alloy, the composite structure is
characterized by the presence of greater (casting composite) and smaller (sintered
composite) number of remaining pores.
3. The distribution of SiC particles in the sintered composite is better than in the casting
composite.
4. Due to remaining porosity and SiC particles presence, the composite yield strength is
lower than the matrix alloy at the room temperature. The strength is especially low in the
casting composite.
5. The sintered composite shows superior strength value with temperature increasing,
than the casting alloy and casting composite.
REFERENCES
1. E Gervais, RJ. Barnhurst, C.A.Loong, Journal of Metals 10 (1985) , p. 43

2. E J. Kubel, Advanced Mat. and Proc. 7 (1987), p. 51
487
3. l .A. Corn ie, Cast Reinforced Metal Composites , ASM International USA (1988), p. 155
4. H.B. McShane, N. Raghunathan, H.B. Garba, Powder Metallurgy,vol 33, Nol(l990) ,p. 35
5. A. Lowley, Atomization, The Production of Metal Pwders, MPIF, New Yersy(l992),p. 41
6. M.C . Flemings, Met. Trans, 22A (1991), p. 957
488
EXPLOSIVE CONSOLIDATION OF ALUMINIUM NITRIDE POWDER
Vlado N. Radic 1
1 Military Technical Institute
INTRODUCTION
The main thrust of research and development work in the last three
decades has been directed towards the ceramic type of materials, mainly because of the
realisation of their industrial potential and of the increasing demand for more
sophisticated and rare compounds needed in the electronic, optical, chemical and
mechanical engineering industries. The middle 1960s, in particular, saw a surge in the
investigations - in the USA and USSR - with emphasis on synthesis. De Carli's work
on synthesis of graphite into diamonds,' Deribas et al. 's synthesis of cubic boron nitrides
and the more recent Soviet synthesis of the rare earth titanates, zirconates and
hafnates, have laid firm foundations for future developments. Synthesis of compounds
from elements and investigations of chemical activation of shocked materials were also
carried out in the late 1960s in Japan and have continued ever since, mainly in the area
of fine ceramics. The problem arising in the consolidation of powders and powder
mixtures by compaction were investigated early on by Carlson et al., Bergmann and
Barrington, Coleburn and Forbes, and Pruemmer. 2-8
The 1970s saw a considerable surge in the research and provided a basis
for our current knowledge of the chemical and physical aspects of shock treatment of
ceramics. These developments have been sumarised recently by Graham et al. 2 whose
own work in the area of shock compression chemistry has contributed substantially to
the understanding of these phenornena.' A considerable revival of interest in these
matters has taken place lately in the USA when the accumulated scientific data brought
together the various strands of information and reinforced the appreciation of the value
of shock-treated ceramics.
Unlike static or isostatic compaction, shock load ing, particularly explosive,
by virtue of accelerating the individual material particles, creates conditions for
interparticle bonding. Three possibilities - often coexistent - can be identified. The
impact at varying velocities and angles results in the generation of local hot-spots
producing friction welding. Equally, a localised increase in the temperature - caused by
the detonation of the charge - often produced surface melting that creates fusion bonds.
In the past twenty years, a new technology for fabricating metal alloys has
evolved for materials that are pre-alloyed in powder form. In the aerospace industry
the material concerns are weight and structural integrity. Low-weight materials provide
Advanced Science and Technology ofSintering, edited by Stojanovic et aJ.

extended range or increase load capacity, and structural integrity provides longer
service life and lower maintenance costs. The main requirement for a low-weight
material is the flow stress (strength) at the operating temperature. A figure merit is the
strength divided by the density. The important material propertise for low-weight
material are: density, flow stress and elasticity. The essential material properties for
structural integrity are : fracture resistance, fatigue resistance and resistance to
corrosion, especially under tensile stresses.
Dynamic powder compaction is a material-fabrication process that uses
high velocities and high pressures to densify powders. High explosives are essential as
the energy source. Pressures reaching a million atmospheres and powder surface
temperatures of thousands of degrees centrigrade can be produced in powders from
shock waves generated by high explosives. These extreme conditions are applied on a
time scale of microseconds. Consolidation of the powder results from the local welding
of adjacent particles. Dynamic compaction offers the major advantage of anabling
materials to be fabricated that cannot be made by any other means.
The advent of a new class of materials and the need for extremely high-
strength ceramics have produced fabrication requirements that cannot be met by the
more commonly used powder fabricat ion techiques. Dynamic compaction has been
demonstrated to be capable of meeting these requirements.
The advances permitted by dynamic powder compaction include the
following:
- Densities approaching theoretical can be achieved in a wide variety of difficult-to-
compact metals and ceramics.
- Compaction often can be achieved starting from room temperature without the need
subsequent sintering or thermal treatment.
- Unique microstructures that may produce unique properties can be achieved.
- Original powder properties can be maintained throug the compaction process.
- The high pressures from the process can be used to synthesize unique and difficult-to-
achieve material phases.
- The process can be used on a large scale.
Powder den sification by dynamic compaction is achieved by a high-
pressure shock wave (generated by high explosives) that exceeds the yield strength of
the powder mass. The magnitudes of the pressures or velocities are dictated by the
properties and characteristics of the specific powder being compacted. The successeful
consolidation of a material starting from a powder involves a number of parameters
associated with the material itself, such as thermal and mechanical properties of the
grains, as well as the initial grain size. A minimum requirement for the successful
consolidation of material is that the release of high pressures not permit strong ten sile
stresses to develop that could rupture and destroy the material that has just been
consolidated. Computer simulations can provide the means to follow the tlow history
of the powder subjected to compression and tension waves from the experimenatal
setup. With this information the original experimental configuration can be redesigned
to minimize adverse effects. The windows of pressure, temperature, and time that
produce the desired results can be examined by the calculations and translated to other
geometries. Figure 1 shows a calculat ion of a typical experimental geometry for studying
dynamic powder compaction. The powder is placed in the annular region formed by a
steel rod concentric with a steel cylinder. The steel is surrounded by an explosive that
is ignited to that a detonation wave sweeps along the steel cylinder surface.
An incident shock wave (Fig. 1) is induced in the powder followed by a
reflected shock wave S, . A release wave enters the powder when the refleced shock
reaches the high explosive, the source of the induced pressure. The difference in
pressure between the reflected shock wave and the prevailing pressure in the explosive
490
High expl osive
0
~S,
; ; ; ; ;
.": : .x :
:
, .\, I ,
: : : : ~ =~::::~ ~... ~
,
1'-1' ..
/~v. \ \ \ \\ ~. \,\,\ \. \ ... \ \ \ , Steel
Powde r
. . " 1- - ..
. . .. \ '/ \---- . . '-Sj
Steel . _
.. / : .. .. man drel
:.(: \- =
. : : :: : : : : y:::'.1.::~~:.:.-;' \ l ~ Powder
I I , , , '/ ' I , I' l I \ .. ~'I' ,', , ,'j','; ,', , I 'f 1
1 , Steel
a Figure 1. Calculation of powder
compaction in cylindrical geometry. D -
0 explosive detonation front, S, - incident
High explosive
shock wave, S, - reflected shock wave.
at point "a" determines the strength of the release waves (shown as dotted lines Fig. 1).
A large drop in pressure results in large tensile stresses in the sample when release
waves from opposite boundaries cross. The problem is to apply the required pressure
for powder consolidation and to minim ize the adverse effects of the tensile stresses that
tend to fracture the newly consolidated material. The major difficulties inherent in
dynamic compaction as a fabrication process are found in attempts to consolidate hard
materials. The consolidation of ceramic powders represents an extreme. With a
methodology for consolidating ceramic powders in place, the task for consolidating
other materials becomes simpler.
In this paper discuss research on the dynamic consolidation of aluminium
nitride (AIN) as a model system. This ceramic offers the best chance for consolidation
using explosives without first preheating the material because of the duc tile behavior
of the material under a hydrostatic pressure.
This ductile property was dem onstrated by Heard and Cline :' where AIN
was subjected to a combined hydros tatic and uniaxial stress. It would be expected that
subs tantial plastic flow would occur fro m the high pressures of dynamic loading. This
result was substantiated in the work of Hoenig and Just" a nd by Gourdin, et al.,' who
reported considerable deformation of grain structures in explosively consolidated AIN
powders. These authors point out the presence of an amorphous phase at the grain
boudaries. The dynamic compaction process produces high temperatures from large
surface deformations and frictional forces . The subsequent rapid cooling of the grain
surfaces provides conditions for developing an am orphous phase (Nesterenko" ). The
induced temperatu res and quenching rates are, among other parameters, dependent on
the initia l powder grain size and the applied pressure. The effect of grain size studied
in the work of Roman, et al.,? . In the present study the as-recieved AIN powder
classified into various size fractions ranging from 0.04 to 0.2 mm. The powders were
dynamically consolidated using cylindrical geometry by an explosive with detonation
velocity D = 3.6 krn/s. The consolidated specimens characterized by me asuring the
Knoop micro hardness. The residual strains were de termined by x-ray line broadening.
The da ta show an increase in hardness and strain as the grain size de creases. This
result is consistent with the work of Nesterenko" . The temperature of a powder
composed of all large grains is higher than for powder composed of all small grains,
other factors being equal. If the surface of coarse grain podwer is at a higher
temperature than the small grain powder, it would be expected that the strain would
be thermally relieved, yielding the results of Table 1 showing less str ain for the larger
particle sizes .
491
CONSOLIDATION OF ALUMINIUM NITRIDE POWDER
Aluminium nitrides have been processed. Although the oxide ceramics

can be produced by the standard sintering procedures, the nitrides and silicides require
special treatment as pointed out already. These difficulties can be obviated however by
the use of shock consolidation.
Shock treatment affects the microstructure of this compound by imposing
a substantial degree of plastic deformation and by refining the structure. This is a
particular interest in view of the brittleness of this material.
Large surface deformations and interparticle friction are associated with
high induced temperatures. R apid cooling that may follow creates conditions for the
formation of an amorphous ph ase, but the temperature and quenching rates depend
on the initial grain size and the operative pressure. Hot-pressing rates are significantly
enhanced in the post-shocked material and contribute greatly to the economics of the
following conventional processing. 1-8
The specific surface area is only slightly affected by sho ck loading," but
the lattice distorsion is detectable even at low pressures of about 4 GPa Y The latter
depends on the grain size and reduces with the size of the particle as a resu lt of the
higher surface temperature of the coarse grains (Table 1).
Table 1. Post-compaction properties of AIN
Theoretical
Particle size HK lOO Lattice distortion
density
(urn) (kg/rnrn") (%)
(%)
40-50 98-99
1310-1390 0.75
100 98
110-130 98-99
1050-1280 0.62
210-250 98-99
950-1030 0,48
300 98
At low impact velocities, ranging from 0.2 to 0.6 km/s and achieved by
means of a gas gun, the densification of the powder is dependent both on the velocity
of impact and therefore the stressing of the compact , and on the effect of the
secondary shocks." Experiments involving commercialy pure powders of initial densities
1.53 g/crrr' (1-20 urn) and 1.30 g/crrr' (1-7 urn) - 47% and 40% of theoretical density
respectively - indicate that consolidation of up to 70% at stress level, below 0.25 GPa,
is independent of the initial density. At stresses up to 1.8 GPa the degree of
densification is rel ated to the velocity of impact.
Explosive compaction at 3.6 km/s de tonation velocity, results in good
densification without preheating (Table 1), and in a cylindrical solid geometry. AIN
powder, ranging in size from 40 to 250 urn, shows a post-shock increase in hardness
and lattice distortion with the decrease in grain size. This again, is due to str ain relief.
Figure 2 shows a section of an aluminium nitride cylinder consolidated
from powder using cylindrical geometry discussed here. The exp losive was
nitromethane, and an aluminium mandrel was used with a diameter three quarters the
inside diameter of the steel container.
492
Figure 2. Section of an aluminum nitride
cylinder consolidated from powder.
Figure 3 shows results of a computer simulation when the detonation

front has just reached the steel end plugs. The calculation is two-d imensional plane
geometry and is similar in appearance to those done with cylindrical symmetry.
Figure 4 (top) shows the calculated material velocity field at a later time
than Fig. 3 shows.
The calculation indicates the mass of the assembly moving in the direction
of the detonation. Figure 4 (bottom) shows that the forward motion of the consolidated
1.5
o
1.0
Steel container
Steel
plug
.5
>-' 0_ _
-0.5
- 1.0
-1.5 o
-2.0 -h"TTTT"r-r-....,..,-r-T'"T"T"""""'T"T'"""'rT"""l....,..,-r-T-rT.,...,...,.,......,,,..,rrt- Figure 3. Calculated velocity

-3.5 -3.0 -2 .5 -2 .0 -1 .5 -1 .0 -0.5 o 0.5
vectors in aluminum nitride
X,in. consolidated in plane geometry.
493
0.8
0.6
.~
>-"
0.4
"' ...... _--------
0.2
0 ------------ ---- - ------- -

------~::-----~
-0 .2
---- ---
----
----
-----
-:...~-:.
-0 .4
/..;----------
0.4 -------.,,;/
---
0.2
.5 0
>-"
------------ ---- ---- --- --- ---
---
-0 .2
------- - --- --- --- ---

0.4 ..... ~
------ -
Steel conta iner
-0 .6 Steel
-1 .0 -0 .8 -0 .8 -0.4 -0 .2 o 0.2 0.4 0.6 0.8 1.0 1.2 1.4

X, in.
Figure 4. Calculated velocity vectors after deto nation . Top: stee l end plug;
Botto m: aluminiu m / stee l end plug
Figure 5. Aluminium nitride powder consolidated to 94% T.O.
494
powder can be reversed by inserting an aluminium plug between the powder and the steel
ens plug. Fracture occurs at the aluminium plug, and the powder region stays in place and
the momentum is carried off with the steel end plug.
The calculation, Fig. 4, used an explosive with a detonation velocity of
D=3.8 km/s and a density of p = 3.4 g/cm' . Experimentally this explosive is obtained
by diluting nitromethane with the inert material magnetite (Fe 3 0 4 ; 5.18 g/crrr') .
Figure 5 shows a section of a flat plate consolidated with the geometry
described above. The density of the material is 90 % T .D. Attempts to increase the
density by decreaseing the diluent in the nitromethane resulted in craced specimens with
this geometry .
One of the advantages of consolidating powders on a fast time scale is that
there is not enough time for large scale melting or other phase changes to occur , as stated
earlier.
REFERENCES
1. P.S. De Carli and J.C . Jamieson', Science, 133: 821 (1961)

2. M.L. Wilkins , A.S. Kusubov and C.F. Cline , Explosive Consolidation of Aluminium
Nitride powder, in: Metallurgical Applications 0/ Shock Waves and High Strain-Rate
Phenomena, L.E. Murr, K.P . Staudhammer and M.A. Meyers (eds), Marcel Dekker,
New York, 57 (1986)
3. Heard, H.C . and C.F. Cline , J. Mat. sa. , 15: 1189 (1980)
4. C.L. Hoenig and C.S. Just , Am. Cer. Sci. Bull. 60: 1175 (1981)
5. W.H . Gourdin , c.J . Echer , C.F . Cline and L.E. Tanner, in: Proc. 1 h Int. Con/ on
High Energy Rate Fabrication , University of Leeds, 233 (1981)
6. W.H . Gourdin , S.L. Wienland , C.J . Echer and S.L. Huffsmith, Emergent Process
Methods/or High-Technology Ceramics, Vol. 17, R.F . Davis, H . Palmour III and R.
L. Porter (eds.), Plenum Publishing Corp . (1984)
7. 0. V. Roman , V.F. Nesterenko and I.M . Pikus, Fizika Goreniya i Vzriva, 5: 102
(1979)
8. R. Pruemmer, in: Explosiv e Welidng, Forming and Compaction, T.Z . Blazynski (ed) ,
Applied Science Publishers, London & New York , 369 (1983)
9. D. Raybould and T. Z. Blazynski, Non-metalic Materials Under Shock Loading, in:
Materials at High Strain Rates, T . Z. Blazynski (ed), Elsevier Applied Science,
London & New York, 71 (1987)
495
CHARACTERIZATION OF METAL AND
SEMICONDUCTING POWDERS USING A COHERER
Pantelija M. Nikolic, Stevan Durie and Momcilo M. Ristic
Joint Laboratory for Advanced Materials of SASA, P.Box 745

ABSTRACT
A classical coherer in the shape of a glass tube of about 10 mm inside diameter.

having two brass plugs in its ends was used for this investigation. The space between the
plugs was filled with the sample of some metal {Cu) or semiconducting (SnS. InS. PbS)
powder. A high frequ ency balance generator was made with two electron tubes with output
power of about 100 Wand 60 MHz frequency. It was noticed that the resistivity of some
powders. decreased from about IMn to about 50 n when the VF generator was switched
on. We have investigated the change ofthis effectfor different sizes ofpowder.
INTRODUCTION
The pioneers of radiotechnics used a rather simple device, a coherer, to activate an

electrosystem at a distance without using wires . The coherer was the result of the
investigation of several scientists: Branly, Lodge, Marconi , Tesla, Popov, etc':' . Branly
1890 discovered that loose iron filings in a glass tube better conduct "cohere" the electric
current under the influence of radiated electric waves . Lodge 1894 connected the coherer to
a receiving circuit to detect Morse code signals transmitted by electromagnetic waves .
Marconi then increased the distance of signaling. Tesla used the coherer to steer a ship at a
distance . A model of such a ship is an exhibit in the Tesla Museum in Belgrade.
The coherer consists of a glass tube partly filled with a small quantity of metal chips or
powder lying loosely between two brass plugs fitted at its ends. Its schematic survey is
given in Fig.1.
The electrical resistivity was measured between the brass electrodes, which was large
(between several kD. and MD.). If this coherer is put in a high frequency electromagnetic
field the resistivity would decrease for several orders of magnitude, very often below 50 D..
The resistivity again increases after the metallic chips in the coherer change their position
with a mechanical concussion. It is still not entirely explained how the coherer works.
Some people think that a microscopic spark passes between the chips and connects them
together decreasing the resistivity . There is another opinion that an electrostatic attraction
Advanced Science and Technology ojSintering, edited by Stojanovic et al.

Kluwer Academic/Plenum Publishers, New York. 1999 497
could produce this effect. The tunneling effect is also somewhere mentioned and
assumption exists that a very thin oxide layer gets burnt (penetrated) with high voltage, and
appear at the ends of the coherer.
~-8J~' It----r
Figure 1. Schematic survey of the coherer
Since electron tubes were discovered , scient ists stopped using the coherer, because
contemporary receivers and transm itters were made. This is the main reason why nobody
properly explained how the coherer actually works. At present there exist a growing interest
in the coherer though mainly from the historic point ofview3 .
In this paper we make an attempt to show that the coherer, in a modified form, can be
successfully used for the characterization of materials, both metals and semiconductors, in a
powder form .
Figure 2. Vertical cohcrcr
498
A vertical coherer, given in Fig .2, was made . It could be separated in pieces . It has two
brass electrodes. The lower one is fixed . The upper electrode has a platform at the top
where we can put a changeable weight. In this way it is possible to press the powder which
is put in the coherer. Both electrodes are connected with the receiver using a high frequency
very elastic cable.
The circuit diagram of the receiver is given in Fig .3.
A PM
C2
L K n
Figure 3. Circuit diagram of the receiver
An antenna, made in the shape of a telescope stick, was connected to an oscillator

circuit and through a condenser C3 to coherer, K. The high frequency part is separated from
the ohmmeter with a damping coil Prl . A diode d, capacitor C4 and voltmeter V are used
for tuning the receiver into resonance with the transmitter. When the coherer is switched
off this system can be used as an indicator of the intensity of the electromagnetic field and
an optimal wireless connection between the transmitter and the receiver can be obtained.
The transmitter was made using two American electron tubes 807 in anti phase
connection (balance generator). The electrical scheme of the transmitter is given in FigA.
The oscillator frequency can be changed in the region at about 60 MHz. Its output power is
about 100 Wand it can be changed using switch S.
Figure 4. The circuit diagram of the transmitter
499
Figure S. A photograph of the system: transmitter, receiverand coherer
The transmitter is active only when the key T is pressed and that does not exceed a
second. A photograph of the whole system - transmitter and receiver is shown in Fig.5.
Powders of various materials were measured in the coherer. Fig.6 contains the results
for two semiconducting samples PbS (galena from the mine Trepca, Yugoslavia) and
synthetic InS. A full line represents the change of resistivity, versus the weight which was
put at the top of the upper coherer electrode, when the transmitter was off. The values of
the resistivity when the transmitter was switched on for a second are given with the dotted
line.
Similar diagrams have been given for carbon powder taken from a telephone
microphone (Fig. 6). It can be seen that the resistivity of galena powder decreased for about
two orders of magnitude when the key was on. The resistivity decreased for about four
orders of magnitude for InS powder, while the change of carbon resistivity was smaller in
the same order of magnitude.
Similar experiments were made for copper powder. We had three particle sizes of
powder: a) with the diameter less than 0.068 mm, b) with the diameter of the particle
0.0681><0,1 mm and c) the diameter between I and 2 mm. In Fig.? two diagrams of the
resistivity changes are given. A full line represents the change of resistivity versus particle
diameter. The broken line shows the change of resistivity when the transmitter was
switched on. The asterisks give the values of resistivity for copper mixed powder e.g. when
the same quantity of each copper particle size was put together.
DISCUSSION
In the case of semiconducting samples the decrease of PbS and SnS resistivity was
between two and four orders of magnitude, respectively, when the transmitter was switched
500
10'
10 5
-
- PbS
10' I
InS
~
~~ - - - . ! - 't~H- t-:-<
I
-r ~-+ . +-
c:
I
, I I I I I I I I
n:: 10
..
..... - -,-
- PbS
.. , - -. -t-
,
I I
-- I
I , -
10
-
-
~ .
-- -.-
.-
.,....
-- .. -. -- ,- .,.. . 1--
- -c
,
t-
,.,,:- - C
10
- .-
- - .
t- . InS
o 10
!
20
- H~
30
'f I~
40
. .. - --
50
Frlt 60
W [g ]
Figure 6. The resistivity vs. the weight: transmitter is oIT- fuIlline and transmitter is on - dotted line.
501
10<-
II II I
10'
Cu
;\ I
10'
- ~
ixed Cu
10'
I 1\ -. mixed Cu
-- -
Cu
10 I III II
,!! I t
1 I!
o 0.04 0 .08 0.12 0 ,16 0.20 0 .24
<D [mm)
Figure 7. The resistivity of copper resistivity vs. a diameter of the particle: transmitter is off- full line and
transmitter is on - dottedline
on. It was even larger when the measured powder was not pressed with weights . The
powder for both semiconductors was mixed so we could not consider the influence of the
particle size on the observed coherer effect. This was examined for copper powder where
we had three different particle sizes. The experimental results given in Fig.7 show that the
largest decrease in resistivity was for the finest powder e.g. the smallest particle size of the
copper powder. When the particle size was increased the difference between resistivity
measured by the coheher and transmitter off and on became smaller and smaller. When the
copper powder was mixed the resistivity slightly increased. Judging by these results it is
obvious that the coherer can be used, properly calibrated, to measure the particle size of
copper powder. One should say that it is still very difficult to discover the reason of the
resistivity decrease when the powder was exposed to a high electromagnetic field when the
transmitter was switched on. The most possible explanation could be that some sort of
microscopic spark breaks the very thin oxide film, which surrounds each particle. To prove
this one can probably use gold powder or platinum powder of various particle sizes where
an oxide film cannot form.
CONCLUSION
The coherer effect was very successfully observed using semiconducting PbS and InS
powders. A similar effect was also observed for copper powder with various particle sizes.
502
The electrical resistivity of these samples was decreased for two to more than three orders
of magnitude when the transmitter was switched on and the powder was exposed to the
influence of a strong electromagnetic field. The copper powder of the smallest particle size
had the largest decrease of resistivity and vice versa. It gives an idea that the coherer
properly calibrated, could be used, to "measure" the particle size of copper powders.
REFERENCES
1. lA.Fleming, The Principlesof Electronic Wave Telegraphyand Telephony, 3'd Edd., London (1916).
2. N.Tesla, Colorado Springs Notes 1899-1900, Noli!,Beograd (1978).
3. T.W. Pegram, R.B. Molyneux-Berry and A.G.P.Boswell, The coherer era - the original Marconi system of
wireless telegraphy, GEC Rev., 12(2):83 (1997).
503
Part VII. SINTERING OF METAL PO WDERS
THE INFLUENCE OF THERMOPLASTIC DEFORMATION ON THE
STRUCTURE AND MECHANICAL PROPERTIES OF POWDER
METALLURGY MATERIALS
Yu.V.Milman
Institute for Problems of Materials Science,

Ukrainian National Academy of Sciences
3, Krzhizhanovsky Str.,252180 Kiev, Ukraine
INTRODUCTION
Powder metallurgy materials as a rule have porosity after sintering. Different

pressure working processes (extrusion, pressing, forging, rolling etc.) are used to decrease
porosity. Pressure working leads not only to consolidation of materials, but to changes in
structure and substructure of materials, i.e. to variation of grain size and formation of
dislocation substructure as well.
In the majority of cases on the surface of pores there are impurity segregations.
During plastic deformation not only size and shape of pores are changed but segregation of
impurity as well.
Plastic deformation is used also for hot and cold powder pressing.
Reviews made in [1, 2] have shown that plastic deformation takes place in the
sintering processes too. The real stress during sintering may be much higher than the stress
of capillary interaction estimated as o = y / R, where y is the specific surface energy and
R is the curvature radius of the particle. Estimations show that the level of local stresses
during sintering may rich 1 GPa and exceed the yield stress. As a result the dislocation
substructure with high dislocation density may be formed in the interparticle contacts
during sintering.
It is well known that grain size, dislocation substructure, deformation texture,
porosity and segregation of impurities in pores influence essentially on the mechanical
properties of the powder metallurgy materials.
These problems will be the topic of present work, together with the discussion of
the possibility of thermomechanical treatment for ceramic materials.
Advanced Science and Technology ofSintering, edited by Stoja novic ct aJ.

HOT, WARM AND COLD PLASTIC DEFORMATION
In the literature devoted to pressure working of metals the terms of hot, warm and
cold deformation are widely used. It was assumed for commercially pure metals that cold
deformation corresponds to the temperature T < O.3Tm, warm deformation to
O.3Tm < T < (0.5+0 .6)T m and hot deformation to T > (0.5+0 .6)Tm [3] (here T m is the
melting point). It is common knowledge that the use of the concept of the homological
temperature allows to compare in similar conditions a number of physical properties of
crystalline materials determined by the phenomenon of self-diffusion. However, such
comparison cannot be used for mechanical behaviour of crystals with different share of
covalent component in the interatomic bond and with different crystal lattice [4]. Indeed,
for example, plastic deformation of molybdenum at (0.2+0.3)Tm and germanium at
(0.8+0 .9)T m leads to the formation of similar dislocation cellular structure that is typical for
warm deformation. For this reason the temperature ranges of cold, warm and hot
deformation shall be determined by the evolution in the deformation process of grain
structure and dislocation substructure and move on the homological scale of temperatures
depending on the values of characteristic temperature of deformation, T*, and
recrystallization temperature, T;
Characteristic deformation temperature (knee temperature) is the temperature below
which crystal lattice resistance to dislocation movement (Peierls-Nabarro stress) becomes
significant. At the temperature T* the mechanisms of deformation, fracture and recovery of
properties in annealing change significantly, and these changes are similar for different
crystals. It has been shown that T* is a fundamental crystal property [5, 6]. It was shown
T*
[5,8], that the value of t * = T may be calculated from the relation
m
t *:::; 0.22Ja (1)
where a = U/kT m- U is the activation energy of dislocation movement, k is Boltzmann

constant. Parameter a characterizes the rigidity of crystal lattice in respect to the motion of
dislocations. Structure and dislocation substructure formation in the course of plastic
deformation of metals is determined in the first instance by the temperature and degree of
deformation. An approach to the definition of hot, warm and cold deformation has to be
developed not in connection with the necessity of metal heating or cooling but on the basis
of structural changes in the deformation process [4, 6].
Hot deformation is the plastic deformation above the dynamic recrystallization
temperature, T r During hot deformation equiaxed grains with low dislocation density and
low internal stress level are formed in the metal (see Figure 1). Hot deformation is often
used for primary working of cast metal or sintered powder billets . But during such
deformation it is impossible to succeed in forming small-grained structure and, even more,
in forming cellular dislocation structure. The case of direct use of dynamic recrystallization
may serve as an exception. In this case equilibrium is reached between the processes of
strain hardening and softening, and grain size is determined by the temperature and degree
of deformation. Hence hot plastic deformation accompanied by controlled dynamic
recrystallization may be used for producing extremely fine-grained metal with little
variation in grain size (but without dislocation cellular structure). At lower temperatures
deformation may be warm or cold. As it was shown in [4, 6], characteristic deformation
temperature T* may serve as the natural boundary between the temperature ranges of warm
and cold deformation.
508
Deformation Hot deformation Warm deformation Cold deformation
kind
Deformation
temperature T>T, T* < T <T, T<T*
equiaxed grain non-equiaxed grain non-equiaxed grain

structure, low structure, cellular struc ture, rando m
dislocation den sity dislocation structure dis location structure
p<106+ 108cm -2 (dis locat ion forest)
~=
p>10 8+ 10 IOcm -2
8
Grain and T<0.8T, T>0. 8T,
dislocation
structure
..LT
non-equi axed equiaxed

cells cells
gro ws rapidly with grows rap idly and
Strain low or zero increase of deformation monotonically with
hardening to the Ec, than grows the increase of
slowly, E c - cr~f'd defo rmatio n degree to
fracture
L V
.icr, .icr,
Fracture ductile
E
V Ec
ductile or
E
brittle or
E
mechanism quasibrittle quasibrittle

Act ivation
energy activation energy activation energy activa tio n energy
of plastic of sel f-diffus ion of dislocation movement of dislocation
deformation movem ent
Figure 1. The influence of cold , warm and hot deformation on grain and subgra in structure and on
deformation and fracture mechan isms.
Recrystallization is not observed under warm plastic deformation as well as under

cold one, and initial equiaxed grain after plastic deformation becomes non-equiaxed; it
elongates along the direction of tension and the grain changes its shape as a whole
specimen according to the Taylor and Polanyi principle [7].
But the character of the dislocation structure formed in the course of plastic
deformation significantly changes near T*. After cold deformation (T<T*) a random
dislocation distribution is typical, polygonization is practically absent, while during warm
deformation (T*<T<Tr) a cellular dislocation structure is formed after a certain degree of
deformation Ec This phenomenon may occur due to the fact that E c "" 0' ~f . d , where O'ef is
the effective flow stress and d is the grain size [8]. Hence a sharp increase in flow stress
below T* prevents cellular structure formation, and dislocations after deformation are
situated randomly. During cold deformation the dislocation density grows monotonically
509
with the degree of deformation, and simultaneously there is a sharp increase in strain
hardening and residual internal stresses, which may be characterized, for example , by X-ray
line broadening. At the same time during warm deformation internal stresses increase with
deformation up to Ec, and then with the formation of cellular dislocation structure are
practically stabilized [8, 9] (see Figure I). The characteristic deformation temperature is
also the lower temperature limit of ductile fracture for the majority of crystals.
Activation energy of plastic deformation which can be determined by the
dependence of strain rate E on the temperature, corresponds to the activation energy of
dislocation movement for warm and cold deformation and to the activation energy of self-
diffusion for the temperature range of hot deformation [8].
From Figure I it can be seen that non-equiaxed grain structure is formed at any
deformation temperature which is lower than T; At the same time, analysis of data in the
literature has shown that non-equiaxed shape of cellular structure arises during warm
deformation at lower deformation temperatures (T < 0.8T r for BCC metals). Just these
deformation conditions lead still to a strong tendency of metal to splitting, and the most
clearly defined anisotropy of mechanical properties appears . If the deformation temperature
is close to T r , the phenomenon of 45-embrittlement may occur [7, 10].
Thus, the optimum temperature of thermo-plastic deformation for BCC metals must
be 0.8Tr<T<Tr .
In this temperature range the equiaxed cellular structure with cell size 0.5-1.0 mkm
and a big misorientation of the neighbouring cells, may be formed, In this case the cell size
plays the role of the effective grain size def, and improving of mechanical properties
(increasing yield stress G s and lowering ductile-brittle temperature Tb) may be described by
equations [II]
G s = Go +K y' rlue f 112 (2)
and l/T; = A - Blgdef (3)
where Go,Ky , A and B are the materials constants .

The segregation of impurities on the surface of pores not only influences on
mechanical properties, but decreases the rate of sintering as well [I, 7]. The formation of
small-grain structure and dislocation cellular substructure during warm deformation makes
possible to redistribute impurities and decrease their concentration on pore surface and on
grain boundaries [I, 7]. By this way during hot or warm working of material not only size
and shape of pores are changed but segregation of impurities as well.
The typical temperature dependence of flow stress for crystals with high level of
Peierls-Nabarro stress is given in Figure 2. Both temperatures T* and T, are given in this
scheme, and ranges of cold, warm and hot deformation are shown. The equations for the
temperature dependence of flow stress obtained in dislocation theory of flow [8, 9] are
given in this Figure too.
Figure 3 gives the dependence of the characteristic deformation temperature t* and
T
the recrystallization temperature t, = _r on the parameter a (see Eqn.l). In this Figure
Tm
the value of t, is plotted by the dotted line, since its precise position depends on the
presence of impurity and on deformation conditions . The regions of hot, warm and cold
deformation are given in this Figure for different crystals. It is seen that pure covalent
crystals Si and Ge have the biggest region of cold deformation,
510
Figure 2. The scheme of the temperature
dependence of the flow stress as for crystals with
high level of the Peierls-Nabarro stress. U is the
activation energy of dislocation movemen t, V is
the activation volume, t is the strain rate, M is
the material constant t* is the characteristic
deformation tempera ture and t, is the
t* t, t = TIT m recrystallization temperature.
1.0
'/
~/ ~
Si
0.8 V A1,O" LaB,
I / II loSb_
~I
t.1~ 0.6 tr .' [J
t* ~ I
WC, NbCo.~, _
0.4 ~/' ~
T iB,
7 urn, Be
I---
J ZrB,
II . ~I III
0.2 ZoSe, ( r
~, CdS, Ta Figure 3. The temperature regions of hot (I), warm (II)
and cold (III) deforma tion in crystalline materials. t* is the
~I
1;1' Mo characteristic deformation temperature, t, is t he
5 recrystallization temperature (in homological scale), and
o 1 2 3 4
a =U/kT m where U is the activation energy of dislocation
- .;a movement.
5 11
COLD, WARM AND HOT DEFORMATION IN THE PROCESSES OF POWDER
PRESSING AND SINTERING OF POWDER METALLURGY MATERIALS
(PMM)
The concept of cold, warm and hot deformation may be entirely used for the
description of the pressing process of powders. We can distinguish cold, warm and hot
pressing of powders. Cold pressing or pressing in the cold deformation region leads to very
small deformation degree in the contact zones of particles in connection with high strain
hardening. The porosity after such pressing is big one, and the densifying of material is
mainly the result of regular packing of powder particles. There are very big residual
internal stresses after cold pressing.
During warm pressing of powders the porosity will be lower as well as the level of
residual internal stresses.
Hot pressing can lead to the receiving of the dense material, but in this case grain
size of material can be bigger as a result of recrystallization process.
Sintering process of PMM depends essentially on the temperature not only in
connection with the rate of the self-diffusion, but in connection with the position of the
sintering temperature in relation to the values of T* and T, . It is possible to speak about
cold, warm and hot sintering too.
The densifying process in sintering powders of covalent and partially covalent
crystals in relation to the homologous temperatures was examined in [12]. It is well known
that the temperature dependence of the density of sintered materials is described by a s-
shaped curve. In accordance with [12], Figure 4 gives these curves for several materials
according to the results obtained by a number of investigators, the data on the temperature
dependence of density are compared with the self-diffusion coefficients as with factors
controlling sintering process (Figure 5).
Figure 4. Densifying of powders CaF 2 (I), Mo (2), ZrC (3),

MoO (4), WC (5), AIN (6), Si (7), and B (8) in relation to
0.4 0.5 homological sintering temperatures [12].
0.3 0.7 t=T/T m
-12
-14
-16
-18
-20
Figure 5. Temperature dependence of the self-difusion coefficients
.221---~-----'--- [12]. I - metals (W, Mo, Ni, Cu, Nb) and metallic atoms in TiC,
0.4 0.6 t = TIT m ZrC, NbC, VC; 2 - Si in SiC; 3 - Si and Ge.
The most important result of the generalization made in this work is the conclusion
according to which the temperatures of intensive densifying of covalent and partially
512
covalent crystals almost completely coincide with their characteristic deformation
temperatures t* presented in Figure 3. This result may be understood on the basis of the
previously presented considerations of temperature t* as a boundary between the regions of
cold and warm plastic deformation, if to assume that the powders can be sintered relatively
rapidly, only if the process of plastic deformation takes place as a result of slip or non-
conservative dislocation movement. Only above t* deformation can take place at relatively
low stresses and without essential strain hardening. Densifying in sintering of solids
containing isolated pores or having the form of a conglomerate of adjoined particles and
voids is accompanied by intensive changes of the shape of the material on both the macro-
and microlevels (for example, in the volume of an interparticle contact). Since the sintering
temperatures are relatively high, and the stresses formed under the effect of capillary forces
and the weight of powder particles are not high, it is usually assumed that the relationships
of changes in the shape of material in sintering are very similar to those of plastic
deformation in creep. Special attention of investigators usually was focused on the
diffusion creep, whose mechanisms have been studied by Nabarro [13] , Herring [14],
Lifshits [15], Coble [16], and Ashby and Verrall [17].
The participation of dislocation mechanisms of deformation in the sintering process
is not doubted at present time [1, 2, 18]. Formation of dislocation ensembles in the contact
area in modelling experiments with sintering alkali-halide crystals was detected in [19]
after revealing dislocations by the etch pits method. Dislocation rosettes on LiF were
revealed [20] after sintering a ball with the (001) plan e of the same crystal. For metals ,
dislocation rosettes of sintering were revealed in a number works of Schatt [21-25] where
sintering of single crystal copper spheres to the (111) surface of copper single crystal was
studied. However, the dislocation structure formed during sintering real powders in
particular the structure of interparticle bridges, has not been studied sufficiently, and this
complicates the examination of dislocation mechanisms of deformation in sintering.
Various mechanisms of dislocations creep have been developed. The strain rate in
these mechanisms is controlled by cross slip or intersections of dislocations, the recovery
processes in a dislocation ensemble, or directly by friction of the crystal lattice dislocation
movement [26, 27] .
According to Weertman's model [28], deformation during creep takes place as a
result of slip of edge dislocations, but the obstacles are overcomed by climb. The majori ty
of creep theories take into account the possibility of the formation of dislocation cells and
subgrains during deformation. The problem as which dislo cation mechanisms operate and
the degree to which these mechanisms may work during powder sintering is still the subje ct
of discussion. However, it should be mentioned that the dislocation mechanisms of
deformation lead to a stronger dependence of the strain rate E on the applied stress a than
the previously examined mechanisms of diffusion creep. For example, in a number of
dislocation theories the exponential dependence E - an was observed, where n:?:3 .
Dependences of the type E- sh orr and E- exp aa are possible too. Therefore, the
importance of dislocation mechanisms of deformation increases with increase in stress
[29].
The concept of the effective stress a = a e - a j, where a e is the external applied
stress and aj is the friction stress, is usually introduced for dislocation mechanisms. Since
in covalent crystals and BCC metals the friction resistance is characterized by a strong
temperature dependence [5, 8,29], the value of a can increase significantly only near the
temperature t* where the value aj rapidly decreases.
In sintering of two particles is decreased the local level of resulting stress can
evidently be considerably higher than the forces of capillary interaction estimated as
a = y/R where y is the surface energy and R is the curvature radius [18]. For example [30],
sintering of NaCI single crystals of different orientation resulted in the formation of high
513
stresses causing asterism of spots on Laue patterns. In accordance with [18] these stresses
are caused by the differences in the distances between atoms in different planes of the
single crystal and by need for structural rearrangement in areas with direct contact of the
sintered single crystals. Estimates show that the level of local stresses may reach in this
case 1 GPa.
The possibility of appearance of shear stresses which are sufficient for including
dislocation mechanisms of plastic deformation indicated, in particular, by the data in [31].
In classic sintering models calculations were carried out in cases in which the surface of a
contact bridge between particles is symmetric in relation to the straight line connecting the
center of a sintered particle with the contact point of a similar particle, and the mutual
position of the other particles in the sintered set was usually disregarded. The authors of
[31] derived an equation for the stress in an asymmetric contact between two particles. The
local force F formed in this case tends to rotate these particles in relation to each other. The
magnitude of the resulting stresses was estimated as cr"" 2 MPa.
Even higher stresses appear in sintering a set of particles of different size. The
authors of [31] examined a case of sintering particles of two dimensions : R 1 and R2. In this
case R 1>R2 and RI=(n-l)R2 where n is the number of smaller particles packed in a
row parallel to a row of two particles of larger size. The difference in the shrinkage
of the particles of different sizes connected in a set results in the appearance of
stresses whose value reaches cr "" 100 MPa.
This stress is bigger than yield stress at sintering temperature for the majority
of metals.
Carrying out modeling experiments with sintering copper particles of different
sizes, the authors of [31] showed that during sintering a set of particles the particles rotate
and their mutual position changes. The strength of interparticle contacts is different and
some of them (more weak) may even fracture during sintering. Certain particles may move
in relation to closely packed sections of the ensemble and fill large pores. These results
confirm the high level of stresses formed in interparticle contacts during sintering real
powders with particles of different sizes.
Formation of zones with increased dislocation density in sintering was observed in
sintering together a sphere and a plane produced from high-purity copper [32].
A direct confirmation of the conclusion on the increase of dislocation density in
sintering dispersed nickel powders was obtained in [33] by transmission electron
microscopy. Powders of high-purity nickel (99.99%) with particle size of 1-1.5 um were
compacted at room temperature under the pressure of 700 MPa and sintered at 11OOC for
two hours. Porosity after compacting was 10.7% , after sintering 6.4%; grain size after
sintering was approximately equal to 44 urn indicating the higher rate of recrystallization
which removed the dislocation structure formed during powder compacting. According to
the results obtained by transmission electron microscopy the dislocation density in the
individual sections strongly exceeds 1010 em", regardless of the recrystallization process. In
most cases, these dislocation clusters were situated in the vicinity of grain boundaries and
also around pores. The distribution of dislocations in various slip systems and the
formation of dislocation networks is regarded in [33] as a consequence of the nucleation of
dislocations, their cross slip and climb during sintering.
Figure 6 shows the microstructure of a sintered tungsten rod, obtained by
transmission electron microscopy. Sintering (after cold compacting) was carried out by
heating to 2500 oC. It can easily be seen that the process is accompanied by the formation of
cellular dislocation substructure with cell size of approximately 0.5 urn, The authors of
[33] also found that in bridges between the sintered iron particles after cold pressing and
sintering at 11OOC dislocation density increases and cellular dislocation structure forms.
514
The values of the characteristic deformation temperature t* for covalent and
partially covalent crystals (where they are relatively high) (Figure 3) can be used to select
the minimum temperature at which intensive densifying of powders takes place during
sintering. At the same time, for metals for which value t* is not high and sintering is
carried out at t>t*, the temperature of intensive densifying may be determined by diffusion
processes, i.e., by the temperature dependence of the self-diffusion coefficients .
Figure 6. The cell dislocationstructure in the interparticlecontacts of sintered tungsten rod [34].
THE INFLUENCE OF THE THERMOMECHANICAL TREATMENT (TMT) ON

THE STRUCTURE OF SINTERED MATERIALS
After sintering the primary working of material with high reduction can be carried
out efficiently in the region of the hot deformation I (Figure 3). In this case not only the
shaping of metal is more efficient, but pores and other defects of crystal structure are
healed at higher rate. Deformation of sintered metals (for example, molybdenum and
tungsten) in this temperature range makes possible to produce an almost pore-free metal.
Only the pores with high concentration of insolubled impurities can not be healed by hot
deformation. For example, in Figure 7 the small pores in the sintered tungsten rod are filled
by potassium, and these pores did not heal during hot forging [34].
However, final stages of plastic deformation of semifinished products of BCC
metals are expedient to be carried out in the warm deformation range (region II) to form
optimum structure and mechanical properties. Preference must be given to the upper part of
this range. In the lower part the formation of a structural texture (elongated dislocation
cells with high level of stresses at the sub-boundaries) leads to the tendency of splitting and
to big anisotropy of mechanical properties. In this case a crack propagates along sub-
boundaries under very small stress. If it is impossible to deform material in the upper part
of the region II (for example during the drawing of tungsten wire), the plastic deformation
has to be combined with an annealing that reduces the sub-boundary energy and changes
the shape of the subgrains (Figure 8). During such annealing not only polygonization and
annihilation of dislocations take place, but partial recrystallization (so called slow
recrystallization [8, 34, 35]) as well. The optimum structure after deformation and
annealing of W wire is shown in Figure 8b.
515
(a) (b)
Figure 7. Structure of the fracture surface [34]:

a) sintered tungsten rod. There are large (",lllJII) and smalI ('" O.lllJI1) pores;
b) forged tungsten rod 7.5 mm in diameter . SmalI pores are seen.
(a) (b)
Figure 8. The fracture surface ofW wire after failure along its axis [34]:
a) drawing without annealing to the diameter D = 1.7 mm;
b) drawing to the diameter D = 1.7 mm and annealing at I500C, 30 min.
The pile grain structure has been preserved after annealing, but non-equiaxality of grains
strongly decreased and was equal approximately to 4. The boundaries between fibers are
wavy after annealing (but not flat as after drawing, see Figure 8) that impedes the
propagation of a splitting crack. During drawing of W wire without annealing the cross
grain size (fibre with d) reduces monotonously. After annealing of the wire the value of d
increases and decreases once again during subsequent deformation (Figure 9). Of course,
the lower is the grain size d, the bigger will be the strength of wire (see Eqn.2). But, as it
was said above, annealings must be given to impede the splitting of the wire.
The TMT is not used, as a rule, for ceramics and covalent crystals. As an exception,
the TMT is applied in the process of hot pressing of ceramics under high hydrostatic
pressure. Difficulties in using the TMT method for covalent crystals and ceramics are due
to insufficient ductility of these materials over a wide temperature interval. But it has been
516
shown [36] that TMT can be used for covalent crystals and ceramics too. Considering
single- and polycrystalline silicon as an example, it was demonstrated the possibility of
increasing room temperature strength by means of preliminary mechanical loading at a
temperature which is close to the ductile-brittle transition temperature at load 10-20%
lower than yield stress. This preliminary loading causes the local plastic deformation on
microcrack tips or other defects that leads to crack-tip blunting and to the increase of room
temperature strength (on 50-100%).
14 5.6 1.7 0.5 diameter D mm

5
4
Figure 9. The dependence of the transverse
~ 3
grain size d (the fibre width) in the tungsten rod
2 and wire on the total deformation degree e.
Additional annealing is done at 1500 C, 30 min
1 for the rod 5.7 mm in diameter and the wire 1.7
mm in diameter and for the wire 0.78 mm in
o diameter at 1350 C. The values of d are given
o 2 3 4 5 6 7 8 before annealing (lower values) and after
e annealing [34].
CONCLUSION
1. Plastic deformation plays a significant role in the processes of production of powder

metallurgy materials, including the process of sintering.
The concept of temperature ranges of cold, warm and hot deformation (and
boundaries between this ranges as characteristic deformation temperature and
recrystallization temperature) is useful in powder metallurgy for characterization and
optimization of consolidation and sintering processes.
2. The plastic deformation of sintered materials makes possible to eliminate porosity, to
redistribute the impurities and to create grain structure and dislocation substructure at
which the best combination of mechanical properties can be achieved.
3. TMT of ceramic materials which leads to microplastic deformation close to stress
concentrators makes possible to increase the strength of these materials.
ACKNOWLEDGEMENTS
The author wish to thank Professor R.A.Andrievsky and V.V.Skorokchod for the
active discussion of the problems of this paper.
This work was supported, in part, by the International Soros Science Education
Program through grant No SPU 072038 and by the Ministry of Science and Technology of
Ukraine grants No 4.3/121 and No 4.4/566.
517
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I. M.M.Ristich, V.I.Trefilov, Yu.V.Milman, I.V.Gridneva, D.Duzevich. Structure and Mechanical Properties of
Powder Metallurgy Materials. Cerbian Academy of Science and Art, Belgrad (1992) .
2. V.I.Trefilov, Yu.V.Milman, I.V.Gridneva, Role of plastic deformation in sintering covalent crystals , Powde r
Metallurgy and Metal Ceramics, 33, 7-8: 357 (1994).
3. M.L.Bernstein. Structure ofdefo rmed metals. Metallurgy, Moscow (1977) (in Russian) .
4. Yu.V.Milman, Structural aspects of warm and cold plast ic deformation of crystalline materials, Metal Science
and Heat Treatment ofMetals , 6:2 (1985) (in Russian) .
5. V.I.Trefilov, Yu.V.Milman, I.V.Gridneva, Characteristic temperature of deformation of crystalline materials,
Crystal Res. & Technol. 19,3 : 413 (1984) .
6. Yu.V.Milman, Characteristic temperature of deformation of materials and cold brittleness of BCC metals and
ceramics, in: Mechanics ofCreep Brittle Materials -2, A.C.F.Cocks and A.R.S.Ponter, Eds., Elsevier Science,
Leicester, UK (1991).
7. V.I.Trefilov, Yu.V.Milman, R.K.Ivashchenko, Yu .A.Perlovich , A.P.Rachek and N.I.Freze . Structure, Texture
and Mechanical Properties ofDeformed Molybdenum Alloys . Naukova Dumka, Kiev (1983) (in Russian) .
8. V.I.Trefilov, Yu.V.Milman, S.A.Firstov . Physical Basis of Strength for Refractory Metals . Naukova Dumka ,
Kiev (1975) (in Russian).
lh
9. V.I.Trefilov, Yu.V .Milman , Physical basis of thermo mechanical treatment of refractory metals , in: 12 Plansee
Sem inar, H.Bildstein, H.Ortner Eds., Metallwerk Plansee, Reutte, Austria (1989).
10. Yu .V.Milman, A.P.Rachek, G.G.Kurdumova, A.V.Abalikchin, N.I.Freze, To the problem of 45 brittleness of
the low alloyed molybdenum sheet, Physics ofMetals and Physical Metallurgy 48, 2: 309 (1979) .
11. Yu.V.Milman, The influence of directed alloying and thermomechanical treatment on the structure and
mechanical properties of high-purity chromium, molybdenum and tungsten, J.De Physique IV 5: 67 (1995) .
12. R.A.Andrievsky, On the temperature dependence ofdensification in sintering, Sci.Sintering 16,1 : 3 (1984) .
13. F.R.Nabarro, Deformation of crystals by the motion of single ions, in: Reports of a Conference on Strength of
Solids, The Physical Soc. of London , Cambridge (1948) .
14. C.Hering, Diffusional viscosity of a polycrystalline solid, J.Appl . Phys . 21, 5: 437 (1950) .
15. I.M.Lifshits, Theory of dynamic-viscose yielding of polycrystalline solids, Zh. Eksp. Teor. Fiz. 44 :1349
(1963).
16. R.L.Coble, A model for boundary diffusion controlled creep in polycrystalline materials, J.Appl. Phys. 34 :
1679 (1963).
17. M.F.Ashby, R.A .Verrall , Diffusion-accommodated flow and superplasticity, Acta Met. 21, 2: 149 (1973).
18. Ya.E.Geguzin. Physics ofSintering, Nauka, Moscow (1984) (in Russian) .
19. Ya.E.Geguzin, A.S.Dzyuba, V.P.Matsokin, Dislocation structures formed in the contact zone of two single
crystals , Ukr. Fiz. Zh. 29,9: 1419 (1984).
20. Ya.E.Geguzin, A.K.Emets , V.G.Kononenko, D.V.Pluzhn ikova, Dislocation mechanism of high-temperature
deformation of elements of the roughness of compressed real surfaces, Poroshk. Metall. 6: 35 (1982) .
21. W.Schatt , Untersudningen an Kupfer-Einkristall Sintermodellen, Kristall und Tecnik. 10,9: 845 (1975) .
22. W.Schatt, E.Friedrich, Versetzungsbildung wahrend des Sinterns, Planseeberichte fur Pulvermetallurgie 25, 3:
145 (1977).
23. W.Schatt, E.Friedrich, Crystal Research and Technology 17, 9: 149 ( 1982).
24. E.Friedrich , W.Schatt, Sintering of one-component model systems : nucleation and movement of dislocation in
necks, Powder Met. 23,4: 193 (1980).
25. E.Friedrich, W.Schatt, Vergetzungsverrvielfachung als Sinterreaktion, Z. Metallkunde 73,1 : 56 (1982) .
26. M.P.Poire. High-temperature plasticity ofcrystalline solids, Metallurgi ya, Moscow (1982) (in Russian) .
27. F.Garofalo. Laws ofcreep and long-term strengths ofmetals, Metallurgiya, Moscow (1968) (in Russian) .
28. I.Weertman, Steady-state creep of crystal , J.Appl. Phys . 28, 10: 1185 (1957) .
29. M.F.Ashby, A first report of deformation-mechanism maps, Acta Met.20 , 7: 887 (1972) .
30. S.Erdmann-Jesnitzer, F.GUnther, GesetzmliBigkeiten bei Verwachsungsvorgangen von Kristallen . n.
Rontgenographische Untersuchungen an verklebten Steinsalzkristallen, Z.Metallkunde 46, 12: 801 (1955) .
31. Yu.I.Boiko, R.B.Lakhterman, Stresses formed in diffusion sintering sets of real powder particles, Poroshk.
Metall. 8: 31 (1976).
32. W.Schatt, E.Friedrich, Dislocation-activated sintering processes , in: Sintering-85, Plenum Press, N.Y.-L.
(1987) .
33.I.P.Arsentyeva, M.M.Rist ic, Dislocation structure of nickel powder and its role in the sintering process , in:
Sinter ing-85, Plenum Press, N.Y.-L. (1987).
34. Yu.V.Milman, N.P.Zakharova, R.K.Ivashchenko and N.I.Freze, Structure and mechanical properties of K-
dopped W wire, in: Proc.14 Plansee Sem inar , G.Kneringer, P.Rlldhammer and P.Wilhartitz, Eds ., Metallwerk
Plansee , Reutte, 1: 128 (1997) .
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Physics ofMetals and Metallography (in Russian), 32, 5: 998 (1971) .
36 . Yu.V.Milman, I.V.Gridneva, I.V.Goncharova and V.A.Goncharuk, Effect of crack-tip stress relaxation under
load on silicon strength characteristics, Sc i. Sintering 30 (1): 29 (1998).
518
THE INFLUENCE OF SINTERING CONDITIONS ON THE MICROSTRUCTURE
AND MAGNETIC PROPERTIES OF SINTERED SmCc, MAGNETS
Nadezda M. Talijan 1, V. P. Menushenkov' A. D. Milutinovic-Nikolic',

A. S. Lileev1 and Z. D. Jovanovic'
'Institute of Chemistry, Technology and Metallurgy

11000 Belgrade , Yugoslavia
lInstitute of Steel and Alloys
117936 Moscow, V-49, GSP-2, Russia
INTRODUCTION
Since the magnetic features of the magnet of Sm-Co type are in direct connection with
microstructure, it is indispensable to achieve, in the procedure of synthesis of these materials,
the microstructure which ensures the maximal values of the magnetic features .
The aim of sintering is, on one side, the achievement of a high texture density without
opened connecting pores whereas , on the other hand, the growth of crystal grains should
be avoided l . 4 Opened pores cause intrinsic oxidation and therefore reduce the magnetic
remanence. The growth of crystal grains directly reduces the coercivity, making the
nucleation of reversed domains easier' . The heat treatment after sintering must be chosen to
correspond to the chemical composition of alloy, and its purpo se is to obtain a
microstructure which improves the coercivity' r'" . High values of coercivity are obtained
with microstructures that create grain boundaries with great pinning effect and low defect
density. If the heat treatment temperature is too high, the coercivity is reduced because the
pinning of the grain boundary is decreased . With lower temperatures the coercivity is also
reduced, the number of nucleation centres is increased, most probably by arising the
Sm1Co 17 precipitates 3
Most authors agree that only with heat treatment around 900C it is possible to get
adequately low nucleation defects and simultaneously achieve high coercivity due to a grain
. suffici
boun dary whiIC h IS icient Iy I'nrutmg?"
.. 1 35?"678 .
The microstructure of Smf'o, based magnetic materials is more complex than it might
be expected from the Sm-Co phase diagram because unwanted ingredients such as oxygen
affect the occurrence of undesirable inclusions and local heterogeneities'v'".
This study is dealing with the influence of sintering regime on the microstructure and
the magnetic features of sintered Srnf'o, magnets. Direct influence of microstructure (type
and participation of certain phases, but also their distribution) on the magnetic properties of

Kluwer Academic/Plenum Publishers, Ncw York, 1999 519
sintered magnets enable comprehension of the process of obtaining the sintered Smf'o,
magnets in the light of a triad "synthesis - structure-properties".
EXPERIMENTALPROCEDURE
The investigated SmCo, magnets were prepared by the powder metallurgy standard
methods, using the commercial powder, which passed through the phases of grinding,
pressing and orientation in the magnetic field. Compacts were sintered and heat treated.
Sintering was investigated in the temperature range from 1120 to 1140C, with sintering
times oDO, 45 and 60 minutes for each investigated temperature. The results for the samples
sintered at 1120C for 30 minutes exhibited poorer mechanical properties, which makes
magnetic measurements more difficult, and therefor are not presented in this paper. Heat
treatment for all the investigated sintering times and temperatures was always at 900C for
90 minutes . After heat treatment, the specimens are rapidly cooled to room temperature. A
vacuum of 150 Pa was used as a protection atmosphere during the sintering and heat
treatment.
For all investigated sintering regimes 7 specimens each were subjected to SEM analysis,
micro-x -ray analysis and to testing of magnetic properties. SEM analysis was performed
using Philips SEM 515 . The microstructure of the samples was observed, after mechanical
polishing and chemical etching with nital 1%.
Micro x-ray analysis was performed using Camskan - 4, Link AN-lOOOO, ZAF -4 .
Magnetic properties were measured on Hysterezisgraph with Hmax = 26 kOe .
Quantification of visual information CQVI) was conducted by utilization of the
appropriate software. The results of QVI and micro-x-ray analysis were correlated with the
sintering conditions and the measured magnetic properties.
Figure 1. SEM microphotography SmCo s sintered at 1120C, 45 minutes; x 1320
520
The microstructure of SmCo s based magnetic materials is more complex than it might
be expected on the basis of the Sm-Co phase diagram 9,10 because constituents, oxygen first
of all, affect occurrence of undesirable inclusions and local heterogeneities which reduce the
coercivity of these magnetic materials.
The Fig.I . shows a representative SEM microphotography of sintered and heat treated
SmCo s, so selected to make the present phases well noticeable. Main magnetic phase with
dominant Smf'o, (A) and intergranular secondary phases (B-dark gray) are marked on the
figure. The presence of oxide type phase (C-white) is also visible.
The micro-x-ray analysis was conducted on the indicated points of the SEM photo and
repeated on all other specimens . The results of the micro-x-ray analysis for all tested
sintering regimes are shown as the mean values in the Table 1.
Table 1. Results of Micro-x-ray analysis of sintered SmCo, magnets
No. Sintering Phase Sm, mass % Co, mass % 0 , mass%

temp., oC time,min
1120 45 main magnetic phase 32.44 66.78 0.78

oxide phase 78.56 4.23 17.21
secondary phase 23.67 75.58 0.75
2 ll20 60 main magnetic phase 32.58 66.58 0.84
oxide phase 58.28 31.81 9.92
3 1140 30 main magnetic phase 33.09 65.44 1.47
oxide phase 64.37 25.31 10.32
4 1140 45 main magnetic phase 33.03 65 .85 1.12
oxide phase 71.25 15.22 13.53
5 1140 60 main magnetic phase 32.43 66.66 0.91
oxide phase 51.24 40.39 8.37
secondary phase 32.65 65 .22 2.13
On the basis of SEM analysis and comparing the results of the micro-x-ray analysis
from Table 1. with stoichiometric composition of certain constituents , the following
compounds were identified as present:
Smf.o , primary phase and the carrier of magnetic properties (makes approx . 90-98% of
main magnetic phase),
Sm1Co 17 undesired secondary phase which reduces coercivity (makes the major part of
gray phase), Sm1C07 phase (present only in traces because the initial powder was of
subeutectoid composition) is less detrimental secondary phase because its presence of up
to 7 vol.% does not affect coerc ivity,
Sm103,C030 4 and adsorbed oxygen-undesired constituents as a result of insufficient
efficiency of protective atmosphere.
Deviation from the ideal stoichiometric composition was noticed for each phase
identified by the micro-x-ray i.e. SEM analysis. Comparing the results obtained by the micro
x -ray analysis and the appropriate stoichiometric composition, it can be concluded that the
composition of the main, secondary and oxide phases are not mono lithic but that there are
different degrees of heterogeneity :
521
Table 2. Volume fraction of the main magnetic, secondary, oxide phase and pores
No Sintering Phase Fraction, vol. %

temperature.X' time, min
1120 45 main magneticphase 70.07

oxidephase 7.16
secondary phase 15.94
pores 6.83
2 ll20 60 main magneticphase 78.27
oxide phase 8.91
pores 2.03
3 1140 30 main magneticphase 68.94
oxide phase 6.38
pores 11.17
oxide phase 2.50

oxide phase 4.28
pores 7.02
Br,kG
1'+-1----- 3
-10.0 -7.5 -5.0 5.0 7.5 10.0

He, kOe
Sintering regimes:
\- 1120 C, 45 min.
2- \120 C, 60 min.
3- 1140 C, 30 min.
4- 1140 C, 45 min.
5- 1140 C, 60 min.
-10.0
Figure 2. Hysteresis curves for SmCo5specimenssintered at differentregimes
522
The main magnetic phase (A) consists of a dominant SmC0 5 phase (up to 98 mass%);
Sm zCo 17 (0.5 -9. 5mass %) and adsorbed oxygen (:::::;1 mass%) .
The secondary phase (B) consists of the same intermetallic compounds SmC0 5 and
Sm zCo17, but in another ratio . The Sm zCo17 content ranged from 66 to 92 mass% , The
content of adsorbed oxygen (:::::; 1mass %) , and the remaining part was SmC0 5 phase.
The oxide phase (C) contains also SmC0 5, in addition to SmZ03 and C0 30 4 and the
present adsorbed oxygen the result of the applied (P/M) technique. The content of
SmC0 5 varied considerably subject to the sintering regime , in the range from 5 to 45%.
The volume fraction of the main magnetic phase , secondary, oxide phase and pores has
been ascertained on the basis of SEM analysis and QVr. The Table 2 shows the QVI results -
volume fraction of all present phases . The main magnetic phase content for all sintered and
heat treated specimens was established on the level of 70 -85 vol.% The secondary phase
content ranged from 7.5 to 16 vol.% . The oxide phase ranged from 2 to 9 vol.%
MAGNETIC PROPERTIES AND MICROSTRUCTURE
For the purpose of investigating the sintering regime influence on the structure i.e.
magnetic properties, the tests of magnetic features have been conducted. The Fig.2 . shows
the representative hysteresis curves of the investigated SmC0 5 specimens (Table I) in the
sintering regime function .
During testing the magnetic properties it was ascertained that there is dependence of
coercive force and remanence on the volume fraction of individual phases.
The coercive force (He) grows with the increase of the main magnetic phase with
dominant SmCo 5 . This dependence can be shown by the third degree polynomial. The
graphic presentation of this dependence with the appropriate polynomial is given in Fig .3.
Fig. 4 shows the influence of the fraction of the main magnetic phase on the
remanence. The remanence grows with the increase of the main phase content and this
dependence can also be fitted by the third degree polynomial, but the increase in remanence
with the increase of participation of the main magnetic phase in sintered magnets is less
effective .
lie = -574.6697 3+22 .969859 X - 0.30574888 x 2 +0.00 \ 3576 146 X 3

2.5
2.0
v
0 \ .5
...::<:
U
:r:
10
>:
~
/~
0.5
70 75 so 85
Main magnetic phase, vo l. %
Figure 3. Dependence ofHc on the volume fraction of the main magnetic phase
523
8.0 Br=-596.5352I + 23.39285 X - 0.30195 X2 + 0.0013 X'
7.8
7.6
I
7.4

07:2
...:.:
~7 .0
6.8
6.6
6.4

70 75 80 85
Main magnetic pha se. vol. %
Figure 4. Dependence of Br on the volume fraction of the main magnetic phase
Contrary to this, with the increase in participation of the oxide phase and lor pores, the
coercive force is lowering. Also, the best results for coercivity are obtained when the
presence of the secondary phase is low enough . The influence of participation of pores,
oxide phase and secondary phase on the remanence is very similar. With increase of
participation of these phases in the sintered magnet the remanence lowers but at smaller
rate.
It should be pointed out that the values of the magnetic properties obtained in the
conducted researches are below the expected values for this magnet type. The reason lies in
the fact that the tests were conducted with SmCo, powder ofsubeutectoid composition .
The achivement of optimal structure that improves magnetic properties is designed during
the sintering process . By observing Table 2. it can be noticed that participation of the main
phase with dominant presence of Smf'o, increases with the increase of sintering time and
temperature up to 1140C for sintering time of 45 minutes. For this sintering temperature
and time, the content of SmCc, phase, as a carrier of magnetic properties is the highest,
while the content of oxide phase is the smallest and the measured magnetic properties are
the best.
We wished to point out, through the trend of the obtained dependence of the structure
and magnetic properties in the function of the sintering regime for the constant conditions of
heat treatment, to the importance of the synthesis - structure - properties triad in designing
the microstructure and in realization of magnetic materials of this type.
CONCLUSION
It has been ascertained, on the basis of SEM and micro - x - ray analysis, that none of
the microscopically noticed phases (main magnetic phase, secondary and oxide phase) is
chemically homogeneous, but that there are different degrees of heterogeneity subject to
sintering conditions.
On the basis of micro-x-ray analysis and comparing these results with stoichiometric
composition of certain constituents the following phases were identified as present: SmCo s,
Sm2C0I7, Sm2C07, Sm2 0 3, C0 30 4 .
524
According to SEM and QVI analysis, the volume fraction of the main, secondary , oxide
phase and pores were established as a function of sintering regime.
In these investigations the highest content of SmC05 phase as the carier of magnetic
properties, the smallest fraction of oxide phase as well as the best magnetic properties were
obtained with sintering conditions: 1140C, 45 minutes.
The influence of participation of the main magnetic phase on magnetic properties (He
and Br) has been investigated. It was found that the samples of sintered SmC0 5 with the
highest volume fraction of the main phase have the best magnetic properties. Coercivity and
remanence increase can be expressed by the third degree polynomial.
REFERENCES
I. V.V. Sergeev, T.I. Bulygina, Magnitotverdye Materialy, Energiya, Moskva (1980).

2. J.Onnerod, The physical metallurgy and processing of sintered rare earth permanent magnets, J.Less -
Common Met. 111:49 (1985).
3. E.Adler, G.W.Reppel, W. Roderwald and H.Warlimont, Matching PIM and the physics of magnetic
materials, The Intemational Journal ofPowder Metallurgy 25[4]:319 (1989).
4. K.J.Strnat and R.M.W. Strnat, Rare-earth cobalt permanent-magnets, J Magn. Magn. Mater. 100[1-3]
:38 (1991).
5. W. Ervens, H.Wilmesmeier, "Magnetic materials" in: Ullmann's Encyclopedia of Industrial Chemistry,
Fifth, CompletIy Revised Edition Vol. A16, p.l , B. Elvers, S. Hawkins and G.Shulz ed., VCH Verlag
GmbH, D. Wernheim, Germany (1990).
6. R.M.Rose, LAShepard and J.Wulf, The Structure and Properties of Materials, John Wiley & Sons, inc.,
New York-london-Sydney (1966).
7. N.M.Talijan, AMilutinovic-Nikolic and Z.DJovanovic, The influence of protective atmosphere on
oxidation of sintered SmCos magnetic materials, Sci. Sint. Spec.Iss, 28:179 (1996).
8. N.Talijan, AMilutinoviC-Nikolic, RJancrc, 1. Petrovic-Prelevic and J. Stajic-Trosic, The influence of the
sintering regime on the stability of the Smf'o , phase, Material Letters, 32: 85 (1997).
9. M.F.De Campos and FJ.G.Langraf, On the microstructure of Smf'o , magnets, Proc. of 14th
Intemstionsl Workshop on Rare-Earth Magnets and Their Application, Sao Paulo, Brazil Vol I: 321
(1996).
10. W.G.Moffatt,Handbook of Binary Diagrams Vol. 2, General Electric Comp., USA (1978).
525
THE INFLUENCE OF DIFFERENT BINDERS AND METALS ON THE
PROPERTIES OF SINTERED METAL-GRAPHITE MATERIALS
1 J .U zeIac,
2 N .D emc,
,1 R .V aSlc
v
C .LV
acnJevac,
' ,1
1) IMS Institute, Bul.vojv.Misica 43, Belgrade, Yugoslavia

2) V.Z. "Moma Stanojlovic", Batajnica
ABSTRACT
The possibility of composite materials' sintering has been examined in order

to obtain a product resistant to wear in contact with an electric current cable or any
other surface. Except for graphite, copper and iron, these sintered materials also
contain certain binders, different kinds of resin.
Examination into the effects of two kinds of resin on wear of the obtained
sintered samples has been conducted. Apart from wear some other physical-
mechanical and electrical properties have been tested as well.
Keywords: graphite, iron, copper, resin, sintered, physical-mechanical and electrical

characteristics.
INTRODUCTION
By its physical-mechanical and electrical properties graphite is very

convenient and frequently used material in the production of different kinds of
contacts, conductors, particles and other sintered articles for the conduction of
electric current in various systems (1-3).
In these sintered articles graphite is used in mixture with other components,
such as copper, iron, lead, tin etc., which depends on their purpose and the place of
building in. The basic components in these sintered materials are binders and metals
which affect certain physical-mechanical and electrical properties of the obtained
products. Two kinds of resin made by different manufacturers have been tested in
this study.
In order to obtain composite material products with precisely defined
physical-mechanical and electrical properties one must start from defining
composition, granulation of starting components and conditions in which sintering
will be carried out (pressure, temperature and time) .
Ad vanced Science and Technology of Sintering, ed ited by Stojanovi c et al.

Kluwer Academic/Plenum Publ ishers. New York, 1999 527
For that purpose sintering of a certain number of samples was performed and
their physical-mechanical and electrical properties were tested whereupon they
were compared with the original imported samples.
The aim of this research was the substitution of imported products for
domestic composite materials.
EXPERIMENTAL
Based on the chemical analysis of the original samples of composite

materials, applying modern instrumental methods, their chemical compositions were
discovered.
In that way the indentification and characterization of the original samples of
composite materials were made in the first phase.
In the second phase on the basis of the known chemical composition and
finished product properties as well as of considering the problem of sintering these
composite materials, a certain number of samples were made .
The main components of these samples were graphite and petroleum coke
used singly or in the mixture of equal parts.
The quantity of graphite (type CR or S-40) in the samples amounted to 70%
when they were used separately or each 35% when added together.
Other components (copper and iron) were added separately. The granulation
of all the used components was 200 meshes.
As binders two kinds of phenolformaldehyde resins were employed: vulcadur
"A", manufacturer "Bayer", Germany and the resin SP 6600, manufacturer
"Schenectady", France. The concentration of these resins in the samples was 20% .
All powdery components were put into laboratory stirrer where
homogenization was carried out in the period of one hour. After that, a binder,
resin and a certain quantity of ethyl alcohol were added. This mixture was
subsequently homogenized for further 30 minutes. Later, the mixture was dried at
50C, and then grinding to a precisely defined granulation was done .
Sintering of samples was performed at pressures of 700 kg/ern' , at
temperatures of 140C to 200C in the period of 15-20 min.
Thus obtained samples were submitted to testing of physical-mechanical and
electrical properties: volume weight, hardness, wear, specific resistance and
potential drop.
Wear was tested in accordance with the standard B.B8.01S in the machine for
wearing test by whetting made by the firm "Alfred Amsler" Switzerland. The
applied method for wearing test was adapted to the tested material.
Namely, because of the low hardness of the tested material it was not
necessary to perform the complete wear process, but the tests were conducted at
only 66 revolutions (three cycles at 22 revolutions each), and not at 440 revolutions,
as the standard advises.
Testing of the specific resistance and potential drop was carried out in
accordance with the standard IEC 136/1986, annex C, modified procedure with the
apparatus H8P model 3466A, class 05. All the other tests were performed by
classical methods.
Chemical analysis of the original samples proved that they consisted of

graphite, copper, iron and a binding agent.
528
Table 1. Composition of tested samples
Resin
Composition Graphite Graphite Petroleum Copper Iron
Sample N CR S-40 coke Vulcadur
SP 6600
"A"
1 + + +
2 + + +
3 + + +
4 + + +
5 + + +
6 + + +
7 + + +
8 + + +
9 + + +
10 + + +
11 + + +
12 + + +
Based on these analyses and the available starting components, the samples
were made and their compositions are given in Table 1.
Physical-mechanical and electrical properties of the above given samples
were tested. The tested properties and the obtained values are given in Table 2.
The displayed results clearly demonstrate the change of physical-mechanical
and electrical properties depending on the composition of the samples. Similarly,
the connection of the change of electrical properties with the changes of physical-
mechanical properties is noticed. The obtained results for hardness point to their
numerical diminution comparing to the original samples (up to 17%). The reason
for that may be in the way of preparing samples (pressure and temperature) as well
as in the granulation of the applied components. The values for volume weight are
higher than for the original for 10-13% which is connected with the quantities of
copper or iron in the samples.
Hardness test of samples was performed by defining resistance to wear by
whetting. A clear change of wear resistance value comparing to hardness of samples
is noticed from the obtained results: as the hardness decreases, resistance to wear by
whetting increases. However, this regularity need not be general, because the
original samples show the highest values of hardness and the change of wear
resistance is medium comparing to the tested samples. This shows that the
inereasing value of wear resistance is affected by other parameters as well. The best
values of wear resistance were obtained for the samples N 7 and N 6, while using
the same graphite S-40 but different binders and metal components.
The obtained values for electrical properties show mutual correlation. It is
noticed that the value decrease of potential drop leads to diminution of specific
resistance as well as of temperature of the tested samples and that represents the
direct correlation.
529
Comparing the obtained values for wear with the measured values for the
temperatures of the samples it is noticed that as the temperature value lowers, wear
resistance rises which is quite understandable. All the conducted tests indicate that
the samples N 7 and N 6 show the best physical-chemical and electrical properties
although their binders were different.
Table 2. Values of tested properties
Properties Hardness Wear Potential Specific Sample

drop resistance temperature
Sample (HR 10/60) (cm3/50cm2) (mV) (mOcm) (0C)
1 106 7.9 405 16.4 113
2 107 8.3 423 19.5 115
3 110 9.6 495 21.0 121
4 104 3.78 269 4.6 109
5 104 9.24 306 4.8 111
6 101 2.29 141 4.3 107
7 100 2.21 138 4.1 105
8 104 3.95 291 4.6 110
9 110 10.7 510 23.1 125
10 111 11.0 526 25.4 129
11 111 11.4 1105 37.3 135
12 114 12.05 1264 49.2 150
CONCLUSION
On the basis of the chemical analysis the chemical composition of the original
samples was defined and, based on that, six trial samples were made all of which
were submitted to examination of their physical-mechanical and electrical
properties. On the basis of all the tests the materials were determined which by the ir
composition and properties can be the substitution for the samples of foreign origin.
Further study should be directed to defining the dependance of starting
components' granulation change on the physical-mechanical and electrical
properties of the obtained samples, as well as to testing in practice the trial samples
purposed for making contact with an electric current cable .
REFERENCES
1. J.B.Donnet and A.Voet: Carbon Black, Physics, Chemistry and Elastomer

Reinforcement, Marcel Dekker, N.York-BaseI, 1976.
2. Goldschmidt,A., Glasurt-Handbuch: Lacke und Farben, 1984, Hannover.
3. Ilack-Schwerpunktthemen: Bandz, Priifechnik, Hannover, 1991.
530
THERMOPHYSICAL PROPERTIES OF HOT-DEFORMED POWDER
MATERIALS
Vladimir'Yu.Dorofeyev'iand Yuriy G.Dorofeyev l
1 Novocherkassk State Technical University,

132 Prosveshcheniya str., Novocherkassk, Russia, 346428
INTRODUCTION
Earlier it was established that heat and electric conduction (accordingly A and y) of hot-
deformed materials decreasing is caused by the high presence of defects and fine-grained
structure in comparison with standard cast materials of analogous composition. High
temperature annealing brings to conduction increasing, which is caused with removal of
some structure defects. Conduction linearly increases with porosity decreasing. Under
porosity <5 - 7% this growth becomes slow in the course of sharp increasing of structure
defect presence. Varying technology and treatment parameters it is possible to control
structure formation and to obtain materials with required properties.
Last time it is observed the development acceleration of item production by the methods
of hot treatment by pressure of powder preforms and usage different approaches of cast
material treatment. This causes high-priority problem of further study properties of hot-
deformed powder materials. The usage of experimental results in context of worked out
positions of splicing quality criteria, their connections with properties and parameters of
technology are especially promising.
MATERIALS AND EXPERIMENTAL PROCEDURE
The investigations were performed on specimens out of reduced iron powder

PZhV2.l60.26 and powder carbon steel 20p (carbon content - 0.20w/o) on its base. Such
choice was caused with the following reasons : generality of structure formation laws of hot-
deformed powder materials; labour content of thermophysical property definition and the
most wide abundance of alloys on iron base in powder metallurgy. Synthetic graphite was
introduced into the mixture for receiving steel. Its quantity was OAw/o, which allowed to
compensate decarburization. After heating preforms before hot repressing during l5min at
1100 c the quantity of chemically bound and free carbon was 0.20 and ~0 . 0 5 w/o
accordingly.
Advanced Science and Technol ogy ofSintering, edited by Stojanovi c et al.

Practically non-porous preforms of 4x55x105mm size were produced at the expenses of
specific densification work W=250MJlm J For providing given porosity P (3, 6, 10 and
18%) hot preform pressing was made up to the fixed height against the special stop and
value W composed 200, 150, 100 and 50MJlmJ accordingly. Three specimens of size
4x4x100mm were cut out of preforms for investigations.
Heat flux for the measurement A and potential gradient for measurement Y were created
at laboratory equipment with direct current supplied to the specimen end faces.
Temperature was measured with thermocouples weld in the centre of specimen and at the
distance of35mm from it. Determined values A and yrefered to the corresponding values of
their standard analogs. The coefficients of relative heat conduction Arel and specific relative
electric conduction Yrel were defined as
Arel= ~ ; Yrei = ~ , where Ap, YP- heat and electric conduction of powder iron or powder
e re
carbon steel 20p; Ae, Ye - heat and electric conduction of iron-armco or cast carbon steel
20.
The Results of Heat Conduction Definition
Temperature dependences Arel, Figure I, witness about their basic similiar character for
powder iron and steel 20p. Almost in all cases (with pore-free steel 20p excluded) Arel at
T=const remains unchanged up to 500 - 600C and then it begins to increase. Obviously it
is connected with recrystallization running during investigations, while for pore-free
powder steel 20p it finished before the investigation began. It confirms that at T<500c and
Pr:::J 0% values Are! for steel were higher than for the iron. Only at high temperatures
structure material conditions become homogeneous. As this takes place Arel of iron
4
1.0 - - - --
Figure 1. A,./ as a funct ion of temperature

7
0. I - -........---AL..--...:...------ for por e-free powder iron in reference to the
iron-armco (1) and for powder steel 20
(carbon content-0.20 w/o) on reference to
0.5 L - _ - . . l_ _---l._ _--L_ _- l -_ _....L_ _
the cast steel 20 (2 - 6). Porosity, %: 2 - 0; 3
100 200 300 -l00 500 600 T, C - 3; 4 - 6; 5 - 10; 6 - 18.
increases and relationships between heat conduction values of powder materials come to the
correspondence with relationships for standard cast materials of similiar composition.
Porosity increase of investigated specimens brought to heat conduction decrease at all
temperatures, and plots Arel=f(J) displace equidistantly. The last condition caused isolation
expediency of two zones of these dependences (JOO -500 C and 600 -700 0c) and their
separate consideration.
532
Figure 2. Influence of porosity on .-l,et for
0.6 L - _ - - - - l_ _----l ---"- -' powder steel 20. Investigation temperature
o 3 (, 10 P. 'Yo intervals: 100 - 500C (I); 600 - 700 C (2).
The analysis results of dependences Arel=f(P), specified in Figure 2, show that in both
selected temperature ranges Arel linearly decreases with porosity increase. These
dependences can be expressed as follows:
(1)
where A;el is ultimate value of relative heat conduction of powder material at zero porosity,
maximum reached at fixed structure condition; K}. - proportionality coefficient, defining
decrease rate Arel when porosity increases. Equation (l) performance values at different
temperature ranges at porosity, measured in %, are specified in Table 1.
Analyzing data of Figure 2 and Table I, it is possible to establish that Are! is always less
than heat conduction of corresponding compact analogue and increases a little, if
investigations are realized at temperature, exceeding recrystallization threshold. But it's true
only for the materials, which were not subjected to preliminary annealing. Proportionality
coefficient value K ). decreases in high temperature range of investigations that defines
lowering decrease rate Arel as porosity increases.
Table 1. Equation (l) performance values
Performance s Temperature range, c

100 -500 600 700
-; 0.950 0.960
K1 0.017 0.0136
Expression (I) seems more legitimate and to a greater degree reflects the nature of
described process in comparison with classic equation of generalized conductivity by
V.I.Odelevskyl and by formula, suggested in2 There are two reasons here:
properties are defined in reference to the non-porous powder analogue, but not to the
compact cast material. Structure condition of the latter can significantly differ from
corresponding performances of investigated specimens;
proportionality coefficient values K}. are made more exact applying to the concrete
material (steeI20p) and introduced as constants, depending on investigation conditions.
Proposed in3 expression for Arel of austenitic materials as power function of (i -P) was
not well confirmed by investigations. Per contra, in investigated range of porosity (up to
20%) plots had linear character as in our experiments .
533
Yrel
1,0 ---~~---c-----
0,9 L-..--....::.:.------c---
'3./
0,7 L __r----r--~-------.,..---
I I I I I
200 300 400 500 600
Electrical Conduction of Powder Iron and Steel20p
Temperature dependences of relative electric conduction rre/, Figure 3, differ from

corresponding heat conduction dependences with the absence of curve inflection at
recrystallization temperatures. Obviously it may be connected with less structure sensitivity
of electrical conduction, namely with absence of phonon conduction component. Great
values Yre/ in comparison with Are/ at all specimen porosities and investigation temperatures
witness the same fact. One more feature of the functions Yre/=f (T) is practically full absence
of porosity influence on value rre/ till reaching definite value P*, conventionally called
liminal. The effect of original compensation of conduction decreasing at given concrete
section on the account of neighbouring section can serve hypothetical reason of such
situation. At this neighbouring section corresponding pores in the flux direction are absent.
This effect, which can be called the effect of "porous shunting" is revealed only up to the
value P*.
Yrel ..... _
0,8
Figure 4. Influ ence of porosity on Yrel for

0,6 L - _ - - - - I_ _----I --'- ----J powder steel 20. Investigation temperature
o 3 6 10 P, % intervals: 100 - 500 C (I); 600 - 700 C (2).
Graphic dependences rre/=f(P) for limit investigation temperatures (100 and 700C) are
specified in Figure 4. All the intermediate (at T=200, 300, 400, 500 and 600C) plots are
equidistantly placed between these two plots and because of nearness of experimental
points are not presented . They can be analytically described by the equation:
(2)
534
where Y;el - is ultimate value of relative electrical conduction of powder material at zero
porosity, maximum reached at fixed structure condition; K; - proportionality coefficient,
which defines rate decrease Yrel with porosity increase.
Equation (2) performance values at "limiting" investigation temperatures are cited in
Table 2. Performances at intermediate temperatures have intermediate values, as
corresponding plots Yret=f(P) are equidistantly placed in the range between cited ones in
Figure 4.
Table 2. Equation (2) performance values.
Performances Investigation Temperature, c

100 700
-:K 0.95
0.018
1.00
0.019
y
P 4.0 5.0
Analyzing data of Figure 4 and Table 2 it is possible to come to the conclusion that
investigation temperature increase from 100 to 700C brings the value growth of ultimate
electrical conduction from 0.95 to /.00 and the extreme insignificant change of values K,
and p'. Such stability of these performances testifies to common mechanism of
investigation temperature influence on their values and to the reliability of performed
investigation results.
Thermophysical Property Correlation with Structure Performances
Some heterogeneity of hot-deformed materials, caused by the presence of structure-free

carbon, must bring to the conduction increase. Nevertheless the quantity of structure-free
carbon is not large and can't significantly change the conduction value. Per contra,
conduction decreases with decrease of steel grain values, and as it is known", studied
materials are distinguished by fine grains. But this influence is insignificant and does not
cause substantial change of investigated performances.
Increased presence of substructure defects have definite significance because electrons
and phonons, realizing conduction are scattered with defects of lattice. But the difference in
its value remain the same even at similiar density of defects, provided in the annealing
result, for example.
Considerations, mentioned above, cause expedient research of correlational connection
between conduction exponents and such structure defects as pores, nonmetallic inclusions,
transistorized oxide films on interparticle surfaces and so on. Pointed defects are easily
revealed at fractographic analysis. They are differed from each other with difficulty and
their influence is similiar in many cases, that is why in our opinion the most correct is the
s;
dependence (A. rel , Y rei) = f ( K p + Kn ) ; K p =
Sp
t'
Kn =
S
where S is total fracture surface
square; Sp and S; - projection square of pores and nonmetallic inclusions on the fracture
surface image plane. Pointed dependences were obtained on the base of described above
results of heat and electrical conduction definition and fractographic analysis of crushed
specimens. These dependences are specified in Figure 5.
535
Arel, Yrel
,
0,900
0,800
0,700
Figure 5. Dependences Arell.(Kp+Kn) - 1,2 and

YreFf(Kp=Kn) -3,4 . Investigation temperature intervals
0,600 100 - 500C (I); 600 -700C (2) ;. Temperature, 0C: 100
5 10 15 20 Kp+K n (3) and 700 (4) .
Account of influence on relative thermal conduction of nonmetallic inclusions content

and some value difference of plane porosity' Kp from its volume value brought to definite
position change of corresponding plots in Figure 5 (plots 1 and 2) in comparison with
specified in Figure 2. Though ultimate values Are! were not reached in this case,
extrapolation of experimental dependences allow to obtain their values for the case when
Kp+Kn=O, as the material corresponds to cast analogue . At all investigation temperatures
A;el = I (crossout point with axis ordinate of continuation of plots 1 and 2) is obtained.
Accordingly at these conditions Ap of powder material is equal Ac of cast one, and it means
correctness of adopted above assumptions and confirms exclusive dependence Are! on pore
and nonmetallic inclusion on fractographic images .
Dependence character Yrel=f(Kp+K,J (Figure 5, plots 3 and 4) in comparison with
Yre!=f (P), specified in Figure 4, practically do not change. Some displacement of plots is
caused by increase of all experimentally determined values Yre! for a quantity of K; "" 2%,
that is Kp "" P. It also means identity of influence mechanisms of pores and nonmetallic
inclusions revealed during fractographic analysis on investigated material coductivity.
REFERENCES
I . V.l.Odelevsky, The generalized conductivity of heterogeneous systems calculation,Journal a/Technical
Physi cs, XXI: 6: 123 (1951) (in Russian).
2. V.V.Skorokhod, About dispe rsed mixture electrical conductivity of conductors & nonconductors,
Engineer-Physical Journal, 8: 67 (1959) (in Russian).
3. U.Kutsch, P.Beiss, J.J.Jiiger, Effects of density on mech anical properties, thermal conductivity &
machinability of sintered stainless steels, Proc. 0/the i997 Europ ean Conference on Advan ces in
Structural PM Component Produ ction, Euro PM9 7, EPMA, Munich (1997).
4. Yu.G'Dorofeyev, L.G .Marinenko, V.I.Ustimenko, Structural Powder Materials & items, Metallurgy,
Moscow (1986) (in Russian) .
5. M.Sle sar, M.Be stertsi , E.Dudrova, Growth of interparticle bond s durin g sintering of powder copper,
Powder Metallurgy , 7: 100 (1982) (in Russian).
536
COPPER MATRIX STRENGTHENING IN Cu-AI 20 3 SYSTEM BY
MECHANICAL ALLOYING AND MILLING OF PURE COPPER AND
PREALLOYED COPPER POWDERS
V.Rajkovic, S. Zec, M. Mitkov
Institute of Nuclear Sciences "Vinca", Material Science Laboratory

P.O.Box 522. 11001 Belgrade, YU
ABSTRACT
Mechanical alloying of Cu+3wt.% AlP3 powder mixture and milling of pure

and prealloyed copper powder with 3.5wt.%AI (CuAl3.5) have been performed in
planetary ball mill in air up to 20h. All powders have been then treated in H2 at 400
"C for 1h, in order to eliminate formed oxides. Hot pressing was used for compaction
(800C, 3h, Ar, 35 MPa). The copper matrix strengthening was estimated by
microhardness measurements. The microhardness of pure copper powder and
prealloyed CuAl3.5 powder showed 5 times, and Cu+3% Al20 3 powder mixture 4
times greater values respectively, in comparison to the pure untreated copper
powder. The strengthening effect in Cu compacts is due to grain refinement and
increased dislocation density. The hardness of CuAI3.5 powder and Cu+3% Al20 3
powder mixture is additionally influenced by of Al 2 0 3 dispersoids presence.
INTRODUCTION
Oxide dispersion strengthened alloys, made by mechanical alloying, are

characterized by very fine grain sizes (clum in diameter) and a presence of
extremely small oxide dispersoid sizes (30-40nm)l. Depending on the size and
interparticles distance, dispersoids are effective barriers to dislocation motion.
Therefore, the strength of MA alloys is a consequence of grain boundary
strengthening e.g. Hall Petch effect as well as Orowan mechanisms.
The goal of this investigation presents an attempt of highlighting the possible
strengthening mechanisms in Cu-AI system. The additional work was done to
establish differences associated with Al20 3 introduced particles into Cu matrix. The
internal oxidation technique', mechanical alloying and milling of pure Cu powder
were used.
Advanced Science and Technology ofSintering , edi ted by Stoj anov ic et al.
Kluwer Academic /Plenum Publ ishers. New York , 1999 537
The electrolytic copper powder, inert gas atomized prealloyed copper powder
containing 3.5 wt.% Al (CuAI3.S) and commercial Al20 J powder served as starting
materials. Mechanical alloying of Cu+3wt.% Al20 J powder mixture and milling of
pure and prealloyed copper powder have been performed in planetary ball mill in
air up to 20h (powder / steel balls ratio, 1:3S). Milling in air promoted formation of
Al20 J dispersoids in prealloyed copper powder (internal oxidation). In order to
eliminate copper oxides all powders have been treated in H 2 at 400C for 1h. Hot
pressing was used for compaction (800C, 3h, Ar, 34MPa).
The as milled and as compacted powders (after 0,3, S, 10 and 20h milling time)
were characterized by X-ray diffraction analysis, optical and scanning electron
microscopy. The average lattice distortion, grain size and dislocations density were
calculated from x-ray line broadening. The copper matrix strengthening was
followed by microhardness measurement (SOg).
X-ray diffraction analysis of milled powders shows the progress of line

broadening with milling time (111, 200, 220 and 311 lines). (111) line broadening has
been shown in figl. The line broadening is a result of the severe distortion and grain
size refinement'. Dependence of grain size and lattice distortion has been shown in
fig.2 and fig.3 respectively. As can be seen, the reduction in grain size occurs in the
early stage of milling (up to 20h) (fig.2). At the same time, the lattice distortion
increases (fig.3). Dislocation densities, determined from grain sizes, slowly increase
with milling time, except in the case of pure Cu (figA). The distinctive increase of
dislocation density in the copper matrix occurred after 10h milling time.
0 0.6
CD Cu
N
E 0.5 Cu+3wt.%A1 0
2 3
::l
.5 ~ ~ . - - - _. . - - - - - -
x 0.4
""
E
......
] 0.3
A'
.. ~ '
.
i- t
CuAl3.5 '
...
""
~ 0.2
"
.~
= 0.1
~
0.0
0 5 10 15 20 25
Milling time, h
Figure 1. Full width of (III) line at half maximum vs. milling time.
SEM examination shows that powder particle morphology has been changed
during milling ( Fig.S). Up to lOh milling time, the powder particles of pure Cu as
well as CuAI3.S are similar in shape (fig.Sa and c), while Cu+3%AI 20 J particles
appear different (fig.5b). lOh milling leads to enlargement of the powder particles.
538
2000
6.... 1500
[
.~
III
1000
e
'Cij
cS 500
O+--'---r-~",,--'---r-..-....--.--i
o 5 10 15 20 25
Milling time, h
Figure 2.Grain size v.s. milling time.
The typical refinement and spheroidization of the particles occur during subsequent
milling up to 20h. These changes correspond to general accepted model",
0.5-r-------------...,
CuA13.5
~
..
:.
0.4 Cu
.-
.- - -- - - _. - - - - - - - --
~
~ ~;
.g 0.3 Cu+3%AI
20)
...
2
.~
"0 0.2
.~....
(\l
.-l 0.1
5 10 15 20 25
Milling time, h
Figure 3. Lattice distortion v.s. milling time.
During milling, the powder particles undergo deformation, fracturing and rewelding.
By repeated welding and fracturing particle size refinement occurs and typical
microstructure is developed. The steady state particle size distribution establishes as
a result of the balance between the amount of welding and the amount of fracturing.
It does not seems (fig.5b, d and f) that steady state, in our examined materials, has
been completely reached even at 20h milling time.
The typical lamellar particles structure has been formed during milling in all
examined materials . This structure is retained after compaction as well. The
lamellae, in this case, represent a plastically deformed starting powder particles.
Fig.6 presents the microstructure of mechanically alloyed Cu+3%AI 20 3 particle and
compact after 3h milling time.
539
100T-"-------------,
-e
u
80
Cu
~
o
......
i- 60
' <;j
c:
Q)
"0 CuAl3.5
c: 40
.9
i
u
..9 ~ .
.~ 20
c Cu+3%A1 0
. ............ z )
::. ,.
5 10 15 20 25
Milling time, h
Figure 4. Dislocation density v.s. milling time.
The hardness of CuA13.5 and Cu+3wt.% Alp) compacts (fig.7) shows that
Al.O, dispersoids cause considerable strengthening in the early stage of milling time
(up to lOh). The Alp) dispersoids, formed by internal oxidation (CuAI3.5
compacts), effectuated more pronounced strengthening than AlzO), dispersoids
incorporated in the metal matrix by mechanical alloying. The similar behavior has
been already proved beafore". This observation indirectly suggests that the particle
size should be finer here. Dislocation density and grain sizes also influence the
microhardness of CuAI3.5 and Cu+3wt.%Alz0 3. They superponed with dispersion
strengthening which predominates up to 5 h milling time. The change of hardness as
well as grain size and dislocation density is neglectible after lOh milling time.
The microhardness intensively increases after lOh milling time for Cu compacts
as well. Since very small grain sizes (fig.2). and dislocation density increasing (fig.3)
have been observed in the same milling period, the maximum strengthening effect
could be regarded as their consequence. Thus , treating of elemental powders in
high-energy ball mill, yields more pronounced strengthening effects then powder
mixture treating. Dispersion strengthening dominates the first stages of the milling
process (up to 5h), while grain size effects as well as dislocation densities influences
remarkable the late stages (from 10 to 20h).
CONCLUSION
1. Typical lamellar structure is formed during milling which retains after

compaction in all examined powders (Cu, CuAI3.5, Cu+3wt.% Al z0 3) .
2. The microhardness measurements indicated remarkable strengthening

effects in investigated systems.
540
Cu
(a) (d)
(b) (e)
CuA13,5
(c) (f)
Figure 5. Particles of examined materials after loh (a.b,c) and 2Gh (d.e.f) milling time
541
Figure 6. Microstructur e of mechanically alloyed Cu+3wt.% Alz03 particle (a) and compact (b),
milling time 3h.
350
Cu
300
......
.......... -

250 '
>
::r:
=
"'0
vi 200
en
<l.l
"
". Cu + 3%AI
ZO
)
I-<
150 e" "
-=
CIl
"
0 ""
""
I-<
(.)
~ 100 "e
""
50
0
0 5 10 15 20 25
Milling tim e, h
Figure 7. Microhardness of compacts vs milling time
3. Th e pure Cu and prealloyed CuAI3.5 powder show 5 times and

Cu+3wt. % Al 20J powder mixture 4 times great er microha rdness values
respectively, in comparison to untreated copper powder.
4. Th e strengthening effects in Cu compacts are due to grain refinement

and high dislocation densities. The hardn ess increasing in the early stage of
milling (CuA13.5 powder and Cu+3wt.% AlPJ powder mixture) is
additionally influenced by the presence of Al 20 J dispersed part icles.
542
5. The Al 20J dispersoids formed by internal oxidation (CuAl3.5) yield
much more noticeable strengthening effects than Al 20 J dispersed particles
incorporated in a metal matrix by mechanical alloying.
REFERENCES
I. R.S.Benn, P.K.Mirchandani, Dispersion Strengthening by Mechanical Alloying in: New
Materials by Mechanical Alloying, Techniques Oberursel, DGM e. V., (1989).
2. V. Rajkovic , N. Ilic, M. Mitkov, The Copper Matrix Strengthening by Internal Oxidation of AI-
prealloyed Powders, in: 1998 Powder Metallurgy World Congress exhibition, Granada, Spain,
October 18-22, to be published (1998).
3. G. Ziegler, Structural and Morphological Investigation of Ceramic Powders and Compacts,
Powder Metallurgy International, 10:70(1978).
4. D. Maurice, T. H . Courtney, Modeling of Mechanical Alloying: Part III Applications of
Computational Programs, Metallurgical and Materials Transaction A , 26A: 2437(1995).
5. A. Upadhyaya, G. S. Upadhyaya, Sintering of Copper-Alumina Composites through Blending
and Mechanical Alloying Powder Metallurgy Routes, Materials & Disgn, 16 (1) : 41 (1995).
543
HARDENING MECHANISMS IN SOME PREALLOYED PM TREATED
COPPER POWDERS
D.Bozic, V.Rajkovic, M. Mitkov
Institute of Nuclear Sciences "Vinca", Materials Science Laboratory

P.O.Box 522, 11001 Belgrade, Yugoslavia
ABSTRACT
The modalities of strengthening mechanisms of a highly conductive copper

matrix have been presented. Dispersoid, precipitation as well as combination of both
hardening mechanisms have been discussed. The prealloyed copper powders Cu-
1,5wt%Ti, Cu-1,5wt%Ti-2,8wt%TiSiz and Cu-1,9wt%Al z0 3 have been used as a
starting materials. The powders have been hot pressed up to theoretical density and
subsequently heat treated (Cu-Ti and Cu-Ti-Tisi, systems). The hardness of the
samples has been measured at room and elevated temperatures up to 700C. The
hardening effects of the copper matrix depend on type and particle sizes of the
precipitates and dispersoids , as well as their stability at elevated temperatures.
INTRODUCTION
Copper is widely used because it has the advantages of high electrical and
thermal conductivities, outstanding corrosion resistance , and ease of production. In
pure form, however, it shows relatively low yield strength and fatigue resistance . The
production of dispersion , precipitation or multiple hardened copper alloys may offer
higher mechanical properties, while retaining good electrical and thermal
characteristics.
Precipitation and multiple hardened copper alloys may be processed both by
ingot and powder metallurgy, while dispersion hardened alloys include only powder
metallurgy route. The commercial use in electrotechnics has been achieved
precipitation and dispersion hardened copper alloys obtained by ingot metallurgy,
while precipitation hardened alloys obtained by PM and multiple hardened copper
alloys obtained both by ingot and PM processing have been still developing':".
Advanc ed Science and Technology of Sintering, ed ited by Stojanov ic et al.

The main problems associated with development of sintered precipitation and
multiple hardened copper alloys comprise alloying elements choosing, precipitation
and dispersoids formation , as well as oxygen contamination of powders'.
The aim of the present work includes the hardening of a highly conductive
copper matrix by using PM techniques, appropriate choice of alloying elements for
dispersoids formation as well as analysis of their single or combined effects on the
hardness of obtained material at room and elevated temperatures.
EXPERIMENTAL
The Cu-l,Swt%Ti and Cu-l,Swt% Ti-2,8wt%TiSi2 have been produced by argon

atomization process at l400C and 30 bar. The Cu-l,9wt%AI20 3 has been obtained
during milling (planetary ball mill) of pre alloyed and atomized Cu-lwt%AI powder.
The milling process has been performed in air for Sh, in order to enable in situ Al
oxidation e.g. formation of fine Al20 3 dispersed particles. The obtained powder has
been reduced in H 2 at 400C, lh with the aim to eliminate copper oxides.
Optical microscopy analysis is applied for the microstructure characterization.
The powders were hot pressed in Ar, at 950C, 4h and 30 MPa. The Cu-
l,Swt% Ti and Cu-l,Swt% Ti-2,8wt%TiSi2 compacts have been solution treated at
900C, 2h in H2, water quenched and aged in inert atmosphere from 300C to 700C,
for 60 min.
The hardness (HV, 3g) of the samples before and after solution treatment, as
well as mechanically alloyed and hot pressed samples, has been measured at room
and elevated temperatures (20-700C).
Optical microscopy was applied for microstructure characterization of the
compact material.
The microstructure of the atomized, precipitation hardened Cu-Ti and multiple

hardened Cu-Ti-TiSi2, alloys have been presented in Fig.la and lb. Both
microstructures are characterized by a cluster free homogeneous distribution of the
alloying elements . The secondary Cu4Ti phase particles which are characteristic for a
cast Cu-Ti alloys (produced by ingot metallurgy"), have not been observed in the
microstructure of a rapidly solidified powders. The larger TiSi2 particles can be
observed in the microstructure of multiple hardened copper alloy (Fig.lb). The TiSi2
particle presence is a consequence of their formation during the atomization process.
A dendrite morphology predominates in the microstructure, although in some
particle areas a cellular type structure developed . Supersaturated titanium rich solid
solution occupies the areas between the primary and secondary dendritic arms',
The microstructure of dispersion hardened Cu-AI20 3 alloy, after mechanical
alloying for Sh, is presented in Fig.lc. The obtained structure is typical for
mechanically alloyed materials' with lamellae presenting starting powder particles
plastically deformed.
Figure 2a-c show the microstructures of the hot pressed, full densified, copper
alloys compacts. The previous particle boundaries (PPB) can be observed in the Cu-
Ti and Cu-Ti-TiSi2 samples. The PPB presence (containing mainly copper and
titanium oxides" characterizes the hot pressed microstructures, especially in the case
546
Figure 1. The microstructure of gas atomized powder particles (a) Cu-l,5wt%Ti, (b) Cu-l ,5wt%Ti-
2,8wt%TiSiz and (c) the microstructure of mechanicaIly aIloyed Cu-I ,9wt% AIP3 powder particle.
of lower pressures applying (our case). This effect was not observed in the
mechanically alloyed powder compacts due to extensive developed lamelar
structure.
Figure 2. The microstructure of hot pressed samples: (a) Cu-l,5wt%Ti; (b) Cu-l,5wt%Ti-
2,8wt%TiSiz; (c) Cu-l,9wt%AlP3'
The secondary Cu4Ti phase particles have been observed in some

microstructure parts of dispersion and multiple hardened copper alloys compacts
(Fig.2a and b), which formation was not surpressed during quenching from the
homogeneous solution field due to relatively low cooling rate. Besides, the multiple
hardened copper alloy shows the presence of larger TiSiz dispersoids (Fig.2b) formed
during powder production (rapid solidification process, as shown in Fig.lb). The
microstructure of Cu-l,9wt%Alz0 3 (Fig.2c) retains the characteristics of the
microstructure of mechanically alloyed powder.
The hardness vs temperature relationship for all investigated, hot pressed
copper alloys is given in Fig.3.
547
The hardness of Cu-Ti and Cu-Ti-Tisi, (curves 1 and 2, Fig.3) increases from
room temperature to SOOC, and than decreases. The hardness increase with
temperature is due to the modular structure formation and coherent precipitation of
Cu4Ti cm) (responsible for Cu-Ti alloys hardening effects"), The Cu 4Ti Cm) phase
precipitates from super saturated Cu-Ti solid solutions", The decrease of the
hardness in the investigated alloys, after heating at SOOC, appears as a consequence
of precipitate coarsening and eventually the discontinuous precipitation of secondary
Cu4Ti phase? .
The Cu-l,9wt%Alz03 alloy generally retains the starting hardness value up to
SOOC (Fig.3, curve 3). The heating above SOOC results in hardness decreasing.
Having in mind that hardening effects in this type of alloys are due to
dislocations movement impediment and formation of dislocation loops as well as fine
grains microstructure stabilization", the hardness increasing with increasing
temperature is not expected. The steady hardness values up to SOOC, indicate
microstructure characteristics stability with elevating temperature. The hardness
decreasing after heating above SOOC is a consequence of intensified grain growth
processes . The Al z0 3 particles located at grain boundaries are so far ineffective for
furth er grain boundaries immobilization.
250
225
M
>
I
200
rn 175
rn Q)
c
"0
L-
150
eo
I 125
100
75 pure cu
'"
50 -h............................-H'--r--.---.---.---.---.---.---.---.---.----!
o 20 40 60 80 300 400 500 600 700 800
Ternperature.vc
Figure 3. Hardness vs temperature dependence of hot pressed copper alloys:l - Cu-l,5wt% Ti; 2-Cu-
l ,5wt%Ti-2,8wt%TiSi2; 3-Cul,9wt%AI 20J
It is worth mentioning that hardness decreasing with temperature is less

pronounced as compared to precipitation as well as multiple hardened alloy
compacts.
The hardness measurements have shown (Fig.3) remarkable hardening effects
of the copper matrix in all investigated alloys. For example , the Cu-Ti alloy (curve 1,
Fig.3) shows matrix hardening greater 2,7 times with only 1,Swt% of alloying
element addition (the hardness of hot pressed sample of pure atomized copper
548
powder shows HY3",70). Nevertheless, the more severe hardness loss occurred in this
alloy after heating above 500C, as compared to Cu-Ti-TtSi, and Cu-Alz03 alloy.
Besides, the hardening effects completely disappear at 700C.
Although the absolute highest hardness value is obtained for Cu-Ti-TrSi, alloy
(HY 3= 220, curve 2), one could expect more pronounced effects due to alloying
element and dispersoids content (4,3wt% of Ti+TrSi, effected only 3 times higher
copper matrix hardness). The higher expected hardening effect assumably was not
pronounced due to the presence of large TiSi z particles. But, it should be pointed out
that hardness decreasing in multiple hardened alloy is less pronounced as compared
to precipitation hardened alloy, just because of the TtSi, dispersoids presence.
The typical behavior of dispersion hardened alloy is presented by curve 3 in
Fig.3 z. The Cu-Al z0 3 alloy shows at 700C about 2 times higher hardness value as
compared to pure copper matrix, as well as higher hardness as compared to
precipitation and multiple hardened (Cu-Ti and Cu-Ti-Tixi.) alloys (curves 1 and 2,
Fig.3). Although the dispersoids content in Cu-Al z0 3 alloy (1,9% Al z0 3) is lower
then the TrSi, dispersoids content in multiple hardened alloy (2,8% TiSi z), the
hardening effects are more pronounced as a consequence of a presence of much
smaller sizes of dispersed particles.
CONCLUSION
1. The pr ealloyed Cu-I wt% Al as well as Cu-I ,Swt% Ti and Cu-l ,Swt% Ti-
2,8wt % TtSi , alloy powders have been produced by nitrogen atomization
process. The mechanical alloying has been applied sub sequently to Cu-
lwt%AI
2. Hot pressing was used as a consolidation method in order to obtain fully
dense alloy powder compacts.
3. The hardness of precipitation hardened Cu-Ti and multiple hardened Cu-Ti-
TiSi z alloys increases with incr eas ing temperature up to 500C and then
decreases. The mechanically alloy ed Cu-Al z0 3 system shows stable hardness
values up to 500C, and hardness decr easing from 500 to 700C.
4. The ha rdening effects of the copper matrix depend on type and sizes of
precipitate dispersoid particles, as well as their stability at elevated
temperatures.
REFERENCE
I. W.Drei zler, F.Aldinger and H.E.Exner ,Preparation and Properties of PIM Copper-Beryllium
Alloys, in: Modem Developments in Powder Metallurgy. Eds . H.H.Hausner and W.E.Smith ,
Vol.7, MPIF, Princeton, N.J.: 505 (1974).
2. V.A.Nadkarni, E.J .Synk, Dispersion-Strengthened Copper, in: Metals Handbook, 9th Edition,
U.7. Powder Metallurgy, Metal s Park, Ohio , 44073 43 (1984).
3. N.J.Grant, A.Lee and M.Lon , Multiple Hard ening Mechanisms for High Strength, High
Temperature, High Conductivity Copp er Base Alloys, in: High Conductivity Copper and
Aluminum Al1oys, The Metallurgical Society of AIME, California: 103 (1984).
4. D.Bozie, Z.Vujovie, SiTadic, M.Mitkov, Precipitation Hardened Copper Alloys, in: Copper slloy
strengthenedpowders, Inst itute of Nuclear Sciences "Vinca" , Belgrade (1995).
5. V.Rajkovic. Ndlic , M.Mitkov, The Copper Matrix Strengthening by Internal Oxidation of Al-
Pre alloyed Powders, in: 1998 Powder Metallurgy World Congress and Exhibition, Granada,
Spain, October 18-22, to be published (1998).
549
6. A.Datta, W.A.Soffa, The Structure and Properties of Age Hardened Cu-Ti Alloys, Acta Met.,
24:987 (1976).
7. P.Kratchovil, M.Saxlova, J.Pesicka, The Age Hardening in Copper with Low Concetration of
Titanium, in: Proceedings ofthe jlh International Conference, Aachen: 687 (1979).
8. R.C.Benn and P.K.Mimchandani, Dispersion Strengthening by Mechanical Alloying , New
Materials by Mechanical Alloying Techniques, Oberursel, DMG: 19 (1989).
550
RECRYSTALLIZAnON OF COLD-PRESSED ALUMINIUM POWDER
S.Tadic, S.Zec
Institute of Nuclear Sciences, Vinca, Belgrade, P.Box 522, Yugoslavia
INTRODUCTION
Second phase particles in metal matrix may have a considerable influence on

deformation and recrystallization behaviour. The recrystallization of metals
containing a dispersion of hard particles may be accelerated or retarded, depending
primary on the diameter of particles 1-4. However, the most of related studies were
concentrated on the alloys produced by ingot metallurgy, where the second phase
particles precipitate through heat treatment processes. Such processes bear some
limitations, mainly through solubility, volume fraction and diameter of particles. On
the contrary, powder metallurgy techniques of consolidation do not depend on such
limitations and enable admixing various particles in a metal matrix.
This paper deals with the influence of mechanically admixed hard particles on the
recrystallization behaviour of a metal matrix. The material was consolidated
aluminium powder containing dispersion of alumina particles. This system was chosen
due to its importance and attention that have reached during the last decade. On the
other side, the recrystallization of aluminium alloys have been examined in details 5-10
EXPERIMENTAL
The material was produced in a manner which is usual in powder metallurgy

practice. Aluminium powder of commercial purity (CP-AI) was mechanically
admixed with 1 wt. % of alumina particles in a glass jar. Two separate grades of
alumina were used : larger than 10!!m and smaller than Ium, (nominally 0,7!!m).
Hereafter, these two grades of alumina are specified as large (LP) and small (SP)
particles, respectively. Powder mixtures were subjected to low-pressure vacuum hot
pressing (450 C /2 h / 20 MPa) followed by slow cooling. Finally, specimens 25mm
in diameter and 25mm in height were cold extruded to rods 8mm in diameter (the
extrusion ratio being 1:10, e.g. E=2.5). These rods were cut into discs which later
were ground on fine grained emery paper. The recrystallization experiments were
conducted by annealing at 250, 300 and 350C in duration from 15 min to 4 h. The
atmosphere in the furnace was the air and the temperature remained constant
Advanced Science and Technology of Sintering , edited by Stoja novic et al.

Kluwer Academ ic/Plenum Publishers, New York, 1999 55l
within 5C. The annealing temperatures were selected in the range of typical values
for aluminium alloys. To avoid the influence of the surface effects, annealed
specimens were reduced in thickness by etching for 60 s in NaOH before they were
subjected to texture measurements.
The texture of the specimens was determined by X-ray diffraction using
SIEMENS difractometer. Three pole-figures (200,220 and 111) were measured in
the back-reflection technique 11 using Cu(K a ) radiation. Because of axial sample
symmetry, only the diameter of pole-figures were scanned in the azimuthal angle
from -75 to +75.The background intensities were measured two degrees apart the
peak.
The texture of the axially symmetric sample is a fibre texture which may be
represented by inverse pole figure of the axis direction. In this work, the inverse
pole figures were expressed through series expansion method 12. With three available
incomplete pole-figures, inverse pole-figures can be calculated up to 1max=22, even
only. An odd values were calculated applying ghost-correction mathematical
procedure'v". This procedure basically depends on fitting the experimental pole-
figures with Gaussian curve and refines more quantitative texture data trough
volume fraction and half-spread angle of particular <hkl> maximums. However, in
this work, the half-spread angle was not the variable , but was assumed to be
constant value of 12.
RESULTS
After the cold extrusion , aluminium specimen with small particles have the
texture shown by the inverse pole-figure in Fig.l. Apparently, the texture consists of
a single, very strong <111> fiber. Volume fraction of <111> fiber has been
calculated to be 80% . The rest are randomly distributed in Euler space and, for the
sake of simplicity, will be hereafter designated as "random" texture. (N.B. - volume
fraction of random texture represent the difference between particular <hkl> fibers
and 100%.) Specimens of CP-Al and Al containing large particles have essentially
the same texture. However, volume fractions of <111> fiber in these specimens were
somewhat higher, both roughly 87%.
Texture of the Al samples with small particles isochronaly annealed for 1 h at
250,300 and 350C are shown in Figs.2-4. It is seen that texture contains <111> and
<100> fibers with random component. It should be noted that the specimen
annealed at 350 C contains only <100> fiber and some random component. Such
texture represents fully recrystallized material while those recrystallized at lower
temperatures (Figs. 2 and 3) exhibit transition mode, e.g. partially recrystallized
tamper.
The volume fractions of <111>, <100> and random, calculated by Gaussian
integration over Euler space are shown in Fig. 5. It is evident that <100> and
random component continually grow up consuming the heavily deformed <111>
grains. However, the growth of randomly oriented grains is several times lower than
the growth of <100> fiber.
Table 1 collects the influence of annealing temperature, time and particle size
on the volume fractions of <100> fiber and random. In order to evaluate results
more clearly, some of data are processed on diagrams in Figs. 6 and 7.
Figure 6(a,b) shows the influence of particle size on volume fractions of <100>
and random component during annealing at 250C. It may be seen that small
particles significantly inhibit the growth of <100> at prolonged periods of annealing.
However, it seems that alumina particles do not affect the random component. On
552
9.5 8.6
\
Fig.l Inver se pole-figure (I PF) of cold- Fig.2. IP F of Al + al umina annealed at 250C
ext rude d CP-Al + 1 wt.% alumina. /1 hour.
6.3
5.1
Fig .3. IPF of A l + alumi na annealed at 300C / FigA. IPF of A l + al umina nnealed at
1 ho ur. 300C /1 hou r.
1.0 ,....-- - - - - - - - - - - - - - - - - - - ---,
c
.S
....u 0.8
ell
.
<t:1
Q) 0.6 .
a
::l
'
~ 0.4 .
R
.
0.2
<100>
o 100 200 300 400
Temperature, ("C)
Fig.5 .Th e influence of annealing te mperature on volume
fractions of <100>, <111> fibe rs and ra ndo m (R) .
553
the other side, the influence of temperature on recrystallization kinetics is shown on
Fig. 7(a,b). Temperature, as it was expected, strongly affects the kinetic of
recrystallization. Despite, lower temperatures (250 and 300C), have more
pronounced effect on <100> growth than on random. Also, lower curves on Fig. 7b
obey typical sequences of incubation time and rapid growth. The same, but even
more pronounced behaviour exhibit the curves on Fig. 6a.
DISCUSSION
It is a general observation 14 that the presence of hard particles in a metallic

matrix may affect the texture changes both during deformation and during
recrystallization. It appears, however, that small volume fractions of particles have
little effect on the deformation texture 4,8,9 and the present results support these
findings. However, the effect of particles is much more pronounced during
recrystallization annealing.
The components of the recrystallization textures have been classified as <100>,
random and retained deformation fiber <111>. The cube orientation is
characteristic of pure aluminium, whereas combination of cube and other
orientations is observed in aluminium containing alloying elements either in solid
solution or as intermetallic precipitates 4. In the material investigated, e.g.
commercial purity aluminium , the amount of elements in solute solutions is small
and, accordingly, a relatively large <100> component should be expected. However,
the data in Table 1 show that cubic fiber is always accompanied with random
component. The random component may be attributed to the presence of the
alumina particles. In the alumina-free specimens (CP-AL), it is probable that
residual oxides and precipitates from solid solution (perhaps iron and silicon) effect
the recrystallization texture15.
In order for a recrystallized grain to form at a particle, two criteria should be
fulfilled: (i) a local region of lattice rotation must be formed during the cold
deformation and, (ii) the nucleus formed in a such zone must be able to grow into
the matrix. The first criterion is satisfied for particles of a diameter greater than
0.1IlmI6. But, the onset of nucleation is controlled by second growth criterion.
Experiments have shown that the critical particles diameter in this case is in the
range of 1-5Ilm5.16. However, in alloy with the low volume fraction of particles,
nucleation sites at particles are supplemented with "normal" matrix sites. The final
recrystallization texture will reflect the competition in nucleation and growth rates
of these two sites. It seems that curves in Fig. 6(a) might be explained in spite of
these findings. In the beginning of recrystallization, alumina particles have no
significant influence on <100> growth. But, at prolonged annealingm times, small
alumina particles (- 0.7Ilm) substantially retard the growth of <100> fiber. The large
particles (> 101lm) are perhaps "oversized" and behave relatively non-effective in
the metal matrix. On the other side, random texture component is not affected by
the presence of neither small nor large alumina particles .
The recrystallization textures are also influenced by the temperature of annealing.
Fig.7. indicates that higher temperatures favours the growth of <100> fiber much
more then the random component. This can be explained by the lower effectiveness
of particles for nucleation at higher temperatures 4,17. The smaller number of
nucleation sites and the high growth rate of <100> result in a significant volume
fraction of cube oriented grains.
554
Table 1 An overall data - volume fractions of <100> and random components
(left and right columns , respectively).
/0
e
'()
'/J 0/~ 15 I 30 60 120 24
" (0 IJ I
Al 5 16 7 25 10 26 40 27 70 29
25 0 AI+S 2 9 5 17 9 21 32 29 40 35
AI+L 7 14 7 17 14 25 42 30 67 32
Al 14 14 i 24 15 46 22 72 25
30 o AI+S 10 14 I 21 17 30 20 61 30
AI+L 16 15 20 13 21 30 67 22
Al 54 15 70 22 75 25
3 50 AI+S 49 19 60 27 70 30
AI+L 56 17 72 23 80 21
100
..-.. (a) 100
0>R. 80 (b)
'-'
CP A I " 80
'"
~
#.
I:l 60 v;
.9
..... AI +LP
c 60
.2
.------"
u
til 40 t)
AJ+ SP
J:: ,g 40
CP A I ::::::"""",1_ ......-;::
"0 / " AI+SM "0
>
20
> 20 :~:~: AI+LP
I==--I~
10 100 10 100
Ann ealing time, (min) Annealing time, (min)
Fig. 6 Volume fractions of <100> (a), and random (b), of aluminium (CP-Al) and aluminium
containing small (SP) and large particles (LP) .
100 40
(a ) (b) "
tv;
~
~ 80
/ 3"~->:/~C
350C_ _
.
30
c
v;
.2 60 ./ . c
.g 20 /" 300C
t) u
~
~
<l:: 40 3005-/ / ..:;
~
:7"
"0
> 20 .....-------. ~50 C "0
> 10
.-.--.
10 100 10 100
Ann ealing time, (min) Annealing time, (min)
Fig. 7.Kinetics of <100> fractions (a), and random (b) , during the annealing at three temperatures.
555
Acknowledgements- This work was financialy supported by the Serbian Ministry for Science and
Technology . The authors are grateful to M.Mitkov, Head of the research project, D.Bozic and
M.Jovanovic for valuable suggestions and discussions.
REFERENCES
1) N.Hansen, Mem.Sci.Revue MetalL, 72, (1975), p.189.

2) FJ.Humphreys, Metals Sci., 13, (1979), p.136.
3) N.Hansen, B.Bay, Acta. MetalL, 29, (1981), p.65.
4) J.Jensen , N.Hansen, F.J.Humphreys, ICOTOM 8(Ed. by. J.S.Kaliend and G.Gottstain),
Metall . Soc., (1988), p.431.
5) E.Nes, Proc. otI" Riso, (Ed . by N.Hansen , A.R.Jones and T.Leffers) , Riso, (1980), p.85.
6) R.Rixen, R.Musick, H.Goker and K.Lucke, ZMetallk., 66, (1975), p.16.
7) J.C.Blade, P.L.Morris, ICOTOM 4, (Ed . by G.J.Davis et al.) Cambridge , (1975), p.171.
8) K.Ito, R.Musick and K.Lucke, Acta. Metall., 31, (1983), p.2137.
9) K.Ito, K.Lucke and R.Rixen, ZMetallk., 67, (1976), p.338.
10) D.H.Rogers and W.T.Roberts, ZMetallk., 65, (1974), p.100.
11) C.S.Barett and T.B.Massalski, Structure of Metals, McGraw-Hill, London , (1966).
12) HJ.Bunge, Texture Analysis in Material Science, Butterworths, London, (1982).
13) K.Lucke, J.Pospiech, K.H.Virnich and J.Jura , Acta. Metall., 29, (1981), p.167.
14) K.Lucke, ICOTOM7, (Ed . by C.M.Brackman et al.) Noordwijkerhout, (1984), p.195.
15) R.D .Doherty, Progr. in Ma ter. Sci., 42, (1997), p.39.
16) FJ.Humphreys, Acta. MetalL, 27, (1979), p.1801.
17) A.L.Dones, E.Nes, Mat. Sci. Tech., 2, (1986), p.8.
556
GENERATION OF DISLOCATIONS DURING COLD SINTERING
OF IRON POWDER
Zoran M. Jankovic,' and Bojan A. Marinkovie
I Institute of Technical Science of the Serbian Academy of Sciences and Arts

2 Center for Multidisciplinary Studies University of Belgrade,
Joint Laboratory for Advanced Materials of SASA
INTRODUCTION
Investigations of the consolidation of metallic and alloy powders performed up to now

have suggested the existence of several consolidation stages, which are dominated by
different mechanismsf" , Investigations of structural changes as a function of the pressing
pressure have indicated different directions of structural changes (polymorphic
transformation, evolution of a defect structure, amorphization) as a function of the applied
pressure, pressing method , characteristics of the disperse system, i.e. starting powderf'".
Establishment of a interdependence between the compact density and pressing pressure is of
great importance, both from the phenomenological viewpoint and the fact that these
dependencies are a direct consequence of changes at the material structure level. In
literature, a great number of phenomenological pressing equations have been defined 2.J1. 12.
However, they are generally limited to a certain powder or consolidation stage.
Characteristics of the starting powder (mean grain size and shape, the presence of an oxide
film) have a significant influence on the consolidation course and structural changes .
In this paper the consolidation of iron powder was investigated in the pressure range
of 100-1000 MPa, using pressing equations, with the purpose of obtaining information on
the course of the consolidation process, especially from the viewpoint of the evolution of
structural defects during the consolidation process . Methods of X-ray powder diffraction
(XRPD) and differential scanning calorimetry (DSC) were used for these investigations.
EXPERIMENTAL
An iron powder (Fe 98.5%; C 0.1%; 02 0.1%; Si 0.2%; Mn 0.5%), previously heated
in hydrogen at 650C, with a mean agglomerate size of230 J.1IIl, was pressed in the pressure
range of 100-1000 MPa. Mechanically stable compacts with a diameter of 10 mm were
obtained. Their density was measured, and it is given in tab. I.
Advanced Science and Technology o} Sinteri ng, edited by Stojano vic et at.
Table 1. Experimental and relative density of iron compacts
p(g/cm3) pressure p [MPaJ

100 200 300 400 500 600 700 800 900 1000
pe 4.19 5.04 5.56 5.84 6.15 6.37 6.53 6.67 6.78 7.04
pr 0.53 0.64 0.71 0.74 0.78 0.81 0.83 0.85 0.86 0.89
Evolution of the iron defect structure (mean crystallite size and dislocation density)
was investigated using the X-ray powder diffraction method on a Philips PW 1820
diffractomet er with CuK,. monochromatic radiation.
Samples obtained were also investigated using differential scanning calorimetry
(Shimadzu DSC-50), with the purpose of determining the hidden deformation energy 13.
A mathemat ical-physical analysis of experimental and relative densities of compacts

(tab. I) as parameters of the change of the disperse system on a macro level, as a function of
the pressing pressure , has given significant informat ion on the consolidation of iron
powder.
Analysis of the logarithmic relation between the relative compact density and pressing
pressure (Fig. 1)
Pr = k*p B (1)
has indicated the existence of two different consolidation stages of iron powder. The
boundary between the two stages is at about 290 MPa. As parameter B can be defined as the
compacting module , whose value is 0.259 for the first and 0.189 for the second phase,
respectively, it can be concluded that densification of iron powder is most intensive during
-010
lnp,=lnk+Blnp
- 0 15
-0 20
-025 II phase
-0 30
8 = 0.193
-0 35
...
c,
-0 40
.
-0 45 I phase
-0 50 8 = 0.259
-0.55
// /
-0 60
-065
/
4.6 4 .8 50 5.2 5 4 56 5.8 6.0 6.2 6A 6.6 6.8 7.0
In p
Figure 1. The dependence of the relativedensityon the pressingpressure
558
the first consolidation stage. Thus, densification of iron powder took place in accordance
with the general pressing principles": Densification was most intensive at the beginning of
each stage, while it was reduced and had a lower value at the end of both stages.
However, it is well known that both stages of the consolidation of metallic powder,
their alloys or ceramic powders can overlap' . The boundary point does not mark the
beginning of the activation of the following consolidation mechanism (in this case plastic
flow), but the pressure at which the following consolidation mechanism starts to have a
dominant influence during consolidation of a disperse system. Using the Shapiro-Kolhoff-
Konopicky equation (2), (Fig. 2):
In (l/l-p,) = K *P+A (2)
2.4
Kolthoff-Shapiro-Konopicky
22
20
II phas e
k=0 .00136
v{
A= 0.82425
/
1.8
~ 16
-
..-I
-e--'
:
1.4
12
I phase
10
k=000235
A =0 .53426
0.8
0 200 400 600 800 1000
p[MPa]
Figure 2. Diagram of the dependence of the relative density on the pressing pressure
it can also be established that the consolidation process of iron powder in the investigated
range took place in two stages (different consolidation mechanisms), with a boundary point
at about 300 MPa. The Shapiro-Kolthoff-Konopicky equation has two parameters , K and A.
K has physical meaning in the second consolidation stage. This parameter is inversely
proportional to the relation (3) :
K = 1 / 3 cry (3)
where cry is the boundary of plastic flow of the material.

Parameters K and A are 0.0024 and 0.534 for the first stage, and 0.0014 and 0.824
for the second stage of iron consolidation, respectively. The boundary of plastic flow of the
material can be determined using the value for K in the second stage. It is 245 MPa, which
is in agreement with the value of the boundary of plastic flow of iron 15. It can be concluded
that plastic flow started at 245 MPa, but only after 300 MPa this mechanism became
dominant during the consolidation of iron powder.
In the investigated pressure range (l00-1000 MPa) iron powder consolidation
occurred in the first stage due to processes of particle rearrangement and better packing
559
1400
1200
1000
32
s: 800
0
600
400
I
o 200 400 600 dOO 100(1
p[MPa]
Figure 3. The dependence of the crystallite size on the pressing pressure
(filling in large pores), while the second stage is characterized by plastic flow of the
material. These processes are directly connected to changes in the material structure. The
changes which occurred on the defect structure level were investigated using X-ray powder
diffractometry, by analyzing the diffraction line [110]. It was possible to determine
parameters of the defect structure of iron (mean crystallite size (D) and dislocation density
(Po)) as a function of the pressing pressure based on the broadening of this diffraction line
(Figs. 3 and 4).
18
16
14
Pd=p dO+Ae(p/l)
- 12
~
E 10
~
0
~
8
a
6

~
u
Q.
2
i
.
----
0 200 400 600 800 1000

p[MPa]
Figure 4. The dependence of the dislocation density on the pressing pressure
560
It is well known that the mean crystallite size decreases and the dislocation density
increases under the influence of pressure 14, 16. Analysis of data obtained by X-ray powder
diffractometry and presented in Figs. 4 and 5, shows that changes of parameters of the
DSC
mWr- ..-,
30 .
Peak 549-27C
Onse~ 396.78C
Endse~603.02C
20.
Hea~ 9 .88J
0 .31kJ/g
10.0 9 .90J
O .31kJ/g
73 . 53callg
O O(
0 .00 20 0 .00 400 .00 600 .00

Temp[Cl
Figure 5. The characteristic peak obtained using the DSC method on cold sintered iron powder (p=500 MPa).
defect structure have different trends in different consolidation stages. It is obvious that
during particle slipping and rearranging (the first consolidation stage) contact surfaces
between powder particles form I , which enable the transfer of mechanical energy and
formation of a block-mosaic structure, indicating intensive dislocation generation and the
formation of dislocation networks on crystallite boundaries 17. After plastic flow starts at
245 MPa, and especially after 480 MPa, the reduction of crystallite size (increase of
dislocation density) is not so intensive. This indicates that changes of the defect structure
during the second consolidation stage (plastic material flow) are connected with changes of
the dislocation structure. This change means more intensive formation of networks on
crystallite boundaries (with an increase of the disorientation angle), reduction of the number
offree dislocations in the crystallite volume. This process is very characteristic for metals (a
very small amount of energy is needed to set dislocations in motion), due to the character of
chemical bonds in them".
561
1.0
0.8
0.6

~
~ 04
I
<I
02
0.0

0 200 400 600 800 1000
p[MPa]
Figure 6. diagram of the dependence of enthalpy on the pressing pressure
Determination of the hidden energy of compact deformation':', using differential scanning

calorimetry, enables determination of the change of the dislocation structure of iron
compacts as a function of the pressing pressure. As dislocations are unstable structural
defects (they have an influence on the increase of the free energy of the system), the
introduction of heat energy leads to their partial annihilation and polygonization in
dislocation walls. Dislocation annihilation and the formation of dislocation walls, leads to
structural recovery, which is accompanied by the reduction of the free energy of iron
samples (characteristic exothermic peaks), (Fig. 5). The change of the molar enthalpy of
1.0

0.8
- L1H + A *e-(pd-pdO)/t1
Y- 0 1
0.6

Q>
~ 0.4
I
<I
02
0.0
2 4 6 8 10 12 14 16 18
Figure 7. Diagram of the dependence of enthalpy on the dislocation density
562
iron compacts in dependence on the pressing pressure is given in Fig. 6. It can be noticed
that the released molar enthalpy decreases with the increase of the pressing pressure. This
characteristic of iron compacts is not the consequence of the reduction of dislocation
density, but the intensive formation of networks .
Dislocations in networks on boundary regions between crystallites are more difficult to
annihilate, as they require a higher energy than free dislocations in the crystallite volume.
Fig. 7 shows that the process of dislocation network formation takes place in both
consolidation stages, but it is more intensive during the first stage. Correlation of data
obtained by X-ray powder diffraction and differential scanning calorimetry enables
determination of the different character of changes of the defect structure of iron during the
consolidation process , in dependence on the consolidation stage. The first stage of iron
consolidation is accompanied by the formation of a block-mosaic structure, with an
intensive decrease of mean crystallite size. The tendency for crystallite reduction (i.e.
increase of dislocation density) continues in the second stage, though it is less intensive.
From the structural aspect, processes of dislocation network formation dominate in the
second stage (dislocations can be easily set into motion in the crystallite volume) in
boundary regions between crystallites .
CONCLUSION
The consolidation process of iron powder in the pressure range of 100-1000 MPa
took place in two stages, with a boundary between 290-480 MPa. Plastic flow started at
about 245 MPa, which indicated partial overlapping of consolidation mechanisms .
Changes on the level of the defect structure are directly responsible for the course of
iron powder consolidation
References
I. R.M. German, Powder Metallurgy Science, Metal Powder Industries Federation, Princeton, New Jersey ,
(1984) .
2. P.1.James, Powder Metallurgy Int, 4 (1972),193
3. G.V. Samsonov, Electronic Theory of Sintering, Naukova Dumka, Kiev (1974).
4. E.Y. Gutrnanas , Powder Metallurgy Int.,12 , 4 (1980) 178
5. I.P. Arsentyeva and M.M. Ristic, Proceedings of the VI World Round Table Conference on Sintering,
Herceg-Novi (Edited by G.C. Kuczynski , D.P . Uskokovic, H. Palmour Ill , M.M. Ristic) , Plenum Press,
New York (1987).
6. L.T.Kuhn,R.M. McMeeking and F.F. Lange, J.Am. Ceram . Soc.,73 (1991), 682
7. R. Agatonovic, D. Stefanovic, V. Petrovic and M.M . Ristic , 1. Mat. Sci. Lett., 9 (1990), 40
8. Yu.V. Milman , I.V. Gridneva, S.1. Chugunova, 1.1. Timofeyeva, A.A . Rogozinskaya, A.1. Bykov, M.M.
Ristic and R. Agatonovic, Sci . Sintering, 26, (1994), 307
9. I. Krstanovic, M.V. Nikolic, R.M. Novakovic, Z.Nikol ic, M.M. Zivkovic and M.M. Ristic, Sci . Sintering,
25, (1993),145
10. T. Yamanaka, T. Nagai and T. Tsuchi ya, Zeitsch fur Kristal!.,212 (1997), 401
II. M.B. Shtern and G.G. Serdyk, Phenomenological Theory of Powder Pressing, Naukova Dumka, Kiev
(1982)
12. W.D.Jones, Fundamental Principles of Powder Metallurgy, E. Arnold Pub!., London (1960)
13. V. Ostapenko and M.M. Ristic , Skritaya Energya Deformacii, Center for Multidisciplinary Studies
University of Belgrade (1987)
14. A.H. Birks and SA Muzaffer, Syposium of Powder Flow and Storage, University of Bradford, (1971)
15. 1.1. Timofeyeva, M.M. Ristic, V. Petrovic, I. Krstanovic and S.M. Radic, J. Serb . Chern. Soc. ,51 (1986) ,
175
16. R.W. Heckel , Trans . Mat. Soc. A.I.M.E., 221 (1961),671
17. E.Y. Gutrnanas , A. Rabinkin and M. Roitberg, Scripta Metal!., 13 (1979), II
18. M.M. Ristic, I. Krstanov ic, S.M. Radic and l.l. Timofeyeva, J. Serb . Chern. Soc., 55 (1990),29
563
INVESTIGATION OF MATHEMATICAL RELATIONS
BETWEEN TECHNOLOGICAL PARAMETERS AND
PROPERTIES OF COLD-SINTERED IRON
Milutin R. Duricic l and Zagorka Acimovic-Pavlovic2
tHigh Technical School , 31000 Uzice,

Trg Svetog Save 34, Yugoslavia
2Faculty of Technology and Metallurgy ,
Kamegijeva 4, 11000 Beograd, Yugoslavia
Abstract
Cold sintering draws great attention of researchers from different countries, primarily because the materials
with predetermined properties can be obtained by this technology. In this paper, the mathematical relations
between technological parameters and magnetic and electrical properties of cold-sintered iron under
pressures in range 4,5-12,5 Gpa, are investigated. The obtained relations are optimal, determined from the
set of several thousand of possible ones, and by means of them the optimal technology of cold sintering of
iron can be prognosed.
INTRODUCTION
Cold sintering is very prorrussmg process of obtaining materials with unique ,

predetermined properties, using high pressures produced by mechanical energy' . The role of
pure iron increases, so its cold consolidation is thoroughly investigated. Recent complex
investigations of iron powders are based on the pressure range from 4,5-12,5 Gpa2.3
Computers improved data processing enabling prognosing material properties and
significant speeding up and optimising of the technology. In this paper, special attention is
given to investigating mathematical relations between technological parameters and
properties of cold sintered iron, using least square method and modeling of the process by
various mathematical models .
EXPERIMENTAL WORK
For our investigations we used polidisperse iron powder of sponge-like microstructure,

produced by Hoganas, of purity 99,76%. Powder velocity (0,64 s/g) and density (2,410

kg/m') were determined by means of the Hal device, and so called "green hardness" (6,540
kg/m') was determined by the standard procedure under 412 Mpa.
By laser analyzer "Malvern 3600" it was determined that about 63% particles have
magnitude 54,8-1I8,4I!m, whereas only 5% particles were in range 3-I7,7I!m. In the device
UVP-1 3 we pressed prepared cylindrical samples of dimension 01 Ox10 mm, under pressure
400 Mpa and with pressing velocity 0,083 mm/s. By pressing in the hydraulic press of
maximal force 10 MN, under velocity 0,016 mm1s, cold-sintered samples were obtained
under various pressures in range 4,5-12,5 Gpa.
By hydrostatic scale, densities of obtained cold sintered samples - consolids (table 1)
were determined . Microhardness was determined on the microhardness measuring device
PMT-3, by impressing diamond pyramid, whose angle between sides on the top was 136, to
the previously grinded, polished and chemically etched surface by 5% nita!.
In order to investigate electrical and magnetic consolid properties versus pressure, we
determined thermo electro motor force (TEMF), electrical resistance Pel and magnetic
coercitive field iritensity He (table I) .
Measurement of differential TEMF between cold sintered samples and non-deformed Fe
and Constantan (Cs) sample, in 5 different points, was performed according to the method
developed earlier", with error less than 0,1% (table I).
Specific electric resistance of the consolid was determined by the four picks method .
Determining magnetic coercitive field intensity of the consolid was performed by the
standard method on the precise compact device "Forster-Koercimat" 1095 (table I) .
X-ray investigation was performed on the x-ray difractometer. Copper anticathode x-
rays and graphite monochromator were used. Dislocation density PD (table 1), which
significantly influences physical and mechanical metal properties in general, was also
determined .
Table 1. Measured properties of cold sintered iron for various pressures P (Gpa)
Hv TEMF pel Hc
P (GPa) (GPa) (mY) (m Ocm) (AIm)
4,5 7280 0,79 36,68 58 638 13,2
6,0 7280 0,98 22,89 43 625 10,0
6,5 7250 1,05 23,94 39 611 9,0
7,0 7310 1,09 22,68 31 623 8,8
8,0 7300 1,15 29,64 28 622 8,5
9,0 7380 1,26 25,54 16 533 8,7
10,0 7420 1,39 24,82 12 528 9,0
11,0 7520 1,50 29,25 8 553 10,5
12,5 7670 1,59 16,89 7 465 4,3
MA THEMATICAL PROCESSING AND

DISCUSSION OF THE OBTAINED RESULTS
In this paper, the mechanisms of the process have not been discussed in detail, because
several papers were published about that 2-5 . Instead, we stress our attention to the
investigation of the mathematical relations between structure, properties and technological
parameters of cold sintering of iron (fig. I-fig. 2).
Namely, the results obtained by measuring were processed by the Pc. We applied the
program for curve drawing Table Curve 2D for 2-dimensional drawing(fig. 3 - fig. 4).
566
Rank 1 Eqn 1085 y=a+bx2hlx+chlx!x Rank 1 Eqn 5138 y= a + br +c l xl>+dlo x l x 2 +ee-'
~=0.98683485 OF Adj ~=0.97893576 ~=0.99972016 OF Adj ~=0.99925375
FitStdErr=18.35 1679 Fstat=224.8743 FitStdErr=0 .0061202103 Fstat=3572.4333
a=6556.6673 b=1.7977572 a=-5.2490324 b=-O.17022617 c=7053.3074
c=2002.1466 d=-93 17.5993 e=-3601.2022
7700 1.71
/
7650 1.6
7600 1.5
7550 1.4
7500 1.3
7450 1.2
7400 1.1
7350 1
7300 0.9
7250 0.8 .
7200 . 0.7 ,--,-\1 - - ,
4 6 8 10 12 4 6 8 10 12
Figure 1. Density d (kg/rrr') in function on Figure 2. Microhardness Hv (Gpa) in function

pressure P (Gpa) , on pressure P (GPa).
3
Rank3 Eqn 4081 y=a + bx+ cx lnx +de' +exo,sln x Rank 3 Eqn 1025 y = a +bxlnx + cx
~=0.91193923 OF Adj ~=0 .87524724 ~=0.992021l6 OF Adj ~=0.98723386
FitStdErr= 1.8296579 Fstat=33.656331 FitStdErr= 1.8042635 Fstat=372 .99452
a=58487.82 b=-5546 1.13 I c=7914.0925 a=88.613789 b=-5.0558723
d=-0.00022778318 e=43 I 13.385 c=0.039987345
40'- - - - - - - - - - -
-.
70
60
35
50
30 40 \
~
30
25
20
20
10 '<, .
15'--_-,---_-,-_---,-_ _--'-' ol . . _~_

4 6 8 12 4 . 6 8 10 12
Figure 3. Thermo electro motor force (TEMF Figure 4. Electrical resistance P el (m Oem)
(mv) in function on pressure P (Gpa). in function on pressure P (GPa).
567
We selected the equation which satisfied particular relations test, according to the
minimal standard error Thus, the technology was optimized quickly. The program also
enabled fast establishing of the relations between particular technological parameters and
managing factors in order to optimize them.
CONCLUSION
Development of modem materials with predetermined properties cannot be imagined

without appropriate prognosing .
Today prognosis of the optimal technologies is made significantly easier by application
of computer technology.
In this paper, on the example of cold sintering of iron, it was shown how to select the
equation with minimal mid-square error from the set of more than 40.000 different equations
easily. In such a way, the processes of work and development can be significantly speeded up
in the wide circle of scientific problems.
REFERENCES
1. E.Y. Gutmans and A. Lanley, Cold sintering: a new consolidation process, in : Progress in Powder
Metallurgy - 1983, MPIF, Princeton (1984) .
2. R. Lj. Simeunovic, AM. Maricic, N.M . Susie, and B. Andelic, Kinetics of the thermal recovery of cold-
sintered iron powder, in: Science ofSintering, 28:125 (1996).
3. I.P. Arsentjeva, Basic Laws of the recrystallization process during sintering of pressed metal powders , in :
Science ofSintering, 28:91 (1996).
4. M .R. DuriCic, 1. Milutinovic, M. Sokic, M. Dragojlovic, a nd Z. Acimovic, The investigation of
influence of technological parameters on the properties of cold sintered iron (in Serbian), in :
TM *95-IV, Krusevac (1993) .
5. D .C . Stefanovic, M . Duricic, M. Dragojlovic, and M.M . Ristic, The investigation of cold sintering
mechanism of iron powder compact, in : Proceedings of the 12th AIRAPT and 27th EHPRG
International Conference, Paderbom (1989) .
6. M .R. Duricic, Influence ofTechnological Parameters on Structure and Properties ofCold Sintered Iron,
Ph .D. Thesis (in Serbian), CMS, Beograd (1988) .
7. M.R. Duricic, Dependence of structure and properties of cold-sintered Fe-powder on technological
parameters, in: TEHNIKA, 44 (1989).
8. M .R. Duricic, D .C. Stefanovic, V. Petrovic, and M. Dragojlovic, Influence of technological parameters
on the structure and properties of cold sintered iron, in: Proceedings of Tagung PM 89,
Drezden (1989) .
568
THERMAL RECOVERY OF COLD SINTERED
MECHANICALLY ACTIVATED POWDER
SYSTEM Cu70%Fe30%
R.Ll. Simeunovic,' B. Stojanovic,' and A.M. Maricic'
'Technical Faculty, Cacak

2Center for Multidisciplinary Studies, University of Belgrade,
RESUME
The Cu70%Fe30% powder mixture was ground in a high-power mill. Changes

occurred during grinding were monitored by the x-ray structural analysis . The
process of thermal recovery of the cold sintered mechanically activated mixture of
Cu70%Fe30% powders was analyzed by DSK method and the method of measuring
the electric resistivity in unisothermal and isothermal conditions. It was ascertained
that the recovery in the annealing process up to S20C developed exothermically.
Kinetic parameters were determined in the isothermal conditions by the method of
measuring the electric resistivity: activation energy and velocity constants of the
electronic state stabilization process on the basis of which are analyzed the change
occurrences of the electronic structure in the stabilization process of metastable state
of specimens obtained by cold sintering.
INTRODUCTION
The cold sintering procedure of metal powders represents in fact the

consolidation process of dispersive powder. During this process the plastic
deformation occurs resulting in generation of dislocations and in excitation of atoms
and exchange of electrons among the adjacent excited atoms':". The product
obtained in this way is in metastable state and as such is tending to get recovered i.e.
to pass into lower energetic state.
This paper deals with the study of the recovery process of the cold sintered
mechanically activated':' polycrystal powder of Cu70% Fe30% system.
Advanced Science and Technology of Sintering. edited by Stoj anov ic ct al

Kluw er Academi c/Plenum Publi shers. New York. 1999 . 569
EXPERIMENTAL WORK
The 99.9% pure copper and iron polycrystal powder, after mechanical mixing in
the mass ratio 7 : 3, is tribophysically activated in the vibration mill lasting 5, 15 and
60 minutes. So activated powder is pressed under load of 510 and 700 MPa at which
the maximal pressure is maintained for one minute.
The x-ray structural analysis of the non-activated and activated powder was
conducted on the diffractometer for powder PW 1710 with monochromatic CuKa
radiation.
The recovery process of the deformed structure of specimens obtained by cold
sintering was tested by DSC method and by measuring the changes of the electric
resistivity in non-isothermal and isothermal conditions by the four-point method.
These measurings were conducted in the hydrogen flow rate atmosphere.
It has been established by the x-ray structural analysis of the activated powder
(Fig. 1) that the increase in activation time causes reduction in intensity of the
characteristical peaks on the deffractogram. Based on this it can be assumed that
during the powder activation procedure the process of mechanical alloying is also
developed.
Fig. 2 shows DSC thermograms of specimens obtained by cold sintering of the
activated and unactivated powder. In both cases the process of recovery of the
deformed crystalline structure is developed exothermally being the result of
liberation of energy accumulated during the cold sintering. The same figure shows
that the longer time of powder activation the greater is the liberated energy leading
to a conclusion that tribophysical activation of dispersion substances results also in
generation of dislocations.
600
400
200 I I
Ol- - _ -- ---.- .. I' v'I~ o .. .. I
10 20 30 40 50 60
28
lEJ
600 500
500 5 min 15 60 min
400 min 300
200
400 300 100
300 200
' 1 0 40 160 : 100
'100
200
II 81
0 !
100 40 ~60 Jo 100
~
o 40 60 80 100
28
Fig. 1. X-ray grams of un activated (a) and activated (b) powder
570
For the purpose of studying the recovery as an electro nic process, measuring of
the change of electric resisti vity in nonisothermal and isothermal conditions was
conducted. Fig. 3 shows the dependence of th e specific electric resistivity on the
temperature of specimens obtained by cold sinte ring of unactivated powder und er
pres sure of 700 MPa (a) and of activat ed powd er sinte re d under pressure of 510 and
700 MPa (b, c). Th e results obtaine d are in correlati on with the results of DSC
analysis for the recov ery rate of abo ut 723 K. Ab ove th is temperature , the spe cime ns
of activated powder show another recov er y rat e which is probably the result of
annihilation of defects occurred in thew process of trib ophysical activati on of
powder.
DSC
(mW)
60.700MPa
10
200 400 600
Fig. 2. DSC thermograms of unactivated and activated powder and specimens obtained by cold
sintering of that powder under pressure of 700 MPa
The appropriate kinetic parameters are determined on the basis of isothermal

measurement of the electric resi stivity change in the appropriate time interval. Fig. 4
shows the logarithmic dependence of the electric resistivity on time at con stant
temperatures 663 K and 693 K. Straight lines a, and a, show slower processes and
straight lines b, and b, show a faster process of stabilization of the electronic
structures.
571
0 .8 30
b,
1.5
<:
0.7
1.4 c, 25
0.6 1.3
1.2 20
0.5 1.1
E 1.0 15 E
C:.-. 0.4 c: o
~~
c;: 0.3 -a.~ ....
.ci'
b - 510 lvPa 10
0.2 c- 760 lvPa
5
0.1
0.0
=---- 0
0 200 400 600 800
t(C)
Fig. 3. Depend ence of a specific electric resistivity on the temperature of an unactivated powder
specimen pressed under pressure of 700 MPa (a) and activated powder pressed under pressure of 510
and 700 MPa (b, c)
r-----------------------,-o
-4.5
-4.6 r~-=----=::~=-----~
T 2=693K
-8
0::: -4.7
""'N
0::: ..c
.6 .6
....
~
..c
-4.9 -10
Tf663K
-5.0 ~~--:-':-:-~-L-~-.,-'---~---'L-~---'-----'
o 100 200 300 400 500
t(S)
Fig. 4. Logar ithmic dep end ence of electric resistivity on time at temperatur es of 663 K and 693 K.
572
The velocity constants of the appropriate processes are determined from the
gradient of the straight lines a, and a z as well as b, and b z:
k= ~lnR (1)
~t '
and then from the gradient ~ In k] ~(1 / T) are determined the activation energies
according to formula:
E=R ~Ink (2)

~(1 / T)'
where R - universal gas constant. The obtained kinetic parameters are shown in
Tab . 1.
Table 1. Kinetic parameters of the electronic structure stabilization process
T(K) K I(104SI) Kz(10 4SI) EI(kJ/mol) Ez(kJ/mol)

663 115.85 0.81
25.78 16.21
693 141.84 0.92
As it can be seen the activation energy value is connected to the change of the
structure and activity of material. In the temperature interval where greater
structural changes occur, the value of this energy is higher.
CONCLUSION
The results of x-ray analysis show that during the tribophysical activation of
Cu70%Fe30% powder system lasting 5, 15 and 60 minutes, the process of
mechanical alloying occurs.
It has been ascertained by DSC method of analysi s that the recovery process of
a deformed crystalline structure is exothermally developed within the temperature
interval of about 100 to 550C.
By measuring the electric resistivity subject to temperature it was shown that
two stabilization stages of electronic structure were present for the specimens
obtained by cold sintering of the activated powder. The first stage develops in the
temperature range of about 353 to 673 K for both specimen types (made of
unactivated and activated powder). However, at higher temperatures of about 723 to
923 K the specimen of activated powder shows a new recovery stage which is
probably the result of annihilation of defects occurred in the process of tribophysical
activation of powder.
REFERENCES
1. A.A.Popovich, V.P.Reva, V.N.Vasilenko, T.A.Popovich, G.A.Belon s, Mehanohemiceski metod

poluceni praskov tugoplakih soedineni, Poroskove metslurgi; 37-43 (1993) (in Russian)
573
2. E.G.Avvakumov, Mehsniceskie metodi aktivacim bimiceskih procesov, Nauka, Novosibirsk, (1986)
(in Russian)
3. V.Ostapenko, M.M.Ristic , Skripts energija detormecii, CMS BU i ITN SANU, Beograd, (1989) (in
Russian)
4. R.M.Agatonovic, V.D.Blank, Yl.I, Sholpan, M.M.Ristic , Cold sintering molybdenum powder under
the influence of applied sheak deformation, High Temperature-High Pressures, 24:267 (1992)
5. R.Lj.Simeunovic, A.M .Maritic, M.V.Susic, Recovery of cold sintered powder mixetures of Cu-Fe
system , J.Serb.Chem.Soc. 60:715 (1995)
574
THE INTERFACE CHARACTERIZATION OF
LAMINAR NICKEL-ALUMINA COMPOSITES
Dragana Jankovic, Dusan Kicevic, Mirjana Mitkov
Institute of Nuclear Science "Vinca ",

Material Science Laboratory
P.O.Box 522.11001 Belgrade,YU
ABSTRACT
The objective of the present work is to examine the different aspects of the
interfaces existing in three and five layers laminar composites. A1 203, Ni and Ni +
Al z0 3 (microinfiltrated bonding layer; Ni:Al z0 3-25:75 wt% mixture) layers were
obtained by tape casting . The characterization of laminated Al z0 3 / Ni-r Al z0 3 / and
AlzO/ Ni+ Al z0 3 / Ni / Ni+ Al z0 3 / Al z0 3 composites produced by pressureless
sintering, included SEM, ED AX, R6 and bending tests examinations. The nature of
interface between the individual layers of the composites, as well as nickel particles
in alumina matrix (microinfiltrated laminae), has been discussed. Bonding quality,
interaction between cracks and nickel particles, laminar composite architecture and
thermal residual str esses as well influence the strength of the composites.
INTRODUCTION
The formation of multilayered structure between brittle phase (Al z0 3 ) and

ductile phase (Ni) is associated with problems, such as incompatibility, non or poor-
wettability and great differences in thermal and chemical behaviour. It is shown' that
the structure of bonding layer plays th e main role in the production of material with
good characteristics. The nickel-alumina interface made by solid state bonding is a
subject of many studies. The main limitation to the toughening of the aAlzO/Ni
composites is the poor bonding at the interface, which causes the nickel particles to
be pulled out during crack propagation without obvious plastic deformation", For the
aAlzO/Ni interface in vacuum condition, alumina is not wetted by both, solid and
liquid nickel, and no intermediate phase forms at the interface". However, oxygen
dissolved in nickel promotes both wetting" and the formation of spinel phase
(NiAl z0 4 ) at the interfaces. The beneficial effect of a moderate amount of oxygen in
the environment on the bonding of nickel to alumina has been cited in several
Advanced Science and Technology ofSintering, ed ited by Stojano vic et al.

Kluwer Academic lPlenum Publishers, New York , 1999 575
studies . Some authors believed that wetting promoted by oxygen increased the work
of adhesion and the strength of the interfaces. Some others attributed the benificial
effect of a moderate amount of oxygen to the formation of spinel at the interface
which established stronger chemical bonds than those found in the clean metal
contact.
Mechanical properties of solid state bonded aAlzO/Ni interfaces depend upon
the plastic deformation of the metal , on the damages induced at the ceramic surface
and on both the nature and amount of interfacial phase that appears during the
composite material forming . The complexity of the phenomena controlling the
bond ing processes influences the fracture resistance i.e. defects present along the
interface (pores, unjoined areas), damage and cracks induced either by thermal
stresses or by friction between the two materials especially in the ceramics close to
the interface.
EXPERIMENTAL PROCEDURE AND RESULTS
Single layers of alumina, nickel and Ni+Al z0 3 mixture , were made by tape
casting from elemental powders. The Ni and Alz0 3 powders have an average
diameter of 2Jlm and 0,7-1Jlm, respectively . X-ray analysis has detected about 2%
NiO present in Ni powder. Ni+Al z0 3 powders mixture is prepared by
homogeni zation of 25 mass.% of Ni and 75 mass.% of Al z0 3 powder in a jar mill for
30 min.The tape casting procedure used is described earlier?".
The slip, containing the powder and solvent mixture , was ball milled for 24h.
The binder and plasticizers were then added, and the slip was milled for next 24h,
The speed of doctor blade casting was set at 11 em/min. Typical cast tape thicknesse s
ranged from 200-250llm after drying. Green sheets of Al z0 3 , Ni and Ni+Al z0 3 were
solid state bonded with an applied pressure of 1.2-2.2 MPa for 30-60 sec. in a
graphite die at 75C.The green Alz03/Ni+Alz03/Alz03 assembly was slowly heated
up to 550C, in an argon atmosphere for 3h, in order to prevent the Ni oxidation
during binder removal.
Two different laminar nickel-alumuna composite types were produced by
pressureless sintering at 1425C, for 3h in an inert Ar atmosphere. In order to avoid
delamination, in both cases, special attention has been payed to the cooling rate
from high consolidation temperature to ambient temperature,
During consolidation, several different interfaces are created: (a) between Ni
particles and Alz0 3 matrix in IN i+A lzO/ bonding layer ; (b) between external
alumina layer and bonding layer , Al zO/Ni+Al z0 3 interface , and (c) between central
nickel layer and bonding layer e.i. Ni l Ni+Al z0 3 interface (Fig.1. a-c).
(a) (b) (C)
Figure 1. Nickel particle/alumin a matrix inter face in bonding layer (a) , AI20 ,/Ni+AI20 , interface
(b) , Ni/ Ni-Al .Odnterface (c)
576
EDS interface characterization (Fig.2) and X-ra y analysi s (Fig .3.) detected
presence of thin spinel film around Ni particles in Ni+AI 2 0 3 layer. Thin spinel film on
central Ni layer in five-layer composites architecture is shown on FigsA and 5.
NiLa
AIKa
NiKa
o
NiKb
5~lIn
- --
6.60 BAD
NiLa NiLa
NiKa
NiKa
NiKb
OKa AlKa NiKb 0
3.00 4.80 6.60 8.40 1.20 3.00 4.80 6.60 8.40

1.20
keY keY
Point 2 Point 3
Figure 2. SEM micrograph Ni+AI 203 fracture surface with E D S analysis of Ni+AI 203 , point 1,
point 2, point 3
Mechanical characteristics have been examined using three-point t1exural test

with applied force of 0-20N and cross head spead of 0.05 mm/min . Load-deflection
curves measured for flexural strength of / Ni+AI 20 3/ bonding layer, three layer
composite and five layer composite are pres ented in Figs. 6a-8a. Scanning electron
micrographs of the fracture surfaces are given in Figs.6b-8b. In order to understand
contribution to the toughness increase in the composite, it is necessary to study the
load -deflection curve. Area under the load-deflection curve divided by projected
fracture surface area is defined as the work of fracture W
The curve of the composites can be divided into two regions: one is the elastic
region (left) another one is inelastic region (right); elastic work We , i.e. inelastic
work Wie are corensponding respectively. Three point bending test results are
sumerized in Tab.l . All results are compared with appropriate alumina specimens.
577
40 28 00 (a) (b)
Figure3 .Spinel phase in Ni+AI 203 Figure4. Thin spinel film on central Ni layer (a)
laminat e detected by X-ray structure of spinel phase on Ni layer(SEM) (b)
6
5
~4
~ 3
2
0,1 0,2 0,3 0,

Deflection (mm)
(a) (b)
Figure 5. Load-deflection curve for lNi+AI 20 / single laminate(a)

SEM micrograph of lNi+A1203 / fracture surface (b)
0,10 0,15 0,20 0,25 0,30

Defleclion(mm)
(a) (b)
Figure 6. Load-deflection curve for AI203INi+AI20 / Al 20 3 composite(a)

SEM micrograph of A12031Ni+ AIP/ AlP3composite fracture surface (b)
578
30
Z25
;20
<':l
315
10
5
o 0 .1 0 ,2 0,3 0,4 0.5 0 ,6 0 .7
Deflection (m m)
(a) (b)
Figure 7 Load- deflection curve for A120 / Ni+AI P /N il Ni+A I20 /AI203 composi te (a )
SE M micrograph of AIP/ Ni +A lzO/Nil Ni+A lzO/A I203 comp osite frac ture surface (b)
Table L'Thr ee-p oint bending test results
Sample W We % W, % W ie ar u
(11m 2 ) (J/mZ ) (MPa) (mm)
AI20 , laminate 90.15 90.15 100 0 84.2 0.208
Ni+A l,O lamin at e 131.34 131.34 100 0 68.5 0.23
three layer A l,O , 143.0 95.82 67 33 36.64 0.1178
three layer 109.3 39.5 36.1 63.9 26.96 0.293
AI,O, lNi+AI ,O/ AI,O ,
five laye r AI 2O, 179.2 91.9 51 49 30.54 0.194
five layer com posite 676.0 95,5 14.2 85.8 192.7 0.635
IA I20, Ni+AI 20 /Nil Ni+AIPi
A12O ,
W-work of fracture , We-elast ic work, Wi,-m elastic work; a I-flexure strength, u-deflection
DISCUSSION
X-ra y, as well as , E D S an alysis revealed th e pr esenc e of a spine l ph ase on th e Ni

particle sur face (Fig2.).
Solid state reaction between NiO and Al 20 3 at temper ature abo ve lOOOC lead s to
NiAl 204 spinel forrnatiorr', which is ofte n not well crystalized along th e inte rface .
Neverthless , spine l phase benifites wetting in Ni- AI20 3 syste m".
The latest results' " hav e sho wn that spin el formation in NilAl 203 could be
possible without int ermedi at e NiO. The O 2 presence during th ermal treating sho uld
be in orde r of 1/5 of oxyge n so lubility in nick el, to mak e possible th e reacti on of
spine l formation .
The initati on of spine l forming is provided in o ur case by NiO pr esence at Ni
particles sur face, whil e inert atmos phe re reduced reacti on inte nsity. The fracture
surface of Ni+AlP3 layer (Fig. 2) reveals th in spine l layer around Ni particles. T he
oxygen concentrati on corresp onding to NiAl 204 has been fo und at th e particle
sur face layer (po int 1, Fig.2), go ing fro m th e surface to the center of Ni particles O 2
concentration decreases (po int 2,3).
Spinel ph ase is det ected in three-laye r, as well as, in five-laye r composite.
Three-layer nickel alumina composite sho w different work fra cture distribution
compar e to pure cera mic sample (Tab.1.). In met al cer amic ca mposite inelastic
579
deformation are dominating (Fig.6.), causing the increase of fracture resistance by
combination of energy absorption due to crack deflection (Fig.5b.) and energy
dissipation during streching the very liminited amount of Ni particle ( crack
bridging). Lower values for fracture work, as well as, flexural strength are caused by
residual thermal stress and presence of two, symetric interfaces Al z03INi+Alz03
In five-layer composite architecture new type of interface are created. Presence
of central nickel layer, as well as Ni/Ni+Al z0 3 interface are corresponding with work
fracture and strength increase. Thin film of not very well crystalized spinel phase is
detected on Ni/Ni+Al z0 3 interface (FigsAa,4b).
Since the spinel/Ni interface is weak?", spinel formation could have detrimental effect
to the bonding. Fracture surfaces analysis shows that spinel/alumina interface is
weaker it is obvious (Fig.7b) that fracture propagates through that interface. It
means, the Ni/spinel interface could be stringer be in the case of smaller amount of
spinel formed (FigAa,4b) after the instantaneus interfacial reaction and it does not
form a continuous layer along the interface,
CONCLUSION
Multilayered nickel/alumina composites have been fabricated using pressureless

sintering technique. Small amount of NiO and oxygen promoted wetting and created
a strengthened interface with thin spinel phase. Three different interface types are
created: Ni particle/ alumina matrix , alumina layer/bonding (Ni+Al z0 3 ) layer and
central Ni layer/ bonding (Ni+Al z0 3 ) layer.
Three point flexure tests of single laminate and composites, have shown a
fracture resistance increase, which is determinated by interface characteristics as well
as crack deflection, delamination and nickel plastic deformation.
Presence of different, not symmetric , interfaces are responsible for thermal and
stress system relaxation, as well as better bonding quality.
ACKNOWLEDGEMENTS
The author acknowledge the help of Mrs.S.Zec in X-ray analysis. This

research was supported by the Ministry of Science and Technology of Serbia, within
the project 02E27.
REFERENCES
1. KK Chawl a, Metal Matrix Composites, in Materials Sciences and Technology,Eds .R.W.Cahn,

P.Hassen, E .J.Kr amer,VoLl3, VCH, Weinheim,NewYork,Basel ,Cambridge,Tokyo(1993)
2. X. Sun, J.A.Yeomans, Effect of Interfacial Bonding on the Toughening of AlzO/Ni ceramic
matrix composites,J.Mater.Sci. Technol.,12 :29(1996).
3. X. Sun , J.A.Yeom ans, Effect of Wetting and NiAl z0 4 Spinel Formation on the bonding
between Alz0 3 and Ni, J.Mater.Sci.Technol. ,12:421(1996).
4. P. Lourdin, DJuve,D .Treheux,Nickel-Alumina Bonds:Mechanical Properties Related to
Interfacial Chemistry, J.European Ceram.Soc.,16:745(1996)
5.W.H. Tuan,R.J.Brook,The Toughening Of Alumina with Nickel Inclusions, J.European
Ceram.Soc.,6:31(1990)
6. M. Mitkov,D .Jankovic,D .Kicevic,Microstructure and Strength of Solid state Bonded Ni- Al zOr
Ni 3Al Laminates, M aterials Science Forum,282:165(1998)
7. DJankovic, D .KiceviC,M.Mitkov, nickel-Alumina composit es produced by Pressureless
sintering and Hot Pressing,Science ofSintering,30:105(1998)
8. KP. Trumble,M.Ruhle,The Thermodynamics of Spinel Interphase Formation at Diffusion
Bonded Nil Al z0 3 Interfaces, Acta Mertall.mater.,39:1915(1991)
580
THE INFLUENCE OF AI203 ADDITION ON
ELECTRICAL PROPERTIES OF SINTERED COPPER
Milan T. Ristic, Maria Vesna Nikolic, Zoran Jankovic, Aleksa Maricic
Joint Laboratory for Advanced Materials of the Serbian Academy of

Sciences and Arts, Knez Miha ilova 35, 11000 Belgrade , Yugoslavia
INTRODUCTION
Electric conductivity is often a very significant propert y in the application of metals .

Electrical properties of metals can be explained from the viewpoint of a quant itative
analysis of electronic effects in these materials' . The valent electron for copper, whose
electronic configuration is Il2l2l3 s23p63io4s is 4s, so it can be assumed that one valent
electron is free in each copper atom . Thus, the concentration of conductive electrons is
equal to the number of atoms per volume unit"
Porosity can have a significant influence on electrical properties of sintered copper.
This problem was investigated and experimentally proved by V. V. Skorohod3.
If an oxide dielectric is added to copper, its conductivity should depend on the
additive concentration. The influenc e of the addition of small amounts of Ab03 on the
sintering process of copper and electric conductivity of the sintered material were
investigated in this paper.
EXPERIMENTAL
Copper and Ab03 powders, whose basic characteristics are given in table I were used
for experimental work .
Table 1 Characteristics of Cu and Ab03 powder
Characteristics Cu powder
Specific surface (m2/g) 0.3 2.5
Average agglomerate size (urn) 68.05 60.24
Green density (g/cm') 1.4\ 5 0.85\

Kluwer Academic/Plenum Publishers, New York, 1999 58\
Table 2 Density of copper compacts
Sample %Cu
C-OOA 100 o 5.48
C-OIA 99 .9 0.1 5.46
C-02A 99.8 0.2 5.45
C-03A 99.7 0.3 5.42
C-05A 99 .5 0.5 5.39
Starting mixtures with 0.1, 0.2, 0.3 and 0.5% Ah03 were obtained using the tribophysical
method by dilution of a starting mixture with 50%Cu+50%Ah03. These starting samples
were pressed under the pressure of 102 MPa giving compacts with ~ 10x5 mm. The
compact density obtained is given in table 2. The compacts were then sintered in the
temperature interval 1073-1273 K for 1 hour in a hydrogen atmosphere . The density of
sintered samples is given in table 3.
Table 3 Density of sintered copper samples
Sample
1073 K 1123 K 1173 K 1273 K
C-OOA 7.16 7.42 7.90 7.99
C-OIA 7.08 7.32 7.85 7.91
C-02A 7.00 7.24 7.76 7.84
C-03A 6.94 7.15 7.70 7.79
C-05A 6.77 7.04 7.53 7.64
Measurements of the specific electric resistivity of sintered samples were performed

using a modified Witston bridge with decimal box resistivity. The results obtained are
given in table 4.
Table 4 Specific electric resistivity of sintered copper samples
Sample p(Qcm)
1073 K 1123 K 1173 K 1273 K
C-OOA 91.40x 10-4 86.95x 10.4 84.IOxI0-4 82.75x 10-4
C-OIA 92 .00xI04 88 .20xlO-4 85.00xI0-4 83.00xI0-4
C-02A 95.50x 10-4 90 .05xlO- 4 86 .80xI0-4 84.50xlO- 4
C-03A 1OO.OOx 10-4 94.80x 10-4 88.20xI0-4 86.60xI0-4
C-05A 110.00xI0-4 104.50xI0-4 90.05x 10.4 88.00xI0-4
DISCUSSION
Analysis of experimental results given in table 2 shows that the density of copper
compacts decreases with the increase of the Al203 content (Figure 1) as:
dp=-0.18x+5.49, (1)
where x is the % content of Ah03 in the compact.

As the theoretical density of Ah03 is 2.24 times smaller than the density of copper, it
is logical that the compact density decreases with increasing Ah03 content.
582
5A8
546
<')
E

~ 5A4
~
~
'iii
t 5A2
-0

U -,
m
a.
E
o
5AO <, -,
"
u "II!
-, -,
00 01 02 0.3 OA 0 .5
Figure 1. The influence of Alz0 3 content on compact density
The change of the density of sintered samples with the Ah03 content is shown in figure 2.
The influence of the AhO) content on reduction of the density of sintered copper is
obvious. Analysis of this dependence shows that it can be characterized by the following
equation:
d s=-O .78x+A, (2)
where x is the % content of AhO ) and A is a constant which depends on temperature

(table 5).
1073
80 1123
1173
78 'f 1273
(f)
Q)
c..
E
7.6
.' .
m 7A
-0
~
27 .2
c
.iii
'+-
0 70
~
'iii
c
~ 6.8 --- ---.
. ..
00 01 02 0.3 0::
Figure 2. The influence of Ah03 content on the density of sintered samples
583
The dependence of the electrical resistivity of sintered copper samples on the AhO ]
content (Figure 3) can be defined as :
pi 04 =24.68x+B]
p104 =24.68x+B2 , (3)
where x is the % content of A120] and B is a constant which depends on temperature

(table 5).
1073
110
1123
105 '"
~
1173
1273
100
"'"
a..-
95
><
o
90
:35
0.0 01 02 0.3 0.4 0.5
Figure 3. The influence of Ah03 content on specific resistivity of sintered samples
Table 5 Values of constants A and B in eqs. (2) and (3)
Temperature roC] A
1073 7.16 89.56
1123 7.41 84 .67
1173 7.92 84.19
1273 8.01 82 .33
Electric resistivity of sintered copper grows with the increase of the AhO] content, but
its values also depend on the porosity of sintered samples, which is especially expressed at
lower sintering temperatures. In agreement with this, the influence of AhO] addition is
viewed for the sintering temperature of 1273 K, for which:
pi 04 =1198x+82.33, (4)
so the value of B4 can be taken as the characteristic parameter of the influence of AhO]
addition on electric resistivity of sintered copper, with a density of up to 90% of the
theoretical value.
584
CONCLUSION
The influence of Ab03 addition on copper sintering and its electric resistivity has
been investigated. It was shown that addition of up to 0.5% Ab03 in the temperature
interval of 1073-1273 K is characterized by a linear dependence of density on the Ab03
content. Electric resistivity of sintered copper depends on both the Ab03 content and the
porosity of sintered copper.
ACKNOWLEDGMENT
This work was performed as part of project "Prognosis of Materials Properties from
the Viewpoint of the Triad SSP (Synthesis-Structure-Properties)" financed by the Ministry
for Science and Technology of Serbia and the project "Investigation of the consolidation
process of materials" financed by the Serbian Academy of Science and Arts.
REFERENCES
I. A. Dekker, Fizika e1ektrotehnicheskih materialov, Gosenergoizdat, Moskva , 1982 (in Russian)

2. M. M. Ristic, Principles ofMaterials Science, SASA, Beograd, 1993 (in Serbian)
3. V. V. Skorohod, Poroshkovaya meta//urgiya, NO.3 (1965), 27 (in Russian)
585
THE EFFECT OF THE DEFORMATION DEGREE ON
THE KINETICS OF STRUCTURAL RELAXATION
OF THE Fes9.sNil.sSis.2B3Co.s AMORPHOUS ALLOY
A.M. Maricic,' R.LJ. Simeunovic,' and M.M. Ristic'
lTechnical Faculty,
Cacak, Yugoslavia
2Serbian Academy of Sciences and Arts,
ABSTRACT
Investigations were performed of the kinetics of structural relaxation of the

Fes9.sNi1.5Sis.2B3Co.5 amorphous alloy for different strain rates . Measurements of
changes of the specific electric resistivity and thermal expansion of the ribbon in
isothermal conditions determined the kinetic parameters of the structural relaxation
process for different strains: (J\=65 MPa and (J2=130 MPa. It has been shown that
values of the activation energy of the relaxation process decrease with the increase
of the deformation degree. Furthermore, the crystallization temperature of the alloy
decreases with the increase of the deformation degree. It has been also shown, that
the process of the structural relaxation has an influence on changes of physical
properties. Due to the decrease of the free volume during isothermal structural
relaxation the temperature interval of the linear dependence of thermal expansion
on the temperature expands, the specific electric resistivity decreases and the
elasticity module increases.
INTRODUCTION
The structure of the amorphous metal alloys (AML) is characterized by

thermodynamic unbalance. This results, at heating, in crystallization of amorphous
alloys after real time . Prior to crystallization there occurs the structural relaxation
which leads to conversion of the atomic structure into the metastable equilibrium
state. It has been assumed that these changes are mostly connected to disappearance
(for T < Tg) or occurrence (for T > Tg) of free volume'" (T - annealing temperature
and Tg - temperature of a characteristic conversion). At isothermal annealing at
temperatures which are from 20 to lOOC lower than the temperatures of
Advanced Science and Technology ofSintering, edited by Stojanovic et al .

Kluwer Academic /Plenum Publishers. New York , 1999 587
crystallization, the amorphous alloy shows the exponential flow of the linear
expansion. At isothermal annealing, practically the whole amorphous alloy shows
the linear growth of viscosity with the annealing time", It is expected that viscosity
will achieve a constant value when the amorphous alloy achieves the metastable
equilibrium at the temperature of the isothermal annealing.
The low temperature linear dependence of the ribbon length Lo(T) on the
temperature is defined by the equation:
(1)
where TB - initial heating temperature, Lo(TB) - initial ribbon length of glossy alloy ,
a~ - coefficient of linear expansion in the low temperature range of T B to To, where
To is the temperature of the ideal glossy transition. In the first approximation it can
be assumed that the coefficient of thermal expansion does not depend on
temperature, but only for temperatures considerably lower than the temperature of
amorphization.
According to the results shown" it is quite obvious that the internal bond
between the viscous process and behavior at thermal expansion of amorphous allows
really exists on the basis of the same mechanism of change of the free volume with
temperature. It proves its own reconciliation of the free volume theory in describing
these two phenomena which appear at heating of amorphous metal alloys.
EXPERIMENTAL WORK
The specimens tested were amorphous alloys Fe89.8Ni15Si5.zB3Co.5 in the form of a

ribbon obtained by the melt spinning method - fast melt cooling on a rotating disc.
The specimen length was 0.15 m, width 2 x 10-3 and thickness 30 J..1m. During the
continuous heating with the velocity of 20 Klmin , the ribbon was exposed to a
constant normal tension. Measuring of the electric resistance was performed by
Thompson bridge of 10-6 n susceptibility, and measurement of thermal expansion by
the modified equipment for measuring the Young's modulus of elasticity,
susceptibility 10-5 m.
Fig. 1 shows the experimentally obtained dependences of thermal expansion

and specific electric resistance on temperature at the strains of 65 and 130 MPa. The
same figure shows the isothermal dependences of the thermal expansion and specific
electric resistivity on time.
It has been indicated in our previous work?'8 that the crystallization of this alloy
develops in two temperature close ranges 803 and 820 K.
The investigation results in this paper show that during the isothermal
relaxation within the temperature interval of 623 to 773 K there occurs the
isothermal expansion of the amorphous ribbon sample, while at the same time , the
specific electric resistance remains constant during the time. On the basis of this , it
can be concluded that during the isothermal expansion, there occurs the process of
transformation of the amorphous structure from the unbalanced state into the state
of metastable equilibrium, which means that the structural relaxation occurs in
difference to the process of crystallization during which the system passes into the
state of absolute minimum of free energy. It has been previously shown?' 8 that the
588
't(min)
o 10
1.4 -- 1
-n- 2
1.2 --A-- 1 1.9
2
-E
---b-
1.0
1.8E
-E
0.8
-<J' 0.6 1.7 a.

~
0.4
0.2
0.0 +..-.~~e:-:::;:"--r-~.,--.......- - - - - - - - - - l 1 .5
0 100 200 300 400 500
t (0C)
Fig. 1. Dependence of thermal expa nsion and specific electric resistivity on the temperature at heatin g
up to 480C and tensi on of 65 MPa (curves 1 and 1'), at stra in from 130 MPa to 430C (curves 2 and
2') . The appropriate isoth erm al dep endences on time at those temperatures are shown in their
exte nsions.
crystallization process is followed by the sudden reduction of the specific electric

resistivity not occurring during the process of the structural relaxation. However , the
process of the isothermal expansion is followed by the reduction in the free volume.
The logarithmic dependence In(U.1I) on time shows that the structura l
relaxation of the amorphous alloys testing develops in two stages for both stra in
ti In(ll11/)
rates. From the gradient M of the straight lines a., b, and az, b z obtained by
decomp osition of the curves a and b (Figs. 2 and 3), velocity constant s are
determined for both stage s of the structural relaxati on.
5,--- - - - - - -- - - -- -------,
__
65MPa
4
~3~~-----
~
723K
~ 753K
- 2
2 4 6 8
t (min)
Fig. 2. Isoth ermal dependence In (lIti1) on time at a strain of 65 MPa.
589
3.0 r - - - - - - - - - - - - - - - - - - - - - ,
130 MPa
2.5
2.0
~ 1.5
E 673K
1.0
0.5
703K
2 4 6 8 10 12
1: (min)
Fig. 3. Isothermal dependence In (l/t.I) on time at a strain of 130 MPa.
t.ln(l/M)
From the gradient M the activation energies are determined for both
relaxation grades in accordance with relation:
E= R. tllnk (2)
tl(l / T)
The obtained kinetic parameters for both strain rates and both structural
relaxation grades are shown in Tab. 1.
Table 1. Characteristical structural relaxation kinetic parameters
cr,MPa T ,K k 1,103s] k 2 ,1O3s] E], kllmol E 2 , kllmol
723 15.00 1.80

65 89.60 26.56
753 25.60 2.10
673 12.80 0.92
130 66.40 15.40
703 22.00 1.83
The results obtained show that with the strain increase the activation energy in
the both processes of the structural relaxation drops. The obtained values of
activation energy of the both grades of the structural relaxation procedure are
considerably lower (by a value of magnitude) than the activation energies of the
crystallization procedure E] = 478.7 kl/rnol and E 2 = 622.3 kl/mol for the same alloy
tested by DSC method?
CONCLUSION
It has been ascertained that, at both strain rates, during the isothermal
annealing in the temperature interval from 623 K to 723 K, there occurs the
590
isothermal expansion of the amorphous alloy Fe89.8Ni1.5Sis.2B3Co.5 , while, at the same
time, the specific electric resistivity remains constant. This means that at relatively
small strains, at annealing up to 773 K, only the process of the structural relaxation
develops . Activation energies of both structural relaxation stages for both strain
rates, are considerably lower than the activation energies of both grades of the
crystallization procedure.
With the increase of the strain rate , the activation energy of the both grade s of
the structural relaxation drops which means that the process of the structural
relaxation itself changes with the change of the strain rate. After structural
relaxation, at simultaneous effect of both temperature and strain, low temperature
interval of the linear dependence of the amorphous ribbon length Lo(T) on the
temperature is considerably expanded. The expansion of the temperature interval is
proportional to the strain rate of the amorphous ribbon during the procedure of the
structural relaxation, which is directly connected to disappearance of the free
volume in material.
REFERENCES
1. P. Tuinstra, P. Duine, and J. Sietsm a, 1. Non-Cryst. Solids, 519: 156 (1992)
2. G.A Petrokovskii, Advances ofphysical science, 134:308 (1980) (in Russi an)
3. K. Russew, F. Sommer, P. Duhaj , and I. Bakonyi , 1. Mat. Sci 27:3565 (1992)
4. K. Russew and L. Stojanova, Mater. Letters, 17:199 (1993)
5. P. Duine, and J. Sietsma, and A Van den Beuk el, Acta Metall. Mater. 40:73 (1992)
6. D.Tumbull and M.H . Cohen, 1. Chern. Phys. 53:3038 (1970)
7. M.V. Susie, AM. Maricic, N.S. Mitrovic, S. Dukie, B.D . Stojanovic, Sci. Sin. 28:189 (1996)
8. A.M. Maricle, M.V. Susie, and M.M. Ristic , 1. Serb. Chem. Soc. 62:643 (1997)
591
INVESTIGATING POSSIBILITIES OF SINTERING PROCESS MONITORING
BY ACOUSTIC EMISSION AS AN ON-LINE METHOD
M. Tasic, Z. Andie, D. Bojovic
Scientific-research Center - Uzice, Yugoslavia
ABSTRACT
In this study the investigations on devising the convenient ON-LINE method for
monitoring the sintering process during the equipment production by powder metallurgy
procedure are presented. In the course of the experimental performance W-Ni-Fe
compacts have been sintered at various temperature and the same time of sintering while
the comparative analysis of the recorded acoustic emission signals at the observed
samples has been performed.
The laboratory kit has been constructed and obtained results point out to the
possibility of sintering process monitoring by recording acoustic emission signals and
their correlation between physical mechanisms occurring in the very material during the
process.
FORMER INVESTIGATIONS
The principle of acoustic emission method is based on the changes occurring in the
material and a sudden release of a part of accumulated deformation energy which
manifests through the mechanical waves. The mechanical waves are transmitted through
the material and detected by a sensor. This very phenomenon of the mechanical waves
generation, caused by a part of deformation energy released in the material, is called
acoustic emission.i':"
Regarding that all the materials used for constructional purposes (metals, alloys,
glass, ceramics, wood, concrete and polymers) emit, under certain conditions, the signals
of acoustic emission this method can be used in the following cases:(2.3,4) at tensile
strength testing, for structural composition and material properties control, at testing of
phase transformations in the material, for control of vessels and pipelines, for control of
air- and space-craft constructions, at welded joints testing, at cracks testing, at material
Adva nced Science and Technology of Sintering , edited by Stojanovic ct al.

Kluwer Academic/Plenum Publishers. New York. 1999 593
fatigue monitoring, at monitoring of fracture development at low temperatures, at material
solidification monitoring.(5)
THE GOAL OF INVESTIGATING
The equipment production by powder metallurgy procedure starting with powders'

mixture of appropriate componenets is fundamentally based on sintering during more or
less porous polycristalline materials are obtained. The process of sintering can be
performed in two ways:
- at temperatures below melting point - sintering at the solid phase,
- at temperatures of the liquid phase which occurs as a consequence of
easy-meltable components in the existed system - sintering with the presence of
the liquid phase.
The main goal of research is study on possibilities of sintering process monitoring by
acoustic emiss ion method, because of the great complexity of sintering process and
impossibility of direct realizing all the mechanisms which characterize this process and
have impact on the quality of the obtained product. After the researches be done more
detailed, it would make possible controlling and directing the process that is to determine
optimal temperature of sintering, to monitor the levels of porosity at various temperatures,
to define the beginning of the liquid phase formation, and respectively temperature to be
known has essential importance for the process itself.
Experimental researches have been performed in the laboratories of Scientific-

research Center (NIC) -Uzice and MDD"Sinter"-Uzice.
While the experiment is done W-Ni-Fe compact is used for monitoring the sintering
process by acoustic emission method.
At initial phase the researches include the determination of laboratory kit and
monitoring the sintering process by acoustic emission method upon the same compacts at
various temperatures and the same time of sintering, together with their comparative
analysis.
In Figure 1. the "vessel" used for placing the samples at sintering is shown. In Figure
2. laboratory kit used for monitoring the sintering process by acoustic emission method is
shown .
1~5 47
I: 'I L _ .J
~oJ 50
60
Figure 1. - "Vessel" for sample placing at sintering.
594
(j 5 2
Figure 2. - Scheme of laboratory kit for monitoring the sintering process by acoustic emission method
1. Furnace for sintering, 2. "Vessel" with a sample, 3. Conductor, 4. Sensor, 5. Acoustic emission
detector, 6. Plotter
Rod-shaped conductor of acoustic emision signal is attached to the "vessel" wherein

a sample is placed to be put in the furnace for sintering . To provide conductivity of
acoustic emission signal better and losses reduced, the system of the "vessels'l-the
conductor of the signal is made of the same material (refractory steel). Sintering is carried
out at protected hydrogenic atmosphere in the tube-furnace with one active tube.
Piezoelectric plate BMF lOP-S is used as a sensor. Total amplification of acoustic
emission signal varies from SOOO to I0000. Frequent response of the amplifying level
from 100 kHz to 3 MHz is restricted by using a filter not affecting the total amplification
and the resonance area of the sensor.
Acoustic emission signal treatment is performed by sensor-recorded oscillations
counting method (ring-down counting method) .
The method of the sensor-recorded oscillations counting is based on each overthrow
on the decision level of the signal obtained at the sensor output.
The advantage of this method lies in the fact that the number of overthrows on the
decision levels increases together with the amplitude.
Total number of sensor-recorded oscillations is transmitted through the amplifier to
the plotter HP7090 A which has AID convertor inside.
While the experiment is performed, the sintering process of W-Ni-Fe compacts at

700 C sintering temperature and sintering time of 30 minutes, is firstly monitored by
acoustic emission method.
Test samples have no regular geometrical shapes.
The dependence between acoustic emission signal and the time during sintering W-
Ni-Fe compacts at 700 C for 30 minutes is given in the diagram of Figure 3.
Analyzing the diagram it may be stated that at the very beginning of sintering
process a smaller increase of acoustic activity is registered. This can be connected with
the occurrence of surface increase in the contact among the particles . In the following
course the curve presents linear increase of acoustic activity to the end of sintering
process . Regarding that the diagram structure of examined system state at temperatures
below 1000 C has not still known, it might not be possible recorded acoustic emission
signals correlate to composition and structure of material at the observed temperature.
595
r-
[,r
~
r-
! ,.-
-
,
I-' ~
~
Co'
~
,
J
JV ! ~
V
J i
!
V
Ir
U- I lr~
o 5 10 15 20 25 30
Time, min
Fig ure 3. Recording of acoustic emissio n signal during sintering W-Ni-Fe compacts at 700 0 C in 30 minutes
The dependence between acoustic emission signal and the time during sintering W-
Ni-Fe compacts at l ()()(f C in 30 minutes is given in the diagram of Figure 4.
Considerably more intensive acoustic activity is observable herein.
Signal AE x Hi (V)
I-r
r- , ~
! .r
,
/ ! ~
, )
il ; V-
r i
! rir'"
J
I-'
J II
I
r
I-J
.I I ..r~
!
U I!
r
, 1""'
I) :,..r-
! l.r ,
II V u
o 5 10 15 20 25 30
Time, min
Figure 4. Recording of acoustic emissio n signal during sintering W-Ni-Fe compacts
596
Observing the isothermal section of the diagram W-Ni-Fe system state at iooo-C the
existence of intermetal phases W2Ni and WNi is noticeable among the other ones. The
intermetal phases originate from the appropriate two-system by peritectic reaction at
1000 C. Besides the acceleration of diffuse processes, the formation of these intermetal
phases can be also the cause of more intensive acoustic activity. Along with this, the
increase of acoustic activity at the very beginning of the process registered at the
preceding sample is observed.
CONCLUSION
Based on the obtained results, the following conclusions can be drawn:

- The obtained results show that it is possible to use the acoustic emission method
for monitoring the phenomena occurring during the sintering process;
- At the analyzed diagrams of the dependence between acoustic emission and the
time the increase of acoustic activity related to the increase of contact surface
among the particles at the beginning of sintering process is noticeable;
- Comparing the diagrams of the dependence between acoustic emission and the
time for the samples sintered at various temperatures, the more intensive
acoustic activity is observable at higher temperatures resulting from the more
complex action of all the mechanisms characteristic for the process of sintering .
Further researches will be directed to monitor the phenomena occurring at the
temperature range between 14500 C and 14900 C (wherein the liquid phase of W-Ni-Fe
alloy appears) by the acoustic emission method.
REFERENCES
1. Purvis L.A.,Kannatey-Ashibu E.,Pehlke R.D.: "Evaluation ofAcoustic Emission from

Sand Cast Aluminium Alloy 319 During Solidification and Formation of Casting
Defects" - Department of Materials Science and Engineering Department of
Mechanical , The University of Michigan Ann Arbor, Michigan, p.31, 1990.
2. Mitrakovic D.: "Doctorisl Dissertation" - Faculty of Technology and Metallurgy,
Belgrade , pA-29, 1984., (in Serbian)
3. N. A. Bunina : "Issledovsnie plasticeskoi defonnacii matallov metodom akusticeskoi
emissii'' - Leningradskii inzenemo-ekonorniceskii institut, Leningrad, p.30-58,
1990.
4. C. R. Heiple and S.H. Carpenter: ''Acoustic Emission Produced by the Delta-to-Alpha
Phase Transfonnation in Pu-Ga Alloys", Metallurgical Transactions A, Volume
23A, March, p.779-783, 1992.
5. Tasic M., Zaric D., et al.: "Studying ofthe Possibility ofAcoustic Emission
Application for Control and Monitoring ofCrystallization ofthe Special Brass
Type Alloys at Continuous Casting", XXIV Conference on Production
Mechanical Engineering of Yugoslavia, Novi Sad, Book of Proceedings, Volume
II, p.3A5-3.53, September 1992.
597
THE EFFECT OF ANNEALING ON THE TRANSPORT
PROPERTIES OF THE METASTABLE CUssCo\S ALLOY
Nebojsa Mitrovic, Aleksandar Rankovic,

Aleksandra Kalezic and Slobodan Dukic
Technical Faculty Cacak,

Svetog Save 65, 32 000 Cacak,
YUGOSLAVIA
ABSTRACT
The melt-spinning technique was used to prepare metastable CUSSCo 1S ribbons.

Stabilization of the structure was performed by furnace heating and direct current Joule
heating of ribbons. The resulting transformation s were monitored using DSC, X-ray
diffraction, the direct current four-probe method for resistivity and magnetoresistance
measurements. Reduction in electrical resistance was observed for thermal annealing of the
as-quenched samples over 680 K. The increase in the magnetoresistance ratio for annealing
currents I ~ 3A, indicates that structural and magnetic transformations occur in the ribbons.
INTRODUCTION
In recent years binary CUUX).xCox (5 < X < 20) alloys prepared by the melt-spinning
method are becoming the focus of attention . The electrical resistance of these ribbons
exhibits a large decrease upon the application of a high external magnetic field (GMR
effect, about 16% with 2.4.106 Aim) I. The giant magnetoresistance (GMR) effect in
ferromagnetic granular materials is associated with the reorientation of single domain
magnetic moments of Co-clusters embedded in the crystalline nonmagnetic Cu-matrix. This
structure can be attained after appropriate annealing of as-quenched Cu-Co alloys with a
metastable structure . This alloy system was selected because Co-Cu is a immiscible system
as is shown in the phase diagram on Fig. lao Subsequent annealing treatment of a
metastable supersaturated Cu-Co solid solution leads to the precipitation of ferromagnetic
Co-particles with the grain size of about 5 nm within the Cu-rnatrix 2. Without influence of
an external magnetic field the magnetic moments of neighboring Co-particles are not
aligned. The process of their alignment under an external magnetic field resulted in a
significant decrease of electrical resistance (magnetoresistance effect) 3. The object of the
current paper is investigation of the effect of two different thermal treatments: furnace and
Advanc ed Science and Technol ogy afSintering, edited by Stojanovic et al.

ATOMIC PER CENT COPP ER
20 40 60 80 100
~ 1600(J,...-----.---- r - - - - - . - -- . - - - - ,
-c
(9 (a)
~
I-
Z
W 1200 y + melt
o gas (b)
(/) ..... , - - __ .
w 1000
w MAGN ETIC TRANSFORMATION
a:::
(9
w 800 y
o
z 600
w y +J3
a:::
:::J
~
W
a.
::2
w
I-
-20- 3'=0--}40=--:5::';0,..--:6~0,..--=7';:;-0-8;f0;:----:9:':0,..--;!Cu
PER CENT COPP ER

Fig. 1 a) Phase diagram of cobalt-copper alloys, b) Illustration of the
melt-spinning technique used for preparing metastable alloys in ribbon form
Joule heating on transport properties in metastable CU8SCOl5 ribbons . This particular alloy
composition was selected because the magnetoresistance reaches a maximum I with the
addition of 15 at. % Co .
EXPERIMENTAL
Metastable CU8SC01S ribbons were made by melt-spinning using a quartz crucible with
an orifice diameter of about 1 mm (Fig. l.b). All process parameters, except Cu-drum
rotating velocity, were kept constant: ejection pressure, crucible-to-wheel distance and melt
temperature. The peripheral wheel velocity was changed from 24 m/s to 29 m/s in order to
increase the quenching rate . The resulting ribbon thickenesses were in the range of 50 11m
to 35 11m, that is, the ribbon thickness is inversely proportional to the wheel velocity.
The crystallographic phases of studied samples were ascertained using the X-ray
diffraction method (XRD Phillips 1710 Cu Kal and Cu Ka2 radiation, operating at 40kV-32mA).
DSC was carried out on a Shimadzu DSC-50, in continuous nitrogen flow at scan rate of60K/min.
Electrical resistance was measured using the four-probe de technique with pressure
contacts. Pieces of ribbons five centimeters long and copper wires were attached to a
ceramic block. A de current of 10 rnA was used. Different samples were submitted to dc
Joule heat ing in air under selected electrical currents. Variations in the sample resistance
were recorded using the four-probe technique 4 by simultaneously measuring the voltage
across the sample and the electrical current flowing in it. The magnetoresistance was
measured at room temperature by means of the four-point method. The distance between
voltage contacts of 37 mm was in the region with 99 % homogeneity of an external dc
magnetic field (produced by Helmholz coils) applied in the longitudinal direction of the ribbon.
RESULT AND DISCUSSION
We will first analyze the results of electrical resistance and DSC measurements, as it
has been previously established that structural changes in metastable alloys could be
efficiently observed by these experiments.
600
2.5 r - - - - - - - - - - - - - - - , . . . - - - - - - - ,
;50 tLm
2.0
1.5
400 500 600 700 800 900

Temperature, T (K)
Fig . 2 Temperature dependence of relative electrical resistance of CUS5CO'5
for samples with different thickness
Fig. 2 shows the relative electrical resistance L'lR I R 300K as a function of temperature,
in ribbons prepared with different quenching rates, i.e., ribbon thickness . These curves have
a similar shape to the same function of the amorphous Fe-based soft-magnetic alloyss . Both
ribbons in the first stage show a monotonic rise in resistivity up to 650 K. At about 680 K
there is a resistivity drop associated with the transformation of thermodynamically unstable
(metastable) phase into a stable phase . From about 750 K the resistivity starts rising linearly
in both ribbons . The ribbon produced with a higher quenching rate (40 11m thick) has lower
values of the temperature coefficient of electrical resistance and therefore has a higher
degree of disorder.
The metastable state of the as-quenched sample was also confirmed by the observation
of a sharp exothermic peak on the trace obtained at a heating rate of 60 Kzmin in DSC (Fig.3) .
The onset and peak temperature (678 K) of the first exothermic event is in good accordance
with corresponding onset of a resistivity drop (Fig. 2). As shown by Yu et al.' the second
peak observed at 835 K is associated to the growth of the Co-particles. The enthalpy (area
under the exothermic peak associated to the Co-phase separation) has value of 13.28 Jig.
Fig. 3 DSC curve of CUS5CO, < (healing rate 60 Kzmin.)
In Fig. 4 selected curves of the relative electrical resistance during 30s de Joule
heating for ribbon prepared with the highest quenching rate (35 11m thick) are given . Increase
601
1.8
(d) 3 .7 A
1.6
(C) 3.4 A
1.2
~ I
,/
(b) 2.9A
(a) 2 .7 A
1.0
o 10 . s) 20 30
Tune, t (s
Fig. 4 Resistance vs. time curves of CUX5COl5 samples submitted to different annealing currents
of electrical resistance caused by the increase of sample temperature is recorded . For low
current intensity (curve a) a plateau is noticed caused by the balance between the suprlied
power and the speed of dissipation of heat by conduction, convection and radiation The
increase of current intensity (curves band c) is accompanied by a peak, that is, a significant
structural relaxation occurs and reduction in electrical resistance can be observed . The peak
is followed by continuous resistance decay until a constant value is reached . Finally.
treatment with a highest current intensity (curve d) is followed by a resistance "bump" due
7
to the extra heat released in the sample during the exothermic phase transformation that is,
Co-phase precipitation.
The XRD experiment confirmed that the exothermal peak in DSC curve corresponds to
the Co-rich phase separation. Fig. 5 shows the X-ray diffraction pattern for the as-quenched
250 (111)
Cu
200
I
O l-------,.----~--~~--~---~--___l
20 40 60 80
Two Theta. 2 o (degree)
Fig. 5 X-ray diffraction pattern of CUX5COl5 as-quenched sample
602
ribbon (40 urn thick) . Diffraction lines that correspond to copper (Cu) and copper (I) oxide
(Cu-O) were clearly observed. The lattice constant for the as-quenched sample calculated
from XRD data is 0.3607 nm, and is between values for pure cobalt (fcc Co - 0.3544 nm)
and pure copper (fcc Cu - 0.3615nm). It indicates that Co clusters are noticeably dissolved
in the Cu-matrix. Successive current annealing with intensities of 2.7 A and 3.7 A (Fig. 4)
resulted in a shift in the peak position of the Cu-matrix to lower values of the diffraction
angle 20. Increase in the lattice parameter of this sample (0.3614 nm, that is, almost to the
value of pure copper) reflects Co-particle precipitation. However, X-ray diffraction is
ineffective in the determination of the size of Co-particles due to the high coherency
2
between the Co and Cu phases .
A magnetoresistance maximum is associated with the optimal Co-particles size, that
is, distance between magnetic grains should be longer than the mean free paths of
conduction electrons I . Subsequently, it is necessary to release homojeneous nucleation
during thermal treatments. It was shown by Erukhimovitch and Baram that homogeneous
nucleation in metastable systems could be attained after treatments with a high heating
rates. The de Joule heating was used to anneal the as-quenched samples with a heating rate
of a several hundred degrees per second". The field dependence of magnetoresistance
normalized to the resistivity in the maximum magnetic field (H max=24 kA/m) , i.e.,
magnetoresistance ratio (MR):
MR = P(H) - P(H max)

(1)
P(H max) ,
is shown in Fig . 6. It can be seen that the linear behavior of MR is found in as-quenched
and annealed states. The registration of MR changes even for the as-quenched sample
(curve a) indicated the formation of Co-particles during the ribbon preparation. With
increasing annealing current (curves b and c) MR increases, that is. the improvement of MR
response after thermal treatment is confirmed. The enhancement of MR induced by de Joule
heating could be attributed to an increase of the precipitated Co-phase and the changes in
the grain size I .
12 1-------;==============::::;--1
o as-cast
\lannealing current 2.9 A
~ 10
.... o armealing current 3.4 A
O'-'----'---------'------'----'-------':::L."---l
o 5 10 15 20 25
Magnetic field, H (kAIm)
Fig. 6 The magnetoresistance (MR) of CUK 5CO l 5 for as-quenched and annealed samples
603
CONCLUSION
In conclusion, DSC and electrical resistivity measurements reveal the metastable

structure of a melt-spun CUSSCo lS ribbon. After dc Joule heating MR increases with
increasing Co-precipitation, i.e., volume fraction of the magnetic granules. These results
suggest that Cu-Co ribbons could be used as a suitable material for application in magnetic
sensors devices . Detailed investigations will be performed after completing the high
magnetic field source.
ACKNOWLEDGMENTS
This research was sponsored by the Serbian Ministry for Science and Technology
under the projects numbers 02E12 and C.3.13.32.0099. The authors thank Dr Biljana
Stojanovic and Dr Stevan Durie for their dedicated work on DSC and X-ray diffraction .
REFERENCES
1. R.H.Yu, X.xZhang, J.Tejada, JZhu and M.Knobel, "Structure, magnetic properties, and
giant magnetoresistance in melt-spun metallic copper-cobalt ribbons", J.Appl.Phys .79:
1979-1990 (1996).
2. R.H.Yu, X.X.Zhang, L'Tejada, M.Knobel, P.Tiberto and P.Allia, "Magnetic properties
and giant magnetoresi stance in melt-spun Co-Cu alloys" , J.Appl.Phys.78:392-397 (1995).
3. SZhang and P.M.Levy, "Conductivity and magnetoresistance in magnetic granular
films", J.Appl.Phys .73: 5315-5319 (1993).
4. N.Mitrovie, "The Ettects of Structural Transfonnation on Properties of Solt Magnetic
Materials Appliedin ElectricalEngineering', Ph.D.Thesis, University of Kragujevac (1998)
5. N'Mitrovic, A,MariCie, M.V.Susie, BJordovie and M.M.Ristie, "Research of kinetics of
the crystallization process and the changes of electric and magnetic properties of some iron
based amorphous alloys", Proceeding EUROMA T'95 , Symposium F, Padova/Venice , Italy :
459-462 (1995).
6. J.M.Barandiaran and N.Zabala, "Distribution and evolution of temperature during flash-
annealing of metallic glasses", Proceeding of Symposium on Magnetic Properties of
Amorphous Metals, Benalmadena, Spain:306-308 (1987).
7. PAllia, M.Barico, P.Tiberto and F.Vinai, "Joule heating effects in the amorphous
Fe4oNi4oB2o alloy", Phys. Rev.B 47:3118-3125 (1993).
8. V.Erukhimovit ch and J.Baram, "A model for non-isothermal crystallization kinetics",
Journ. of Non-Cryst. Solids 208:288-293 (1996).
604
THE INFLUENCE OF VOLUME FRACTION AND SIZE OF SiC PARTICLES
ON THE MECHANICAL PROPERTIES OF METAL MATRIX COMPOSITES
Zaklina Gnjidic, Dusan Bozic
Institute Of Nuclear Sciences "VINCA" Materials Science Laboratory

P.O. Box 52211001 Belgr ade
ABSTRACT
Composite materials on the CW67 (AI base matrix) and different content (5,10
and 15 vol%) of SiC particles (0.7J.lm and 33J.lm) have been produced by hot
pressing. The influence of volume fraction as well as particle sizes of the
reinforcement phase on the compressive strength and ductility of the composite
material in peak aged conditions has been investigated. Detailed microstructure
characterization of starting materials and hot press ed composite samples has been
evaluated by optical and scanning electron microscopy (SEM).
INTRODUCTION
The composites of aluminium alloys strengthened by SiC particles are potential

for application in both automotive and aerospace industries, since they are superior
to the conventional aluminium alloys, rega rding stiffness, hardness and deformation
resistance at high temperatures. Thanks to the development of powder metallurgy
techniques in the last few years, the insertion of ceramic particles in metal matrix
becomes available. A new class of composites, known as discontinuously reinforced
aluminium (DRA) materials has been developed accelarately.
Many aerospace applications require high strengths, especially compression-
dominated designs. That is the reason why, DRA materials with AI-Zn -Mg-Cu alloy
matrix are highly developing. The CW67 alloy matrix (AI-8.25Zn-2.2Mg-1.2Cu)
developed as a powder metallurgy product, provides a matrix with high strength,
fracture toughness, and excellent corrosion resistance' . A special attention is paid to
secondary phases, because they influence the structure and mechanical properties of
Al-matrix'.
The objective of the present work is to examine the effects of particulate sizes
and volume fraction on a compressive behavior of reinforced composites, all based
Advanced Science and Technol ogy ofSintering, edited by Stojanovic et al.

on the aluminium alloy CW67. The SiC particulates (0.7Jlm and 33 urn) have been
used as reinforcement phase.
EXPERIMENTAL
The aluminium alloy powder with nominal chemical composition of AI-8.25Zn-

2.23Mg-1.22Cu mass. % (CW67 alloy) and SiC powder, have been used as starting
materials.
The blending of metal and ceramic powders has been carried out in a drum with
cylindrical mixer in air, with constant speed of 70 rpm. The blending process
parameters have been shown in Table 1.
Table 1. The blending process parameters.
Volume fraction 5vol% SiC lOvol% SiC 15vol% SiC

Particle sizes, Ill11 0.7 33 0.7 33 0.7 33
Vol % of mixer fillinz 20 30 20 30 30 30
Time ,min 30 60 30 60 30 60
Hot pressing was done at temperature of 470 Cduring 5h, under pressure of 35
MPa, in argon atmosphere. Microstructure of hot pressed samples was examined by
scanning electron microscope.
A serie of appropriate heat treatments have been applied in order to achieve a
peak aged conditions which were selected for mechanical testing. All samples were
solution treated at 475 C,1h(homogenization) and subsequently water quenching to
room temperature. Peak aged condition was achieved by aging for 24h at 120C.
This selection was made from previous aging studies for hot pressed CW67 alloy 3.
The compressive strength of CW67 alloy and composite was measured at room
temperature. The topography of fracture surfaces was examined by scanning
electron microscope.
The microstructures of CW67 alloy and composites CW67-15vol% SiC after hot
pressing, are shown in Figures 1 a- c.
The microstructure given on Figure 1a is typical for hot pressed alloy CW673.The
presence of an oxide layer around every powder particle is clearly to observe in hot
pressed sample, making visible the prior particle boundaries. Obviously, the applied
pressure was not high enough to cause breaking of oxide layers. The densification
process in CW67 alloys is completed without leaving the open porosity (Table 2.).
Blending of the metallic and ceramic powder components is carried out with the
aim of distributing the ceramic particles uniformly in the aluminium powder matrix.
The details of the blending process were given in the previous work', As known,
mechanical properties of the material are highly dependent on a uniform dispersion
of the ceramic phase in the metal matrix. The blending parameters used in the
present work have enabled nearly uniform distribution of SiC particles in the
aluminium matrix (Figures 1b and c).It has been observed (Figure 2a) that, in the
606
case of 0.7~m SiC particles containing matrix, ceramic particles surrounds the master
particles phase .
Figure 1. Micrographs of the hot pressed a) alloy CW67, b) alloy CW67 reinforced with 15 vol% of
O.7flffi SiC particles. c) alloy CW67 reinforced with 15 vol% of 33flffi SiC particles . Corresponding
particle size distributions have been added to b) and c).
It has been mentioned above that hot pressed master CW67 alloy reached full
density. However, Figure 2b shows the presence of some porosity in the O.7~m SiC
particles hot pressed composite material under the same conditions. The composite
samples show about 90% of theoretical density (Table 2). The residual porosity in
the hot pressed samples is partially a consequence of SiC clusters presence. During
the metallographical preparation of the composite samples, the SiC clusters can be
pulled out from the matrix (Figure 2b, pore A).
Figure 2. Micrographs of the hot pressed alloy CW67 reinforced with O.7flffi SiC a) and b) and 33 urn
SiC c).
The less pronounced effect has been observed in 33~m SiC containing
composite material (Figure I.c, Table 2).
For larger SiC particles present in the matrix, often undergo cracking already
during hot pressing, as clearly shown in Figure 2.c.
The compressive characteristics of aged CW67 alloy as well as alloy based
composites have been presented in Figure 3a-c and given in Table 2. The obtained
yield stress ((JO.2) and rupture strength (RS) values for CW67 alloy are due to
precipitates formation after thermal treating'. After aging, finer grain sizes and
precipitated particles rich in Cu, Mg and Zn (0.01 to O.l~m usually in P/M alloys) are
effective barriers to dislocation motion, leading to increased strengthening. As
known, this leads to reduced ductility in this alloy'.
607
Compression yield stress and rupture strength of the composite material with 5
and 10 vol% of 0.7 um SiC, are lower in comparison to unreinforced alloy (Table
2).The lower strengths of the composite is associated with inhomogeneous structure
(pores, clusters) as compared to the unreinforced alloy" as it is the case in this work
(Figure 2b). The yield stress of the composite with 15 vol % of 0.7 urn SiC is higher
than yield stress of the alloy, despite on residual porosity presence (Table 2).
Table 2. Yield stress and ductility values obtained during compressive tests of CW67
alloy and composite with 5, 10 and 15 vol% SiC.
Material CW67 CW67-5vol% SiC CW67-1Ovol% SiC CW67-15vol%

SiC
0.7J.lm 33J.lm 0.7J.lm 33J.lm 0.7J.lm 33J.lm
Particle sizes, urn
Theoretical density, 2.88 2.90 2.91 2.90 2.92 2.91 2.94
3
PT, wcm
Density after hot 2.87 2.72 2.85 2.66 2.82 2.64 2.79
pressing, PHI' wcm 3
% of theoretical 99.70 93.79 98.12 92.00 96.55 90.72 95.00
density
Yield stress, an?, MPa 511 468 570 506 575 529 638
Rupture strength, 922 786 955 804 975 824 1012
RS,MPa
Ductility, e, % 20.8 17.4 19.7 11.2 12.4 10.8 8.4
The increase in yield stress of composites indicates the additive effects against
dislocation interaction with both the natural alloy precipitates (rich in Cu, Mg and
Zn l ) and SiC reinforcement", The combination increases the lattice strain in the
matrix, causing greater dislocation tangling and requiring higher flow stresses for
deformation.
Better results are obtained for composites reinforced with 33 urn SiC particles
(in all cases values of yield stress and rupture strength were higher then for basic
alloy, Table 2). The main reason for this behavior could be due the distribution of
dispersed better SiC particles (Figure 1e).
650 r - - - - - - - - - - - - - , 1050
(bl
~ .--'
.r': --.
1000
600 (a) 0.7 urn .i.->---
..
.- - _.- 0.7 urn
950
--'
3311m --------- . . 33,tm
~ 550 11. 900
~
~ ~
en
.,:; 500 ~./---- a: 850
450
800
750
------------.
400 +-~-,._~-.___~____,.___~-l 700
o 5 10 15 20 0 5 10 15 20
vol.% SiC vol.%SiC
Figure 3. Effect of the volume fraction of SiC particles on a) yield stress; b) rupture strength; c) ductility .
608
Reinforcement content is another important factor controlling the strength of
CW67/SiC composites. The effect of reinforcement content is shown in Table 2 and
Figure 3 a and b. Yield stress as well as rupture strength increase with increasing
reinforcement content' .
The strength increase of the composites is probably caused by closer packing of
the reinforcement and smaller interparticle spacing in the matrix. This would cause
increased interaction of dislocations with the SiC reinforcement , resulting in
increased strain-hardening.
Ductility of CW67/SiC composites , depends upon reinforcement content and
master matrix alloy' , The volume fraction increase for both O.7J.lm and 33J.lm phase
leads to decrease of ductility. This is mainly due to the greater brittle phase content
in the composite material
Figure 4. Fracture surfaces of CW67 -15vol. % 0.7).lm SiC composite .
The low ductility could be as well as by the preferential distribution of oxides

along grain boundaries which weakens the bonding strength between metal powder
particles (Figure la), by the presence of residual porosity (Figures 2b and 4b) and
SiC clusters (Figure 4c). Our results show ductility of the composites being always
lower than ductility of the unreinforced materials (Figure 3c).
The fractograph (Figure 4a), shows many small voids associated with oxide
particles present along the grain boundaries. Evidence of earlier compressive failure
and low ductility caused by grain boundary fracture, i.e., debonding at the oxide /
metal interface was also found (arrow B in Figure 4a).
The effect of residual porosity on ductility is more noticeable after aging. The
residual porosity reduces ductility in the composite samples, especially for O.7J.lm
particle sizes (arrow C in Figure 4b). The size of SiC particles has an influence on
composite ductility.
Smaller SiC particle sizes tend to form clusters (arrow D in Figure 5c) which
undergo fracturing during pressure exposure. On the other hand, our results have
shown more pronounced decreasing in ductility of composite material with the
presence of larger SiC particles (easily creaked).
CONCLUSIONS
1. Composite material containing 33J.lm SiC particles shows higher compressive

strength in comparison to materials reinforced with O.7J.lm SiC particles and
609
master matrix alloy; the higher SiC particles content, the better compressive
strength values .
2. Generally, composite materials on the AI-SiC basis show lower ductility as

compared to the master matrix alloy; the larger SiC particles, the lower
ductility.
LITERATURE
I. T.E.Tietz, G .Palmer, Advances in Powder Technology in: Advances in PIM Aluminum Alloys
No9, ASM , Metals Park, OH (1986).
2. TJ.A.Doel, P. Bowen, Tensile Properties of Particulate Reinforced Metal Matrix Composites.
Composites Part A, 27A: 655 (1996) .
3. Ni Xiaomin, M.S. Maclean. T .N. Baker. Design Aspects of Processing of Aluminium 6061 based
Metal Matrix Composites via Powder Metallurgy. Materials Science and Technology, voI.10:
452 (1996).
4. Z.S.Gnjidic, D .Bozic. R.Pjanovic, P.Jovanic. Determination of Maximum Rate of Mixing for SiC
particles Distribution in a matrix of Aluminium Alloys, in: Proc. XLI ETRAN
Conference,Yugoslavia: 527 (1997).
5. D.A.Bozic, M. Pavlovic, M.Mitkov, M.Nikacevic, Structure and Mechanical Properties of High
Strength CW67 Alloy Produced by Powder Metallurgy Techniques. Metslurgijs, V.3.: 201
(1997).
6. D.L.Mc Danels, Analysis of Stress-Strain, Fracture and Ductility Behavoir of Aluminium Matrix
Composites Containing Discontinous Silicon Carbide Reinforcement. Metallurgical
Transactions A, vol. 16A: 1105 (1985).
610
INVESTIGATION OF THE MICROSTRUCTURE AND DISTRIBUTION OF
SOLUTE DURING SOLIDIFICATION OF Ai-Cu ALLOY
l 2
Vesna J. Radojevic', Andreja V. VaiCic , Slobodanka N . Nikolic and
2
Aleksandra D. Milutinovic-Nikolic
'Faculty of Technology and Metallurgy

2Institute of Chemistry, Technology and Metallurgy
INTRODUCTION
Phenomenon of solidification process plays an important role in various areas like :

crystal growth, casting processes, liquid phase sintering etc. Results presented in this paper
contribute to investigation of the influence of solidification rate (R) on the interface shape
and the solute segregation.
When a binary alloy is solidified in a temperature gradient the solid-liquid inte rface
tends to a cellular morphology when the solidification parameters (solidification rate - R,
temperature gradient - G, and solute concentration - Co) are controlled within certain limits.
It was observed that the planar interface became unstable above a critical rate given
approximately by I :
G L - m LCo(l-ko)
-= (1)
R pc k oDL
Where G L is the temperature gradient in the liquid phase, Rpc the critical solidification rate
for a planar-to-cellular transition, Co the initial solute concentration, mi. the liquid line slope
in the equilibrium diagram, k o the equilibrium coefficient of distribution, DL the coefficient
of diffusion in the liquid phase.
As the solidification rate was increased above Rpc the interface morphology became
oscillatory unstable, then cellular and at large velocities, dendritic. Near the critical rate,
Rpc, the interface exhibited an irregular morphology.
In the case of normal solidification (Vertical Bridgman method) the whole charge is
molten and it solidifies from one end to another. The distribution of solute concentration in
the solid phase can be described by equation (2)1.2:
C s = Co ko (l-g) kol (2)
Advanced Scienc e and Technology ofSintering, edited by Stojanov ic et al.

Where Cs is the concentration of solute in the solid phase, Co is the initial concentration of
solutes in the liquid phase, ko is the equilibrium distribution coefficient and g is the fraction
of solidified material.
In the real systems the effective distribution coefficient is used instead of the
equilibrium one, equation (3). The k, value varies between ko (the equilibrium distribution
coefficient) and I (when actually there is no segregation of the solute), depending on
solidification rates.
Cs = Co k, (I-g) ke-l (3)
EXPERIMENTAL
The method of normal solidification in a Vertical Bridgman system was used 3.

The experiments were carried out over a range of solidification rates from 1.45x 10-4 to
8.7IxI0-3 cm/s , under a protective nitrogen atmosphere.
An AI-2.86 % Cu alloy was used in the experimental work . The solidified samples
were longitudinal cut, polished, etched and then metallographic investigations of the
microstructure were performed.
Optical emission spectrometry was used for chemical analysis of distribution of the
solute concentration across the specimen.
The assumption was made that the crystallization front moved through the sample at a
rate equal to the descending rate of the ampoule.
Equation (I) was used to calculate Rpc. The values for mi, ko, DL and GL, used in the
calculation, are presented in Table 1. Thus, mi. was calculated from the AI-Cu equilibrium
diagram, while the values for ko4 and DLs-7 were taken from the literature. Temperature
gradient in melt was calculated using mathematical model established according to
experimental measurements of temperature gradient in the furnace. The calculated value for
Rpc was 7.48xlO- 6 cm/s.
Table 1. Data used in the calculation ofRpc
mL (OC/%) -3.4
~ 0.153
D (cmvs) 2.2xlO-s
G (OC/cm) 18.3
It was observed that the solidification rate at which the formation of cellular structures
begins is greatly different from the calculated value for Rpc7 . The transformation occurs
gradually through the stages from the planar interface to regular cells within certain range
of solidification rates. The calculated value Rpc is the rate when the planar interface became
unstable. The cells are beginning to form at much higher rates . The existence of convection
in real system is one of explanation for this deviation, whereas the theoretical model was
developed with assumption that there is no convection. Therefore, the experiments were
612
carried out over a range of solidification rates from 1.45xlO-4cm!s to 8.71x10-3cm!s, and
the planar-to-cellular transition was expected about solidification rate R= 7.5x10-4cm!s. The
microstructures of samples grown on different rates are presented in Figures (1-5).
Figure 1. Microstructure of sample solidified

with R=1.45xlO 4 cm/s, interface - planar
(magnification x 24)
Figure 2. Microstructure of sample solidified with R=2.9xlO4 cm/s, appearance of nodes (magnification x 24)
.
. ......
..,.
Figure 3. Microstructure of sample solidified with R=4.35xlO 4 cm/s, elongated nodes (magnification x 24)
613
Figure 4. Microstructure of sample
solidified with R=8 .7IxlO-4 cm/s,
beginning of the connection of the cells
(magnification X 24)
Figure 5. Microstructure of sample solidified with R=8.71xlO-3 cutis, irregular cells (magnification X 24)
The beginning of connection irregular cells is observed at rate 8.71xlO-4crn/s. It is

obvious that the range of experimental rates lies within unstable region of cell formation .
According to distribution of the solute across the sample, from the equation (3)8 the
effective distribution coefficient k, was calculated for each solidification rate (Table 2). For
the maximal value of experimental solidification rate k, reached value 1, when practically
no distribution of the solute occurred.
Table 2. Effective distribution coefficient k, for each solidification rate
Rx103 em k,
s
8.71
0.87 0.81
0.43 0.86
0.29 0.89
614
CONCLUSION
In this study the influence of the solidification rat e on the microstructure and solute
distribution was investigated . Solidification of AI-2.86%Cu alloy was performed using
Vertical Bridgman method.
According quantitative criterion the critical rate for plane-to-cellular transition (Rpc)
was calculated. It was observed that the solidification rate at which the formation of cellular
structures begins is greatly different from the calculated value for Rpc. Within experimental
range of solidification rate the beginning of plane-to-cell transition was observed .
The effective distribution coefficient k, was calculated for each solidification rate. The
k, reaches maximum at highest solidification rate, while it has minimum for the estimated
planar to-cellular transition rate.
REFERENCES
1. B. Chalmers, Principles of Solidification, Willey & Sons, New York , 1964.

2. W. G. Phan, Zone Melting, Willey & Sons, New York , 1958.
3. A. Valcic , V. Radojevic, S. Nikolic, The influence of crystallization rate and the initial solute concentration
on the crystallization front shape, 1. Soc. Chern. Soc. 60 (I): 33 (1995) .
4. L. Kuchar, J. Drapala, Vyroba vysoce cistych kovu kristaliza~nimi metodami, Hutn icke Listy 7: 498 (1985) .
5. A. Valcic, S. Nikolic, B. Radonjic, Occurrences along solid -liquid phase boundary, Proceeding of VII
World RTC Sintering, H. Novi , p. 156 (1989).
6. A . Valcic, S. Nikolic , B. Radonjic, Kristalizacija kao metoda preciscavanja zonalnim topljenjem, Proc.
XXXIII ETAN, Novi Sad , (1989).
7. V. Radojevic, A. Valcic, S. Nikolic, A.Milutinovic-Nikolic, Solidification of binary alloy by vertical
Bridgman method, Proc. Material's Congress , Cirenc ester, 49 (1998).
8. A. Valcic, V. Radojevic, S. Nikolic, Metode norma1nog ocvrscavanja i zonalnog topljenja kao metode
preciscavanja a1uminijuma, Metalurgija 4(2):237 (1996) .
615
PROPERTIES OF COLD ROLLED SINTERED
COPPER ALLOYS AFTER ANNEALING
S. Nestorovic, D. Markovic
Technical Faculty Bor
Yugoslavia
ABSTRACT
Sintered copper and copper alloys were subjected to cold rolling. The cold-rolled
specimens were isothermal and isochronaly annealed to recrystallization temperature,
during which the values of hardness and electrical conductivity were measured and X-ray
analysis was performed.
INTRODUCTION
Copper has excellent conductivity, but has poor resistance to softening and low
strength at moderate temperatures. This presents a considerable problem to engineers and
designers of electrical equipment1,2.3. Copper has been hardened conventionally by solution
and / or precipitation hardening and dispersion hardening. One of the mechanisms employed
to improve the mechanical properties of single-phase copper alloys is anneal hardening,
whereby considerable strengthening is attained when alloys in cold rolled state are annealed
at 150-300oC. However, the mechanism responsible for this hardening effect is incompletely
understood':'. The effect has been investigated mainly in the cast copper-base alloys and it
was concluded that solute segregation to dislocations give rise to the predominant hardening
mechanism.
In the literature no work has been done on anneal hardening effect on the sintered
copper alloys. The present study gives results of investigations on sintered copper alloys.
Sintered copper alloys were prepared using electrolytic copper powder and powders
of nickel, aluminum and gold with different mass%: Alloy J: Cu-2%Ni-2%Al and Alloy 2:
Cu-2%Ni-l%Au. For comparison the specimens was made from electrolytical copper
powder.
Ad vanced Science and Technology of Sintering, edited by Stojanovic et al.

The specimens, with the dimensions 12 mm wide, 30 mm long and 6.5 mm thick,
were pressed with the pressure of 300 MPa on a hydraulically press. The pressed compacts
were sintered isothermally at 850C in a horizontal tube furnace under an atmosphere ofhigh
purity dry hydrogen for 1 h. After sintering, the hardness and electrical conductivity were
measured on the specimens and than the cold rolling was carried out with different
deformation degrees. The cold-rolled specimens were isochronaly annealed at 30 min
intervals in the temperature range 200-600 oC and the Brinell hardness and electrical
conductivity were measured. X-ray texture analysis was made on the cold-rolled and
annealed samples.
l.Cold rolled sintered samples
The hardness of the sintered Cu-Ni-Au samples during cold rolling increased with
deformation degree due to deformation strengthening (Fig.1). Total deformation degree
after cold rolling for copper samples is under 80% and for Cu-Ni-Au alloy is 92%
(maximum values for hardness was about 135 HB).
Figure 2 shows the dependence of electrical conductivity on deformation degree
after cold rolling. It can be seen that the electrical conductivity is slowly increasing with
deformation degree of 50%, because the porosity of sintered samples decreases during cold
rolling, and after that decreasing, because structure defects increasing. Also, Fig. 2 shows
that the electrical conductivity for sintered copper is higher than for sintered alloy.
CU-Ni-Au alloy ]
140
120
100
80
60
o 20 40 60 80 100
Deformation degree,%
Fig 1. Dependence ofhardness of cold rolled sintered samples of Cu-Ni Au alloy on
deformation degree
618
samples of Cu

50
40
30
~ __-----------4"'-'-----.
20
Cu-Ni-Au
10 +--.----.---r-~-___,r__-~-,__-~-_,_-~-....,
o 20 40 60 80 100
Deformation degree, 'Y.,
Fig.2. Dependence of electrical conductivity of cold rolled sintered samples on

deformation degree
2. Annealed cold rolled sintered samples
Figure 3 shows the dependence of hardness with annealing temperature for the
sintered and cold-rolled CuNiAu samples. The recrystallizaton temperature for the 60%
deformation degree is above 300C. Figures 4, shows the dependence of hardness on
annealing temperature of the cold-rolled sintered samples of'Cu-Ni-Al alloys. It can be seen
that the recrystallization temperature is above 400C for all deformation degrees. For
comparison the recrystallization temperature for sintered copper is above 200C i.e. the
alloying elements (Ni, AI and Au) cause an increase in recrystallization temperature.
Figures 4 shows that in the temperature range of 200-400 oC the hardness values
increase remarkably for all the applied deformation degrees (30, 40, 60 and 70%). This
effect has been investigated mainly in dilute copper alloys containing AI, Au, Ga, Pd, Rh and
Zn45 The results would tend to support the hypothesis that solute segregation to
dislocation, analogous to the formation of Cottrel atmospheres in interstitial solid solutions,
is primarily responsible for the anneal hardening phenomenon.
Figure 5 shows the change of hardness of25, 50 and 70% cold-rolled sintered Cu-
Ni-Au samples with annealing time at temperature 150 and 250C. It can be seen that
hardness decreasing with time and after that increasing, maximum after 150 min, and again
decreasing (temperature 150C).
Fig 6. shows the dependence of texture of Cu-Ni-Au alloy with annealing
temperature (deformation degree 50%).
619
.- =92%
h
140 - =70%
h
A_ =50%
h
y- =25%
h
120
~en
tfl 100
0
-
~ 80
60
100 200 300 400 500 600

o
Temperature, C
Fig. 3. Dependence ofhardness of cold rolled sintered samples of'Cu-Ni-Au alloy on
annealing temperature
---.:=70%
-
180 --.:=60%
---.: = 4 0 %
-"'-&=30%
160
140
120
100
80 -t--,--,.----,---.---.--......--.,.--,.----,--.,----,----,
a 100 200 300 400 500
Temperature, c
Fig. 4. Dependence ofhardness of cold rolled sintered samples ofCu-Ni-Al alloy on
annealing temperature
620
CuNiAu
- . - .=50%, 1=150C
140 -.-.=70% ,1=150C
-A- .=25% . 1=250 0C
-..,.- . =50% . 1=250 oC
_-.=70%.1=250C
130
.,---.---...--.
III
III
o 120
]
~
110
100 -t---,-----,---,--,.---r---,.---,---,.---,,---..-------,
o 100 200 300 400 500
Time, min
Fig. 5. The change of hardness of cold rolled sintered samples with annealing time at
temperature 150 and 250C
2.2
P .. ......,.......
~ 20 ~-~- ~o~ CuNiAu
1.8
-........-...,
1.6 '---""""
\
1.4
(420)
\ ----..
i
\
1.2 31
1.0
0.8
0.6 (200) . .__ . .. . .(~.9J1. .
0.4 L.Y:w------- (111

0.2 '--_"--_-'--_-'-_-'-_--'-_--'-_--'-_--'-_--'_ _L - - - - J
o 100 200 300 400 500
t,oC
Fig. 6. Dependence of Phkl texture factors ofsintered and cold rolled Cu-Ni-Au alloy
on annealing temperature (deformation degree 50%)
621
CONCLUSIONS
( 1) The alloying elements nickel, gold and aluminum were found to have a pronounced
effect on the increase of recrystallization temperature of the cold rolled sintered copper
alloys.
(2)The Cu-Ni-Au alloy has very high plasticity, total deformation degree after cold
rolling is 92% .
(3) The anneal hardening effect was attained at Cu-Ni-Al alloy under recrystallization
temperature in the temperature range of 200-400 oC followed with an increase in hardness,
but at Cu-Ni-Au is not attained.
(4) Anneal hardening may be considered as a gennine hardening mechanism in analogy
to other basic hardening mechanisms such as work, grain size, solid solution and dispersion
hardening.
(5)The texture of cold rolling Cu-Ni-Au alloy changes during annealing.
(6)The results can be applied to derive the composition and processing variables which
determine the practical use such as the strengthening effect of sintered copper alloys.
REFERENCES
(1) N.C.Kothari: Modern Developments in Powder Metallurgy, Toronto, V16

(1984),361.
(2) S.S. Salkova, T. V. Pisarenko, V.G. Segel, N.N. Pavlov and AR.
Shestyuk: Russ. Powder Metall., 9 (1991) ,88.
(3) R.Z. Vlasyuk, V.D. Kurochkin, AA Mamonova and G.A. Shevchenko :
Russ. Powder Metall., 4 (1989) , 43.
(4) M. Bader, G.T. Eldis and H. Warlimont: Metall. Trans., 7A (1976),249.
(5) J.M. Vitek and H. Warlimont : Metall. Trans., lOA (1979), 1889.
(6) S. Nestorovic, D.Markovic and B. Stanojevic: Journal ofMetallurgy,
Belgrade, 3, 4(1997),297.
622
THE EFFECf OF COPPER CONTENTS ON
THE STRUCTURE OF THE ALUMINIUM-
COPPER ALLOY
Biljana Zlaticanin.' Stevan Duric.? Branka Jordovic.l

and Biljana Stojanovici
IUniversity of Montenegro,
Faculty of Metallurgy and Technology,
Cetinjski put bb, 81000 Podgorica, Yugoslavia
2U niversity of Belgrade,
Faculty of Mining and Geology, 11000 Belgrade
3Technical faculty, Cacak , Yugoslavia
4University of Belgrade,
Center for Multidisciplinary Studie s,
11000 Belgrad e, Yugosl avia
ABSTRACf
In this paper, the effects of copper contents in the interval of 0 - 33% on the
structure of the aluminium - copper alloy are examined. Formation of the Al 2Cu
compound is monitored using the X-ray powder diffraction method as well as
quantitative microstructure analysis based on QUANTIMET 500 MC equipment.
Crystal lattice parameters, grain size, dendrite arm spacing (DAS), distribution of
grain size and length eutectic (Le) are determined.
INTRODUCfION
The purpose of the paper is to examine the way of structure formation and the
structure in the aluminium-copper system, depending on copper content. Under
industrial conditions, in standard aluminium-copper alloys, a dendritic grain structure
is typical. Some papersl -', as our previous researches, show a tendency for globular
structure formation with an increase in copper content.
Advanced Science and Technology ofSintering, edited by Stoja novic et al.

Kluwer AcademicIPlenum Publishers, New York, 1999 623
Experimental work can be divided in two phases. The first phase comprises
melting and casting of samples having different compositions from the aluminium-
copper system covering the region of standard, but also higher copper contents , that
are added AlTi5Bl from range of 0,02% to 0,25%Ti acting as a modifier. The second
phase includes characterization of samples obtained by previous melting and casting,
done by X-ray powder diffraction method and modern quantitative microstructure
analysis. Properties of these materials have also been examined including: hardness
measuring and pressure strength determining.
EXAMINAnON OF ALLOYS FROM THE ALUMINIUM- COPPER

SYSTEM BY X-RAY POWDER DIFFRACTION METHOD
An X-ray diffraction has been done for pure aluminium and pure copper, as well
as, for aluminium-copper alloys samples: AlCu5, AlCu8, AlCuI5, AlCuI5Mg3,
AlCu23, AlCu33 in a wide range of angles ( 28 ) from 5 to 100 grades at step width of
0,02 and residue time of 0,40 seconds at one step. A Phillips made diffractometer,
type PW 1710, with a graphite monochromator and a constant divergence slit (D)
lmm, has been used for that purpose. Electricity and voltage of the X-ray tube in the
course of the experiment were 32mA and 40kV respectively, while receiving slit (R)
was O,lmm, corresponding to the tubes having fine focus. A copper X-ray treatment
has been used, that is Cu Kuduz, doublet (Au] = 1,54051 Aand AUz = 1,54433 A).
This method has produced diffractographs on the basis of which microstructural
parameters have been calculated: medium grain size (Table 1), microvoltage (Table
2) and dislocation density (Table 3).
Table 1. Change of medium crystallite size in

crystallographic direction (110) acting as a copper
content in aluminum-copper alloy
TYPE OF SAMPLE medium crystallite size, A

AlCu5 (O,08%Ti) 641
AlCu8 (O,08%Ti) 561
AlCu15 (O%Ti) 748
AlCu15Mg3 (O,08%Ti) 374
AlCu23 (O,08%Ti) 897
AlCu33 (O,08%Ti) 748
The best definition of the crystallite, from the quality viewpoint, established so
far, explains it as a range in crystal matter from which rays are coherently diffracted,
being at the same time separated by dislocations and turned aside from each other at
several angle minutes or grades. Under the microstructural examinations based on X-
ray diffraction on polycrystals, the crystallite is defined by a range of quantitative
values, starting from medium surface dimension of crystallite in a certain
crystallographic direction, through medium volume crystallite dimension, to their
dimensional distributions.
The microvoltages are the most often used parameter of a crystal lattice
deficiency and represent deviations in size d (distance between two crystal planes
having identical hkl indexes) in a crystallographic direction . Such a kind of a crystal
lattice irregularity is a result of dislocations appearance or a deviation in a material
624
chemical composition. Dislocation is also a parameter of a crystal lattice bad
organization, being the most often defined as a minimum density of dislocations
relating to dislocation on crystallite borders.
Table 2. Change of microvoltage in the

crystallographic direction (110) with an increased
copper content in the aluminum-copper alloy
TYPE OF SAMPLE microvoltage
A1Cu5 (0,08%Ti) 0,1920
AICu8 (0,08 %Ti) 0,2194
AlCul5 (O%Ti) 0,1644
AlCuI5Mg3 (0,08%Ti) 0,3305
AICu23 (0,08%Ti) 0,1371
AlCu33 (0,08%Ti) 0,1644
Table 3. Change of dislocation density in the

direction (110) with an increasedcopper content in
the aluminum-copper alloy
TYPE OF SAMPLE dislocation density, cm-2
A1Cu5 (0,08%Ti) 7,3 X 1010
AlCu8 (0,08 %Ti) 9,5 X 1010
A1Cu15 (O%Ti) 5,4 X 1010
AICuI5Mg3 (0,08 %Ti) 21,4 X 1010
A1Cu23 (0,08%Ti) 3,7 X 1010
A1Cu33 (0,08 %Ti) 5,4 X 1010
Microvoltage tests for different aluminium-copper alloys by X-ray powder

diffraction method has shown very high microvoltage values (Table 2), which could be
expected concerning the way of alloys obtaining (mechanical alloying) and a work
procedure.
QUANTITATIVE MICROSTRUcrURE ANALYSIS THROUGH THE

EXAMPLE OF ALUMINIUM-COPPER ALLOYS
In this paper, a special attention has been paid to application of modern

quantitative microstructure analysis as a method for measuring different structural
parameters. This method is more reliable, accurate and faster in comparison to
manual methods of metalographic analysis.
Using an automatic device for quantitative picture analysis QUANTIMET 500
MC by a linear measuring method applied to a sample of pure aluminium and
aluminium-copper alloys, we have determined grain sizes (min, max and medium
values), as well as relative standard measuring errors-RSE (as it can been seen in
Table 4), dendrite arm spacing- - DAS (Table 5) and length eutectic - Le (Table 6),
and also distribution by size (histogram) and volume part icipation of a-hard solution
and eutectic.
625
Table 4. Grain size change showing copper content in the aluminium-copper
alloy
TYPE OF SAMPLE min, um max, urn medium, RSE,%

ftm
Al (O%Ti) 78,94737 2210,52632 537,69559 6,53767
Al (0,08%Ti) 18,98734 303,79747 101,31646 3,45954
AlCu5 (0,08%Ti) 18,98734 215,18987 85,72152 2,59978
AlCu8 (0,08%Ti) 12,65823 189,87342 74,4962 2,81358
AlCu15 (O%Ti) 193,54839 2709,67742 810,48387 5,06863
AICu15 (0,02%Ti) 47,61905 777,77778 230,63492 3,78064
AlCu15 (0,08%Ti) 9,37500 162,50000 53,00000 2,94158
AlCu15 (0,15%Ti) 15,15152 121,21212 49,71717 2,99332
AlCu15 (0,25%Ti) 10,10101 126,26263 48,39966 2,76879
AlCuI5Mg3 (0,08%Ti) 30,30303 212,12121 87,31313 2,42991
AlCu23 (0,08%Ti) 20,20202 151,51515 57,71717 2,91693
AlCu33 (0,08%Ti) 113,92405 721,51899 366,78722 9,03907
Table 5. Dendrite arm spacing (DAS) change showing copper content in the
aluminium-copper alloy
TYPE OF SAMPLE min, urn max, urn medium, RSE, % Vv,ah.s.%

ftm
AlCu5 (0,08%Ti) 1,63 134,69 30,19837 2,93815 84,75599
AlCu8 (0,08%Ti) 1,63 102,04 26,88980 2,37747 83,48839
AlCu15 (O%Ti) 1,63 123,27 20,22536 2,12289 75,14505
AlCu15 (0,02%Ti) 1,63 112,65 23,13044 2,22268 76,67941
AICu15 (0,08%Ti) 1,22 90,61 23,30254 2,32280 74,38530
AlCu15 (0,15%Ti) 1,22 102,86 20,66491 2,16452 74,28727
AlCu15 (0,25%Ti) 1,63 92,24 18,98537 2,09712 71,12862
A1Cu15Mg3 (0,08%Ti) 1,63 102,86 19,65894 2,08456 76,84319
AlCu23 (0,08%Ti) 1,63 79,18 17,37533 2,00740 54,49193
Table 6. Length eutectic (Le) change showing copper content in the

aluminium -copper alloy
TYPE OF SAMPLE min, urn max, urn medium, RSE, % Vv,e .%

ftm
AICu5 (0,08%Ti) 1,63 44,90 5,65236 3,35377 14,59140
AlCu8 (0,08%Ti) 1,63 34,29 5,55443 3,00760 16,34898
AICu15 (O%Ti) 1,63 46,53 7,05516 2,74649 24,58736
AICu15 (0,02%Ti) 1,63 51,43 7,38373 3,24170 22,81881
A1Cu15 (0,08%Ti) 1,63 63,67 8,34064 3,50108 25,01952
AlCu15 (0,15%Ti) 1,22 42,86 6,67921 3,04908 23,15246
AlCu15 (0,25%Ti) 1,22 55,10 7,30999 2,93505 26,14938
AlCuI5Mg3 (0,08%Ti) 1,63 48,98 6,20416 2,80237 23,07952
AlCu23 (0,08%Ti) 1,63 165,71 14,56085 3,91495 44,43566
In this paper, the effects of copper contents in the interval of 0 - 33 % on the

structure of the aluminium-copper alloy are examined. Namely, copper content in the
standard alloys ranges up to around 5% since the maximum solubility of copper in
hard state, at eutectic temperature (548C) is 5,65%. Alloys containing copper up to
33% have been also tested. That is why a considerable eutectic value appears in the
626
microstructure. With standard alloys the primary phase of a-hard solution crystallizes
in a dendrite form. With higher copper contents, eutectic appears in the interdendritic
space and between grains.
Grain size and structure of dendrite and eutectic depend on technological
parameters", first of all on melt temperature and hardening velocity. Material
properties also depend on the last two items. Microstructure can be influenced by
controlling technological parameters and by addition of titanium and boron in form of
AlTi5B1 containing fine insoluble crystals of TiB2 phase acting as nucleants, first for
TiAl 3 phase, and furth er for the aluminium phase and/or of the a-hard solution.
Titanium usually, together with aluminium causes a peritectic reaction with TiAl3
phase which, depending on content, always hardens above hardening point of pure
aluminium or its phase of the a-hard solution.
MECHANICAL TESTING
Properties of these materials have been tested including: measuring of hardness

and determination of pressure strength. Hardness has been measured by use of the
Brinell method (Table 7.) Pressure strength of the samples has been tested on an
electronic cutter of lOt (Table 7.).
Table 7. hardness and pressure strength of the alloys from the

aluminum-copper system obtained during the experiment
TYPE OF SAMPLE HBmedium crO,2p
(N /mm 2 )
AI (O%Ti) 25,025 38,22 119,74
AI (0,08%Ti) 27,00 49,94 141 ,66
AlCu5 (0,08%Ti) 64,35 JOl,92 471,34
AlCu8 (0,08%Ti) 76,725 147,77 478,98
AlCu15 (O%Ti) 90,00 214,01 491,72
AlCu15 (0,02%Ti) 91,25 221,66 491,72
AICu15 (0,08%Ti) 96,625 229,30 557,96
AlCu15 (0,15%Ti) J02,40 230,83 558,98
AlCu15 (0,25%Ti) J03,375 239,49 558,98
AlCu15Mg3 (0,08%Ti) 142,5 371,97 675,16
AlCu23 (0,08%Ti) 110,00 292,99 563,45
AlCu33 (0,08%Ti) 197,50 501,91 672,61
CONCLUSION
Different structural parameters obtained as a result a modern quantitative

microstructure analysis application on the aluminium -copper alloys make it possible
to explain influence of copper and titanium contents on way of formation and the
structure in that system. From the enclosed results of the testing it can be seen that:
-as the copper content increases in the alloyS, medium value of the dendrite arm
spacing (DAS) decreases (see Tab le 5).
-as the titanium content in the same chemical composition of the aluminium-copper
alloy increases , medium value of grain size decre ases (see Tabl e 4). Addition of the
627
AlTi5B1 (that is titanium and boron with ratio of 5:1) performs modification of the
structure, i.e. making finer grains. Thus, titanium is added as a grain refiner and is
very effective with grain size reduction . If a result is a better dispersion of insoluble
components, porosity and nonmetal inclusions, it will improve mechanical properties.
-Pressure strength and hardness of the aluminium-copper alloys increase with copper
and titanium content increase (see table 7). Magnesium also increases pressure
strength and hardness of the alloys and decreases grain size.
By applying X-ray powder diffraction method it has been found out that a
tetragonal Al2Cu with parameters of a crystal lattice: a=6,076 A, c=4,886 A,
V=180,4 A3 is formed.
REFERENCES
1. L. F. Mondolfo, Aluminium Alloys: Structure and Properties, Butterworth and Co (PUblishers) Ltd,
London (1976).
2. X. Yang, J.D . Hunt and D .V. Edmonds, A quantitative study of grain structures in twin-
roll cast aluminium alloys, part II: AA 3004, ALUMINIUM - 69, Jahrgang 1993.2,
pp 158-162, (1993) .
3. AM. Samuel , FH. Samuel , Effect of Alloying Elements and DendriteArm Spacing on the
Microstructure and Hardness of an AI-Si-Cu-Mg-Fe-Mn (380), Journal of Materials Science
1995 Apr 1;30(7):1698-1708, (1995) .
4. B. Radonjic, Directionality of Cast Aluminium Structure, ALUMINIUM 58 (1982) 11,
pp 646-649, (1982) .
5. WQ. Jie, W.Reif, Effect of Cu Content on Grain - Refinement of an AI-Cu Alloy with AITi6 and
AITi5Bl Refiners, ZEITSCHRIFf FUR METALLKUNDE 1993, Vol 84, Iss 7, pp 445-450,
(1993) .
628
ACOUSTO-ELECTRONIC SUPERCONDUCTING SWITCH
P.Y.Nistiriuc, N.P.Bejan, M.I.Sajin, P.H.Deshanu,

Y.N.Bejan, I.YNistiriuc, A.l.Shoulga
Technical University of Moldova

168, Stefan eel Mare av., MD2012 Chisinau, Republic of Moldova
tel: [3732]-24-89-63, e-mail: syrbu@terra.moldova.su
ABSTRACT
The results of design and fabrication of cryotron (Tc = 90K) switch on the Yba2CU307-li
compounds base controlled by surface acoustic waves (SAW) for frequency range from 50
to 500 MHz are presented. The switch is optimized for the minimal switching time and can
be used in memory or switch schemes.
INTRODUCTION
In 1935 Casimir-Janken and de Hassi created cryogen switch or cryotron controlled

by means of magnetic field. Thin film cryotron ensures switching time ~ 2 ns and is formed
by two crossing stripes (divided by insulating layer), manufactured from materials with dif-
ferent temperature values for critical magnetic field.
It is known that superconductivity is ensured by electron-phonon interaction leading to
the electrons interaction and formation of related pairs of electrons. It is supposed to gener-
ate acoustic waves in superconductive material Yba2Cu307-oto destroy electron-phonon in-
teraction and in such a way to switch the superconductor to the conductivity mode.
DESIGN
The main problem in the Yba2Cu307_o cryotron design is to achieve the most effective
generation of SAW and to ensure the minim of switching time. To generate SAW we used
interdigital surface wave transducer (ISWT) with inner pulse linear frequency modulation,

which converts electrical signal into elastic acoustic waves . The period of ISWT is changing
along the transducer in accordance with frequency change during the pulse duration. One
part of the transducer for repper frequency range, another one for lower frequency range .
The signals with linear frequency modulation (LFM)2 of inner part of pulse are the constant
amplitude pulse, which contain linear changing in time oscillation in certain frequency range .
From the condition of parameteres matching of input electric circuit and electrical parametes
of ISWT we defined the converter aperature W and from the condition of equality of acous-
tic channel impedance and electrical oscillator impedance the optimal quantity of transducer
grid stripes is defined' .
In practice the most important are SAW-distribution in the surface layer ofpiezocrystal
with a thickness of the wave's length. It should be mentioned that the chosen superconduc-
tor Yba2Cu301-1I doesn't have the necessary piezoelectric parameters to convert electrical
signal into acoustic one. For this purpose we used additional material simultaneously with
Yba 2Cu301-o, in which effective SAW exciting can be achieved. As the result, comparing the
parameters of materials for SAW devices we chose GaAs with orientation 110, 001 4. For
matching materials with different acoustic impedances one can use a quarter wave layers like
those for optical lenses and VHF transmission line 2, 5.
PRODUCTION
To produce a monolithic switch we used an epitaxial procedure of AlGaAs layer (- 7

um) growth on GaAs substrate above which a quarter wave layer GaAs of orientation 110,
011 was epitaxially grown. Longitudinal and transversal contacts of Cu-Cr were deposit on
the epitaxial layer GaAs by means of reverse photolitography technique and than were acti-
vate in Pd-salts solution. The Yba2Cu301-o layer was deposit onto GaAs epitaxial layer in a
such a way, that its thickness together with that of the GaAs layer is about a wave length
and its transversal acoustic impedance is about the impedance of GaAs 4, 6. Transversal con-
tacts are placed along the b-axis of Yba2Cu301_1I-layer and coincide with the direction of
SAW propagation but the longitudinal ones - along the c-axis of Yba2Cu301-o-layer and are
perpendicular to the direction of SAW propagation. The resulting structure is fixed at the
Yba2Cu3(hllsideby means of the K-18 compound to the lead base. At the same time the K-
18 compound serves as an absorber of reflected acoustic waves from the border of the
"Yba2Cu30 1.1I layer - lead base" interface .
At the final stage the AlGaAs layer was etched and the Cr-Al ISWT was formed on the
high quality surface of GaAs epitaxial layer by means of reverse photolitography, in which
the direction of SAW propagation is perpendicular to the c-axis of Yba2Cu301-o-layer. Di-
mension of the structure is 1,5xl,5 mm.
CONSTRUCTION
The structure of the switch with lead base was put in the case from "brokerit-9". The
measurements were performed at the temperature of liquid nitrogen. To avoid the influence
of cavitation effect in liquid nitrogen on the results of measurements the sample of switch
was put into Cu-tube and was independently fixed from outside . The amplitude of electrical
signal was equal 4V and the ISWT transmission coefficient on the first maximum of fre-
630
quency characteristic was minus 12 dB. The switch time was about some ns and the switch-
ing off from superconductive mode was registered by means of transversal contacts.
CONCLUSION
The possibility of acoustic-electronic superconductive switch fabrication with high op-

eration speed and low losses is shown .
REFERENCES
1. Microe/ectronika. Pod red. N.P.Bogoroditskogo, M.: Sovetskoje radio, 1966

2. Kaino G. Akusticheskie volny, Mir, Moskwa:, 1990
3. Filtry na poverhnostnyh akusticheskih vo/nah . Pod red. G. Methuse - Radio i sviaz', Moskwa, 1981
4. Akusticeskie kristally. Pod red. M.P.Shascoliskoy -Nauka, Moskwa ,1982
5. Sazonov D.M., Gridin A.N., Mishustin B.A. Ustroistva SVC, Vysshaia shkola, Moskwa, 1981
6. Fizicheskie svoistva vysokotemperaturnyh sverhprovodnikov. Pod red. D.M.Ginzberga -Mir, Moskwa,
1990
631
SHARP SHIFT DEVICES
P.V.Nistiriuc, N.P.Bejan, M.I.Sajin,

P.H.Deshanu, I.V.Nistiriuc, Yu.Sholpan
Technical University of Moldova
168, Stefan eel Mare av., MD2012 Chisinau, Republic of Moldova
ABSTRACT
The results of design and manufacturing of the new bimagnetostriction devices which
provide the objects positioning along the X Y, Z coordinate axis and the turning angle round
these axis are presented.
The longitudinal shift range along the X Y, Z coordinate axis is 0. . .300 urn with the
positioning precision 0.05 urn. The angle turning range round X; Y, Z coordinate axis is 90'
with the positioning precision I". The loading capacity is up I 0 newtons.
INTRODUCTION
According to the high technologies trends development a deep interest is shown for sharp
shift devices using the phenomena of magnetostriction and the reverse piezoeffect. In the first
case materials change thei r shape and dimensions under magnetization, in the second case -
under the action of the electric field. Relative dimensions changes of materials ,jIll in both
cases can reach - _ 10' 5.. . 10'2 [I] .
On the basis of the thermobimetallic element's effect and comparison of magne-
tostriction coefficients of used materials doudlelayer stripes were formed .
Such structures allow to obtain high effective compact microshift devices .
DESIGN
The main problem of the high precision positioning (sharp shift) devices design is to
ensure the temperature stability, compactness and effectiveness of the magnetostrictional ele-
ments.
The bimagnetostrictional element operates on the base of the magnetostrictions coeffi-
cients difference between doublelayer stripe's materials. The metal or alloy layer with posi-
tive magnetostrictions coefficient will be called an active one, that with a negative one - pas-
sive. The stripes active layer was prepared from the (45% - Ni l 55% - Fe)-alloy with the mag-

Kluwer Academic/Plenum Publ ishers, New York, 1999 633
netostrictions coefficient Am= 27x 10-6 or the (46% - Fe/54% - Pt)-alloy with Am= 106 x 10-6
and the passive one from Ni with Am= -37x 10-6 [2]. During the magnetization procedure the
stripe is bent in such a way, that the layer with a positive magnetostrictions coefficient is situ-
ated on the prominent side and the layer with a negative magnetostrictions coefficient is on
the concave side.
It should be mentioned that bimagnetostrictional elements can be used as measuring,
compensative, control or protective device.
To raise the effectiveness and compactness of the devices we propose to use sectional
bimagnetostrictional elements represented with the alternation of passive I and active 2 layers
(fig.l ).
2 2
Fig.l Sectional bimagnetostrictional element
The temperature stability of bimagnetostrictional elements is ensured by the choice of

materials (45% - Nil 55% -Fe, 46% - Fe/54% - Pt, Ni), for which Curie-point temperature is
higher than 773K [2].
PRODUCTION
The initial plaque for the bimagnetostrictional elements fabrication consists of the
permalloy (45% - Nil 55% -Fe) or (46% - Fe/54% - Pt)-alloy 0.5 mm thickness base on which
0.2 mm Ni-layer was deposit using galvanic procedure. The layers of the plaque are tightly
joined on the surface of contact and, thus, are the whole. The sectional elements were fabri-
cated by the reverse photolithography method, i.e, on the initial plaque 45% - Nil 55% -Fe)
or (46% - Fe/54% - Pt) were formed and opened on both sides by the indicated method the
windows for Ni-layers deposition.
CONSTRUCTION
The stripe form bimagnetostrictional elements of certain dimentions were cut from the
initial plaque. The stripes were put in the matrix-casing from Al-alloy covered with teflon to
ensure longitudinal, transversal and combined shifts. According to the kind of the shifts the
both or the only one end of the stripe is tightly fixed to the case.
We used combination of two or more stripes disposed in the form of a triangle, square
or other geometrical figures.
CONCLUSION
According to the device's design and the way of positioning of bimagnetostrictional
element one can obtain precision transversal, longitudinal, longitudinal-transversal and angle
shifts. Such devices can be used in electronic and precise engineering, automatic devices, pre-
cision optical-mechanical equipment control systems, follow-up systems, were sharp linear
and/or angular shifts take place.
634
REFERENCES
[1] Spravochnik po elektrotechnicheskim materialaml Pod red. Yu.V. Koretskogo,

V.V.Pasynkova, B.M.Tareeva - L.: Energoatomizdat, 1988, T.3
[2] Preobrazhenskyi A.A., Bichard E.G. Magnitnye materialy i elementy. - M.: Vysshaya
shkola, 1986
635
TIDCKNESS DEPENDENCES OF KINETIC
PROPERTIES OF QUANTUM WIRESOF PURE
AND DOPEDBISMUTH
P.P.Bodiul', AN.Burchakov', D.V .Gitsu', AANikolaeva,b
a Institute of Applied Physics, Kishinev, Moldova

b International Laboratory of High Magnetic Fields and Low Temperatures, Wroclav, Poland
INTRODUCTION
Last time a great number of researches is devoted to the investigation of quantum and
classical size effects [1]. The problem is stimulated by the possibility to detect new effects
having no analogues in bulk crystal and to find new applications. From this point of view the
bismuth-type semimetals are of particular interest [2]. For instance, in thin monocrystalline
bismuth wires , for the first time, the effect of the magnetic flux quantization on a single con-
nected geometry was revealed at the investigation oflongitudinal magnetoresistance. However,
the influence of sizes on thermoelectric effects, particularly in thin wires, is studied only in a
rather limited number of works. Nowadays this problem draws attention due to discovery of
high-temperature superconducting materials with critical temperature T, = 90-130 K. The solid
state depth cooling by the Peltier effect employment is of interest in solving the problem of
practical use ofHTSC materials.
One of the best materials for the thermoelectric cooling is Bi, Te3 with Z3DT= 0.67 at
300 K [3]. A number of theoretical works [4-6] has appeared showing the possibility to in-
crease the material figure of merit ZT, in some complex two-dimensional quantum wells. Spe-
cial attention is paid to the bismuth superlattice [6]. It was shown that Bi is a good thermoe-
lectric material if the overlapping of the valence and conduction bands is removed . [7] The
most important conclusion of [6] is that in order to improve ZT in comparison with the bulk
material it is necessary to separate these two bands by size quantization and to obtain the one-
band system . The ZT increase is determined also by the structure of 2D density of states. By
using the superlattice with quantum wells, it is possible to obtain high Z2DT not only on materi-
als with a large ZT in bulk (as Bi2Te3). Moreover it is better to use a material with low ZT in
bulk (as Bi), but the one in which the condition of the size quantization effect is easier fulfilled.

The aim of our work was to study the thickness and temperature dependences of the
resistance R(T) and thermo-e .m.f. S(T) of thin monocrystal wires of pure and Sn-doped bis-
muth. We were encouraged by the fact that in such thin d < 1urn wires of bismuth the effect of
the magnetic flux quantization was observed, and the thermo-e .m.f. S changes its sign increas-
ing in the positive region at the temperature decrease . This change significantly depends on the
diameter d ofBi wires [8, 9].
SAMPLES, METHODS OF EXPERIMENT
The wires of pure and Sn-doped bismuth were obtained by the liquid phase casting in a
glass coating [2].
With the aid of the X-ray analysis, angular diagrams of the transverse magnetoresis-
tance and Shubnikov-de Haas oscillations was established that all the wires were monocrystals
with the same orientation - the wire axis with the C3 axis make up 19S angle in the bisector-
trigonal plane. The sample diameter was varied from 0.1 up to 10 urn. The perfection of the
crystal structure increases while the sample diameter d decreases . The doped wires were pre-
pared by the method of the successive dissolution of the alloys Bi-0.3at%Sn and Bi-0.05at%
Sn, obtained previously by the method ofzone-meIting recrystallization.
The resistance was measured by the two-contact method . At the measurements of the
thermo-e .m.f. S in order to obtain good wetting and reliable electrical and thermal contacts
with the bulk copper blocks the InGa eutectic was used. The measurement of the thermo-e .m.f.
S in the region 300-80 K was made by the thermocouples copper-constantan, and in the region
80-4.2 K - by Cu-Cu/Fe ones.
The Shubnikov-de Haas oscillations were studied in the field of the Bitter magnet (up
to 14T) and in the superconducting solenoid at the International Laboratory of Strong Mag-
netic Fields and Low Temperatures (Wroslaw, Poland).
RESULTS OF INVESTIGATIONS AND DISCUSSION
The temperature dependences of the resistance R(T) in the range 4.2-300 K, thermo-
e.m.f. S(T) and Shubnikov-de Haas oscillations (H II I) in pure and Sn doped bismuth wires,
(Bi-O.OI at%Sn ; Bi-0.02 at%Sn; Bi-0.05 at%Sn and Bi-0.07 at%Sn) with the diameters from
0.1 up to 10 urn were studied.
Fig.1 shows the Shubnikov-de Haas oscillations of the thin wires of the above-
mentioned compounds.
For pure Bi wires of the used orientation in the longitudinal field H II I the following
periods of oscillations are observed : from the electron ellipsoid (a) pulled along the wire axis,
from almost equivalent oriented two electron ellipsoids (b), as well as from close to the maxi-
mum cross-section of the hole ellipsoid in the T point of the Brillouin zone the difference is
about.
!J.e = (3.8 0.4)10-5 Oe- I ; !J.~ = (8.0 1)1O-50e - 1;!J.~ = (0.6 0.1)10-5 Oe- I [2]
The tin doping of bismuth leads to the shift of the Fermi level BF deep into the T va-
lence band. As it was shown in [8] at BFL ~ 0, the "rigid bands" model is justified, so the iso-
energetic surfaces keep the "ellipsoidal" form, the anisotropy of the electron and hole Fermi
surface in Land T is not changed. Taking into account this and the value of anisotropy of the
hole Fermi surface in T : (SIlIJIXexp / Smiexp = 3.32), the position of B/ for all the above-
mentioned alloys was estimated by the period of Shubnikov-de Haas oscillations from Tholes
and L electrons . In the alloys Bi-0.02 at% Sn only the oscillations from T holes are well
638
observed. The value EFT is about 53 meV, i.e. the Fermi level CFT is found in the region of the
forbidden energies in L, right near the top of the valence band in L or some meV lower. This
conclusion is also confirmed by the longitudinal magnetoresistance absence in the weak mag-
netic field (curve 1, Fig.1). When the Fermi level is shifted lower the valence band top in L the
quantum oscillations of magnetoresistance from "light" holes in L appear(Fig.I 2, 3). The pe-
riod of the Shubnikov-de Haas oscillations does not depend on the diameter. Thus we have
studied monocrystal wires with c/ = 30 meV, i.e. CF is in the conduction band of the L point
of the Brilloiun zone (Bi-O.oI at% Sn); with E/ - in the forbidden band (53 meV) more pre-
cisely, near the top of the "light" holes in L (Bi-0.02 at% Sn); CF =98 meV (Bi-0.05 at% Sn);
EFT =117 meV (Bi-0.07 at% Sn). At the two latter compositions EF is in the depth of the
"light" L and "heavy" Tholes.
R, kOrn R, kOrn
18 4.5
/~
r
.r"\ /
i\\3
!
1.6
R!~
\ i i
\
'I i
\J
/ 1.4
16 I \\ /I
I \ ~o
'. i
'~ 1.2
J ' 2 1.0
14 3.5
'I
\ \ 0.8
\
'. i
.
\
" "\ . 0.6
"'~
1 . ,. ../'/\,~
'~ ' " I~ .0
1\
12 v' \/ \ TK
\ H, kOe
0.4
0 20 40 60 80100120140160 0 50 100 150 200 250 300
Fig.I Longitudinal magnetoresistance of Fig. 2 Normalized resistivity RTf R300 plotted against T for the
Sn-doped Bi wires at 4,2K I)Bi-Q,02at%Sn, wires Bi-O,02 at% Sn of various diameters d. l)d= 0,107f.l., 2)
2)Bi-o,05at%Sn,3)Bi-O,07at%Sn d=0,14f.l., 3) d= 0,21f!, 4) d= 0,22f!, 5)d=0,607f!, 6) d= 0,97f!
Figure 2 shows the temperature dependences of the resistance RTIR300 on T for wires
Bi-0.02 at% Sn for various diameters d. In all the compositions, Bi included, the temperature
dependences RTIR300(T) contain an anomalous maximum, depending on the sample diameter d
and the doping degree. For the samples of pure bismuth the maximum on R(T) has a tendency
to an insignificant shift into the region of higher temperatures with the decrease of d, treated
from the viewpoint of the classical size effect. At T=80 K the specularity coefficient of elec-
trons in Bi is 0.5 [2].
In all the examined compositions, except Bi-0.02 at%Sn, one and the same tendency is
observed: with the diameter decrease the maximum value on RTIR300 increases and shifts by
about 5-10 K into the region of higher temperatures . The wires of the (Bi-0.02 at%Sn) alloy
are characterized by more considerable (~I 00 K) nonmonotonic shift of the maximum. The ab-
solute value of the maximum increases up to MVR= 1.4 in the thinnest sample with d=O.I 11m.
For this composition Bi-0.07 at% Sn the region of the maximum localization makes up 230-
260 K, and its position weakly depends on the wire diameter.
Fig.3 shows the temperature dependences of the thermo-e .m.f. S(T) of Bi wires of
various diameters. As it is seen from the figure, the thermo-e.m.f. depends significantly on the
sample diameter d, and in the temperature region T < 150 K it changes the sign. With the di-
639
ameter decrease the thermo-e.m .f sign change occurs at a higher temperature, being followed
by the maximum formation arising in the positive region at the 40K.
S JlV/K S JlVI K
60
.-- ... 60
.--...

/I -

/I-
40 \ 40 \
20 ~... \ 20 ~... \
\ Ii, \ . Ii!
.
~
I . ?\ o I . ?
o '\ -\ 1 & -\ 1
-20
~-, -20
42- ..
--
& - . . " & -
& &&' - -, & - '.
-40 -40
f A' I '
:::::::I,,-~ -
&& f .
" 1 -c-,

1
-60 - .. T K -60 -"'J. T K
I-r-.-..........--,...........-,-..,...::,
o 50 100 150200250300 o 50 100150200250300
Fig.3 Temperaturedependences ofthe thermo- Fig. 4 Temperaturedependesofthenno-power in

power in Bi wires. 1)d=0,21-1, 2)d= 0,21-1, 3)d= 1,81-1 Bi-O,02at%Snwires. 1) d=O,351-1, 2) d=0,5I-1, 3) =1,81-1
Doping with tin leads to S decrease in the absolute value, and the sign change shifts
into the region of higher temperatures. The size effect in the thermo-e .m.f is manifested most
clearly in the compound Bi-0.02 at% Sn. At 100 K the size effect is observed at d< 1 urn and
in the region d < 0.5 um, the thermo-e .m.f. in the positive region increases nonmonoton
sharply reaching the values of 100-120 ~VIK. (Fig. 4)
For explaining the specificity of the thermo-e .rn.f behaviour in thin Bi wires the ex-
pression for Siiof the bulk Bi samples was used [11]
S. = S' e
o (Jj j + s: h
o (J jj (1)
n aj~ +Uj~
where S; h - are partial thermo-e .m.f of electrons and holes, (Jj~ .h - are partial electroconduc-
tivities.
If we assume bii= cr\1 cr";; = ~i/Yii " where ~ii, Yii - are mobilities of electrons and holes
correspondingly, and ~ii characterizes the averaged mobility in all the ellipsoids, then it can be
written :
S=
S; -IS;lb jj
w
II l+b jj
The partial thermo-e.m.f.s of electrons and holes in semimetals under strong degenera-
tion, at the non-quadratic law of the charge carrier dispersion are given by the expression [12]:
(3)
where r is the parameter of the carrier scattering, k, is the Boltzmann constant , EFe.h is the en-
ergy of electrons and holes, Eg is the energy gap between the conduction and valence bands in
the L-point of the Brillouin zone.
640
In bulk Bi the sign Su- in (2) is determined by the numerator which is negative in the
whole region of temperatures, due to larger mobility of electrons in comparison with that of
holes J1ii / Vii S; /S; .
Assuming that the partial thermo-e .m.f.s coincide with the analogous one in bulk Bi,
the difference in behaviour of the temperature dependences SeT) of the bulk samples and thin
wires must be conditioned by the parameter bii . The classical size effect causes the decrease of
the average mobility of the charge carriers due to their scattering from the surface. As it was
shown in [8], the parameter bii fall leads at the beginning to the thermo-e.m.f. decrease in the
absolute value, and then - to the change of sign and increase of its positive value.
However, as it was shown in [8, 9], the influence of the surface scattering mechanism
on the electron mobility is only a qualitative explanation of the experimental dependences Sd(T)
for the temperatures T > 30 K. The quantitative calculations do not give an agreement between
the experimental data and reasonable values of the parameter bii , as far as the electron contri-
bution to the transport phenomena prevails over the hole contribution even in the thinnest
samples. The existence of positive maximum S= +60 IlV/K in the region of 40 K cannot be ex-
plained by the phonon entrainment effect [13]. Probably, in thin Bi wires the scattering pa-
rameter r changes considerably. As a result, values of the partial thermo-e .m.f.s of electrons
and holes in wires and bulk samples will differ greatly. The influence of the intervalley scatter-
ing of electrons determined by the partial diffusion of the boundary, can be significantly higher
in wires than in bulk samples.
The optimum coefficient of the thermoelectric efficiency was calculated in [6] at 300 K
as a function of the layer thickness for the Bi quantum well obtained in the x-y plane (binary-
bisector plane). The value Z2DT starts to grow sharply reaching the value of8 at d = loA .
It should be expected that in the size-quantized Bi wire (lD-system with the quantum
spectrum Ss,tkz) grown along the bisector axis, weak doping shifts the Fermi level down the en-
ergy scale and if the levels smearing is not strong, the effect may take place at higher values of
d.
In the alloy Bi-O.02 at% Sn, according to the calculations, the Fermi level is localized
right near the top of the valence band in L (srS3 meV). Due to the geometrical factor the
band bottom shifts at the constant concentration (temperature smearing kT at 80 K is about
7 meV). That is in wires with the quantized spectrum there is no light carriers above SF. The
considerable increase of the resistance R(T) in this region is also caused by the vanish of L-
electrons from conductivity at the temperature decrease.
If it is assumed that the heat conductivity X in thin and thick samples is the same (in Bi
even the decrease of the heat conductivity with d decrease is observed) [3], then the increase
ofS up to 120 IlV/K (d= 0.3SIl) at 100 K leads to 3 times increase ofZmT relative to the wire
of the same composition with d= 1.71lm.
At further increase of doping the Fermi level shifts deep into the L valence band L(Bi-
0.05 at% Sn), the conditions for dimensional quantization will be more strict and in this case
also. The maximum of S obtained at 80 K made up 60 IlV/degree and the dependence S(d) is
more smooth . In the alloys Bi-0.07 at% Sn the size effect in both the resistance and S is sup-
pressed .
Thus, varying the doping degree one can shift the Fermi level near the top of the va-
lence band in L and bottom of the conduction band in L- point. At the high structural perfec-
tion of thin wires and at a certain optimum position of SF one can achieve the size quantization
of the energy spectrum and manifestation of this effect in the thermo-e .m.f. at the temperatures
T > 80 K and at the thicknesses about 10.5 em.
641
REFERENCES:
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nucleus and high energy physics. Leningrad, part III, p.290-33I, 1971.
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bismuth single crystals located in a magnetic field. JETP, v.77, 6, p.2332-2344, 1977.
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Phys. Rev. B. (1993),47, (19), p. 12727-12731.
6. L.D. Hicks, T.C. Harman, M.S. Dresselhaus, Use ofquantum-well superlattices to obtain a high figure of
meritfrom nonconventional thermoelectric materials. J. Applied Phys. Lett., 63 (23), p. 3230, (1993)..
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"Shtiintsa", p.264-286, 1982.
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impurities ofthe acceptor type. JETP, v.71, 6(12), 1976.
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temperatures. JETP, 56, 1, p.8-20, 1969.
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13. V.N.Kopylov, L.l.Mezhov-Deglin. Investigation of bismuth kinetic coefficients at helium temperatures.
JETP, v.65, 2(8), p.720-734, 1973.
642
CONTRIBUTORS
Z. Acimovic-Pavlovic
Faculty of Technology and Metallurgy, Belgrade, Yugoslavia
O. S. Aleksic
Institute of Technical Sciences of SASA, Belgrade Yugoslavia
R. R. Aleksic
Faculty of Technology and Metallurgy, Belgrade, Yugoslavia
Lj. Andric
Institute for Technology of Nuclear and Other Mineral Raw Materials, Belgrade, Yugoslavia
R A. Andrievskii
Institute for New Chemical Problems, Russian Academy of Sciences, Moscow, Russia
E. Andronescu
Politehnica University, Bucharest, Romania
Z. Andjic
Scientific Research Center Uzice , Uzice, Yugoslavia
V. M. Antonov
Institute of Metal Physics, National Academy of Sciences ofthe Ukraine, Kiev, Ukraine
M. Atanasovska
Institute of Technical Sciences of SASA, Belgrade, Yugoslavia
T. Babutina
Dj. Bahloul-Hourlier
Laboratory for Ceramic Materials and Surface Treatment of the Limoges University, France
N. P. Bejan
Technical University of Moldova, Chisinau, Republic of Moldova
V. N. Bejan
R. S. Biscaro
Chemistry Institute, Unesp-Araraquara, Sao Paolo, Brasil
V. Blagojevic
Joint Laboratory for Advanced Materials of SASA, Belgrade, Yugoslavia
I. Bobic
Institute for Nuclear Science "Vinca", Belgrade
P. P. Bodiul
Institute of Applied Physics, Kishinev, Moldova
643
D. Bojovic
Scientific Research Center Uzice, Uzice, Yugoslavia
J. Bossert
Universitat "Friedrich Schiller, Technisches Institut, Jena , Germany
S. Boskovic
Institute of Nuclear Sciences" Vinca" , Belgrade, Yugoslavia
D. Bozic
Institute of Nuclear Sciences" Vinca", Belgrade, Yugoslavia
G. Brankovic
Center for Multidisciplinary Studies of Belgrade University, Belgrade, Yugoslavia
A. N. Burchakov
O. Caltun
Al . I. Cuza University, Faculty of Physics, Iasi, Romania
A. S. Camargo
Chemistry Institute, Unesp-Araraquara,Sao Paolo, Brasil
J.M. Chaix
Laboratorie de Thennodynamique et de Physico-Chimie Metallurgishes, ENSEEG BP75, Saint
Martin d'Heres, France
M. Cilense
G.Cosmeleata
Politehnica University, Faculty of Science and Engineering of Materials, Bucharest,
Romania
A. Crisan
Institute of Physical Chemistry, Bucharest, Romania
S. Covic
Scientific Research Center, Uzice, Yugoslavia
Z. Cupic
Institute of Chemistry , Technology and Metallurgy, Belgrade, Yugoslavia
N . Denic
Institute for Materials Testing, Belgrade, Yugoslavia
P. H. Deshanu
V.Dimic
Faculty of Electronic Engineering, University of Nis, Nis , Yugoslavia
R. Dimitrijevic
Faculty of Mining and Geology, Belgrade, Yugoslavia
S. Djukic
Technical Faculty Cacak, Cacak, Yugoslavia
M. Djuric
Faculty of Technology University of Novi Sad, Novi Sad, Yugoslavia
S. Djuric
Faculty of Mining and Geology, University of Belgrade, Belgrade, Yugoslavia
644
D. Djurovic
M. Djuricic
High Technical School, Uzice, Yugoslavia
M. Djuricic
L. O. Dobrianska
Department of X-ray Metal Physics, Lviv State University, Lviv , Ukraine
V. Yu. Dorofeyev
Novocherkassk State, Technical University, Novocherkassk, Russia
Yu. G. Dorofeyev
Novocherkassk State Technical University, Novocherkassk, Russia
M. Feder
AFERRO SA, Bucharest, Romania
E. Fidancevska
Faculty of Technology and Metallurgy, University "St Ciril and Methodius", Skopje, Republic
of Macedonia
T. R. Giraldi
Chemistry Institute-Unesp-Araraquara, Araraquara, Sao Paolo, Brasil
A. E. Gitlevich
Institute of Appl ied Physics, Academy of Sciences of the Republic of Moldova, Moldova
D. V. Gitsu
Z. Gnjidic
Institute of Nuclear Sciences" Vinca" , Belgrade, Yugoslavia
H. Hahn
Darmstadt University of Technology, Materials Science Department, Thin Films Division,
Darmstadt, Germany
I. Hini6
Institute for Physics, Belgrade, Yugoslavia
M. Hi6
L. Isayeva
Inst. for Problems of Materials Science, Ukrainian Academy of Sciences, Kiev, Ukraine
D. Jankovic
Institute of Nuclear Sciences" Vinca" , Material Science Laboratory, Belgrade, Yugoslavia
R. M. Jancic
Faculty of Tehnology and Metallurgy, University of Belgrade, Belgrade, Yugoslavia
Z. Janko vic
B. M. Jatcyk
Ukrainian State University of Forestry and Wood Technology, Lviv , Ukraine
D. Jevtic
Faculty of Civil Engineering, Institute for Materials and Structures, Belgrade, Yugoslavia
645
B. Jordovic
Technical Faculty of Cacak, Cacak, Yugoslavia
N. N. Jovanovic
Institute of Chemistry, Technology and Metallurgy, Belgrade, Yugoslavia
P. Jovanovic
Z. D. Jovanovic
M . G. Kakazey
Institute for the Problems of Material Science of the National Academy of Sciences of the
Ukraine, Kiev, Ukraine
A. Kalezic
E. V. Kartuzov
Inst. for Problems of Materials Science, Ukranian Academy of Sciences, Kiev, Ukraine
V. V . Kartuzov
B. B. Khina
Physicotechnical Institute, National Academy of Sciences, Minsk, Belarus
D. Kicevic
Institute of Nuclear Science "Vinca", Material Science Laboratory, Belgrade, Yugoslavia
s.xu
Institute of Nuclear Sciences-Vinca, Belgrade, Yugoslavia
J. Kiurski
Faculty of Sciences, Institute of Physics, Novi Sad, Yugoslavia
Lj. M. Kocic
Faculty of Electronic Engineering, University of'Nis , Nis, Yugoslavia
Lj. Kolar-Anic
Faculty for Physical Chemistry, Un iversity of Belgrade, Belgrade, Yugoslavia
M. Komljenovic
Center for Multydisciplinary Studies University of Belgrade, Belgrade, Yugoslavia
I. Konchakovskay
Y . Komyushin
Racah Institute of Physics, The Hebrew University, Jerusalem, Israel
Dj. Kosanovic
Refractoory Institute Magnohrom, Kraljevo, Yugoslavia
T. Kovacevic
Faculty of Civil Engineering, Institute for Materials and Structures, Belgrade, Yugoslavia
V. I. Kovtun
Institute for Problems of Material Science of the National Academy of Sciences of Ukraine,
Kyiv, Ukraine
I. V. Krasikov
646
D. Krsmanovic
S. Kulkov
Inst. of Strength Physics and Mat. Sciences, Russian Academy of Sciences, Tomsk , Russia
C. Lacnjevac
V. A. Lavrenko
Institute for Problems of Materials Science, National Academy of Science of Ukraine, Kiev,
Ukraine
S. M. Lee
CISEM, Korean Advanced Institute of Science and Technology, Taejon, Korea
N . B. Lekovic
IRITEL Telecomunications and Electronics Co., Belgrade, Yugoslavia
A. S. Lileev
Institute of Steel and Alloys, Moscow, Russia
E. Longo
Chemistry Department, UFS Car/SP - CEP
L. Lukic
IRITEL Telecomunications and Electronic Co, Belgrade, Yugoslavia
D.Mancic
Faculty of Electronic Engineering, Nis, Yugoslavia
LvMancic
1.1. Margolych
Department of X-ray Metal Physics, Lviv State University, Lviv, Ukra ine
R. Marie
Japan Fine Ceramics Center, Nagoya, Japan
A. M. Maricle
B.A. Marinkovic
Center for Multidisciplinary Studies University of Belgrade, Belgrade, Yugoslavia
Z. Marinkovic
Center for Multidisciplinary Studies, University of Belgrade, Belgrade, Yugoslavia
R. Marinkovic-Neducin
Faculty of Technology , University of Novi Sad, Novi Sad, Yugoslavia
D. Markovic
Technical Faculty of Bor, Bor, Yugoslavia
C. L. Martin
GPM2 , INPGIUJF, ESA CNRS 5010, ENSPG BP 46, Saint Martin d'Hl~res, France
V. A. Melnikova
Ukraine, Kiev , Ukraine
V. P. Menushenkov
Institute of Steel and Alloys, Moscow, Russia
647
R.Micic
NIS Rafinery, Novi Sad, Yugoslavia
S. Mihaiu
Romanian Academy, Institute of Physical-Chemistry, Bucharest, Romania
V. Mikhailov
Institute of Applied Physics, Academy of Sciences of the Republic of Moldova, Moldova
S. Miletic
S. Miljkovic
Laboratory for Electron Microscopy, University of Nis, Nis, Yugoslavia
Y.Milman
O. Milosevic
S. Milosevic
Institute for Technology of Nuclear and Other Mineral Raw Materials , Belgrade, Yugoslavia
M. Milosevski
Faculty of Technology and Metallurgy, University "St Ciril and Methodius", Skopje, Republic
of Macedonia
T. Milovanovic
Cement Factory "Novi Popovac", Popovac, Paracin, Yugoslavia
A. Milutinovic-Nikolic
V.Minic
V. Mitic
Faculty of Electronic Engineering, University of Nis, Nis, Yugoslavia
M. Mitkov
Institute of Nuclear Sciences " Vinca", Material Science Laboratory, Belgrade, Yugoslavia
I.Z . Mitrovic
Faculty of Electronic Engineering, University of'Nis, Nis, Yugoslavia
N. Mitrovic
I. H. Moon
Dept. of Materials Engineering, Hanyang University, Seoul, Korea
M. Muntean
Politechnica University Bucharest, Bucharest, Romania
M. Muravljov
Faculty of Civil Engineering, Institute for Materials and Structures, Belgrade,Yugoslavia
G. C. Nair
Radiochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai
S. Nestorovic
Technical Faculty of Bor, Bor, Yugoslavia
A. Nikolaeva
Institute of Applied Physics of Academy of Science, Kishinev, Moldova
648
A. A. Nikolaeva
International Laboratory of High Magnetic Fields and Low Temperatures, Wroclav, Poland
J. Nikolic
M. V. Nikolic
Joint Laboratory for Advanced Materials of the Serbian Academy of Sciences and Arts,
N . Nikolic
Institute of Technical Sciences of SA SA, Belgrade, Yugoslavia
P. M.Nikolic
Institute of Technical Sciences of SA SA, Belgrade, Yugoslavia
S. N. Nikolic
Z. S. Nikolic
I. V. Nistiriuc
P. V . Nistiriuc
Technical University of Moldova, Chisinau, Republic of Mo ldova
C. Novae
Metav S.A. Bucharest, Romania
T. Novakovic
Si Omic
Center for Multydisciplinary Studies University of Belgrade, Belgrade, Yugoslavia
H . Pastor,
CERMeP, Grenoble, France
F. G. Paul
Building Technical University, Bucharest, Romania
V. Paunovic
Faculty of Electronic Engineering , University of Nis, Nis, Yugoslavia
V. B. Pavlovic
Faculty of Agriculture, Department of Physic, University of Belgrade, Belgrade, Yugoslavia
V. P. Pavlovic
Faculty of Mechanical Engineering, Department of Physics, University of Belgrade, Belgrade,
Yugoslavia
V. Pejovic
IRITEL Telecomunications and Electronics Co ., Belgrade, Yugoslavia
L. Perazolli
Lj. Petrasinovic-Stojkanovic
M. Petrov
ITNMS, Belgrade, Yugoslavia
649
A. Petuchov
Z. V. Popovic
Z. Preradovic
IRITEL Telecomunications and Electronic Co., Belgrade, Yugoslavia
S. Prokic
Center for Multidisciplinary Studies, University of Belgrade, Yugoslavia
V. Radic
Military Technical Institute, Belgrade, Yugoslavia
S. M. Radic
Institute of Technical Sciences of the Serbian Academy of Sciences and Arts, Belgrade,
Yugoslavia
V. Radojevic
Faculty of Tehnology and Metallurgy, University of Belgrade ,Belgrade, Yugoslavia
K. Radulovic
M. Rajkovic
Institute of Food Technology and Biochemistry, Zemun, Yugoslavia
V. Rajkovic
A. Rankovic
M. M. Ristic
Serbian Academy of Sciences and Arts, Belgrade, Yugoslavia
M. T. Ristic
Joint Laboratory for Advanced Materials of the Serbian Academy of Sciences and Arts,
T. Sablina
Inst. of Strength Physics and Mat. Sciences, Russian Academy of Sciences, Tomsk, Russia
M. I. Sajin
N. Savchenko
Inst. of Strength Physics and Mat. Sciences, Russian Academy of Sciences, Tomsk , Russia
A. P. Savitskii
Institute of Strength Physics and Materials Science, Russian Academy of Sciences, Siberian
Branch,Tornsk, Russia
M.Savyak
E. Segal
University of Bucharest, Faculty of Chemistry, Bucharest, Romania
Z. Sekulic
I. Shcherba
Lviv State University, Department of X-ray Metal Physics, Lviv, Ukraine
650
Yu. S. Sholpan
A. 1. Shoulga
D.l. Siapkas
Department of Physics, Aristotle University ofThessaloniki, Greece
R. Lj. Sirneunovic
N.Simic
Joint Laboratory for Advanced Materials, SASA, Belgrade, Yugoslavia
Z. Simoes
D. Simovic
Institute of Food Technology and Biochemistry, Faculty of Agriculture, University of Belgrade,
T. Sreckovic
G. M. Stanisic
D. Stefanovic
Faculty of Electronic Engineering, University of Nis , Nis, Yugoslavia
B.D. Stojanovic
S. Tadic
N. Talijan
M. Tasic
Scientific Research Center, Uzice , Yugoslavia
S. Tebcherani
Chemistry Institute, Unesp-Araraquara, Sao Paolo , Brasil
l.M. Telychyn
Department of X-ray Metal Physics, Lviv State University, Kyryla & Mefodiya, Lviv , Ukraine
N. Teoharie
AFERRO S.A., Bucharest, Romania
P. Thomas
Laboratory for Ceramic Materials and Surface Treatment of the Limoges University, France
1. Timofeeva
G.P. Tiwari
Metal Physics Section, Materials Science Division, Bhabha Atomic Research Centre, Trombay,
Mumbai, India
T. V. Tomila
Ukraine, Kiev , Ukraine
651
M. rene
B.Trifanescu
AFERRO S.A. Bucharest, Roman ia
A. Tucic
I. Uvarova
J. Uzelac
V.Z. "Morna Stanojlovic", Batajnica
A. V. Valcic
Faculty ofTehnology and Metallurgy, University of Belgrade , Belgrade, Yugoslavia
1. Varela
Chem istry Institute, Unesp-Araraquara, Sao Paolo, Brasil
R. Vasic
D. Vasiljevic-Radovic
M. Vasylkovska
Inst. for Problems of Materials Science , Ukrainian Academy of Sciences, Kiev, Ukraine
V. M. Vilceanu
AFERRO S.A. , Bucharest, Romania
G. T. Vladisavljevic
Institute of Food Technology and Biochemistry, Faculty of Agriculture, University of Belgrade,
M. Vlasova
Inst. for Problems of Materials Science, Ukrainian Academy of Sciences , Kiev, Ukraine
J. Vodnik
Institute of Nuclear Sciences " Vinca", Lab. for Thermal Engineering and Energy, Belgrade,
Yugoslavia
T. Volkov-Husovic
Faculty of Tehnology and Metallurgy, University of Belgrade, Belgrade, Yugoslavia
Z. M. Vukovic
Lj. Vulicevic
Technical Faculty of Cacak, Yugoslavia
M. Winterer
Darmstadt University of Technology, Materials Science Department, Thin Films Division,
Darmstadt, Germany
D.M. Won
Dept. of Material Engineering, Hanyang University, Seoul , Korea
M. A. Zaghete
Chemistry Institute, Unesp-Araraquara, Sao Paolo , Brasil
M. Zaharescu
652
Ya. V. Zaulichny
Institute for Problems of Material Science of the National Academy of Sciences of Ukraine,
Kyiv, Ukraine
S.Zec
B. Zlaticanin
Tehnical-Metallurgical Faculty, Podgorica, Yugoslavia
T. T. Zorba
Department of Physics, Aristotle University ofThessaloniki, Greece
S. Zuca
Z. Zakula
Center for Multidisciplinary Studies, Belgrade University, Belgrade, Yugoslavia
B. Zivanovic
D. Zivanovic
Lj. Zivkovic
653
INDEX
Acoustic emission method, 593-595 Alumina based refractory (conI.)

Activated phosphate ore, 197- 198 thermal properties, 29 1
Activation energy Alumina catalyst, 347
of dislocation movement , 508-51 1 AI-Zn-Mg-Cu alloy, 605
of plastic deformation, 508-5 10 AI-8.25Zn-2.2Mg- 1.2Cu alloy: see CW67 alloy
of self diffusion, 509- 510 Ammonium-sulphate corrosio n, 307
Advanced electron ic ceramics, 367-369 Amorphous metal alloys, 587
circ uitry, 370 Anisotropy
ionic and electronic phenomena, 369 pore contribution to, 16
structure, 368 Annealing, 599, 6 17
Aeroso l, 153 Automatic grain counter, 193-1 98
generation of films, 109 response hypothesis, 195-1 96
spray pyrolysis, 119
synthesis , 103
Akima interpolant, 400, 402 BaAlz04, 172
AI-Cu alloy, 6 11, 623 BaAIZSiZO g, 167, 172, 205
dendrite arm spacing , 626 BaCOJ, 167,413
dislocation densit y, 625 BaC0 J"AIZOJ-SiO Z' 167,205
eutectic length, 626 mechanical activation of, 167-173,205-210
grain size, 626 X-ray patterns, 169- 171
hardness, 627 Ba-Pb-Ti-O ceramics
microstructure, 6 11, 613-6 14 DSC analysis, 4 16
pressure strength, 627 semiconducting properties, 413-4 18
solidifica tion of, 6 11-6 15 SEM micrograph, 416
XRD,623 resistivity vs. temperature, 417
AlzCu, 6 13 X-ray diffraction pattern, 415
AI matrix, 605 BAS: see BaA1 ZSizOg
AI powder, 551 Ba zSi0 4,1 72
inverse pole figure, 553 BaTi0 3, 364, 371, 373, 374, 385, 391,403,408,
volume fraction, 553, 555 419,431
AIN,489,491-495 area of the co ntact zone, 401
calculation of powder compaction, 491 band domain size, 395
post-compaction properties, 492 dielectric loss angles, 410
AlzOJ, 167, 172, 197,413,483, 537, 575 dielectric permitivity, 388, 406, 410
AlzOJ glass system, 33-34 diffraction pattern, 405
Alumina, 199-201, 290 dilatometric curves, 404
granulometric compositio n, 20 1 domain structure, 391
shape factor, 202 doped with 5% LiF, 387
specific surface area, 202 doped with Nb, 385
optical absorption spectrum, 203 far infrared reflectivity, 385-390
XRD,203 ferroe lectric behaviour, 39 1
Alumina based refracto ry, 289-292 heating rate influence on sintering, 403
damage resistance parameters, 291 intergrain contacts, 398
fracture parameters, 292 microstructure, 41 1
mechanical properties, 29 1 microstructural characterization of, 407
655
BaTiO J (cont.) Cellular dislocation structure, 508-510
preparation, 404 Celsian : see BaA1zSips
SEM images of domains , 393 (CeOz)o.s(Sm015)o.z-NiO, 113-118
SEM micrographs, 393, 398, 432 Ceramic properties , 251
structural configuration model, 397 C fibre, 167,241
transmi ssion spectra , 390 Characteristic deformation temperature, 508
BaTiO J ceramics Charge carrier dispersion, 640
stereological constituents, 438 Chemical deposition, 271
structural model of, 431 Chemical gypsum , 323; see also Phosphogypsum
BaTiO J ceramic grains, 436 Chemical kinetics , 75
BaTiOrnovolac composite, 419 Chemical vapour synthesis, 138
dielectric properties, 421-423 Clausius-Mossotti approximation, 14
relative permitivity, 422 Coalescence, 175
synthesis, 419-421 Coble 's two-sphere model, 432-434
BaTiO J structure prognosis, 431 Coherer, 497-498
BET method, 355, 378 characterization of metal powder, 497
Bi,637 characterization of semiconducting powder, 497
Bimagnetostriction devices, 633 Cold pressed Al powder, 551-556
Binder, 527 Cold rolling, 617
Bioactive ceramics, 237-243 Cold sintering
Biomaterials, 237 of Fe powder, 557
Bi ZOJ,445 of metal powder, 569
Biot number , 290 Combustion synthesis by mechanical alloying , 181
Bi-Pb-Sr-Ca-Cu oxide powder Compact
DTA curve , 155 growth,24
SEM photomicrograph, 157 shrinkage, 24
synthesis of, 153-157 volume changes of, 23
XRD pattern , 156 Composite ceramic s, 407
Bi ZTe J,637 Composite materials, 527-530
Bi wire, 637 Composite powder, 113-118
thermopower, 640 CoO ,425-426
Boehmite sol, 347-348 CoO-MoO/y-AIPJ,341
effects of calcination temperature, 350 average pore diameter, 343
kinetics of sintering, 351 pore size distribution, 344
PYA doped, LaZOJ added, 349 pore volume, 343
Bouge's correlations, 306 surface area , 342, 344
Brass, 497 Cordierite ceramics: see MgO-AlzOrSiO z system
Bray-Liebhafsky oscillatory reaction, 76 Creep, 513
Brownian motion, 37 Critical solidification rate, 611
Bulk heating , 4 Crystallization kinetics, 337-340
driving forces of, 4, 14 CSMA :see Combustion synthesis by mechanical al-
loying
C,527 CU,497,527,537,581,617
Calcium sulfoalum inate, see also 4CaO 3AIPJSOJ dislocation density, 540
compressive strength , 286 grain size, 539, 541
mechanical properties, 286 lattice distortion, 539
X-ray intensity, 284 microhardness, 542
Carbon, 531 particles , 541
4CaO 3AIPJSOJ,283-287 XRD analysis, 538
CaO-AIPrSOJ system : see 4CaO 3AIZOJSO J CuAI J.5 , 537
CalQ(P0 4MOHh : see Hydroxyapatite dislocation density, 540
CdO,245 grain size, 539, 541
lattice constant, 262 lattice distortion, 539
mean grain size , 260 microhardnes s, 542
sintering diagram, 248 particles , 541
width of diffraction peak , 262 XRD analys is, 538
CdO -BiZOJ system , 259-263, 265-269 Cu+3 %AIPJ
grain size distribution, 267 dislocation density, 540
microstructure, 266 grain size, 539, 541
SEM microphotograph, 261 lattice distortion, 539
volume fraction, 268 microhardness, 542
656
Cu+3%A I20 3 (cont.) Diffusion zone, plastic flow in, 2 1
microstructure, 542 Dilatometry, 41, 143
particles, 54 1 Dislocation mechanisms, 5 13
XRD analysis, 538 Dislocations
Cu-alloys, 6 17 immobile, 8
Cu-Co alloy mobile. 8
phase diagram, 600 Dispersivity degree, 175
CUS5CO l5 alloy, 599 Distribution of solute co ncentration, 6 11
annealing of, 599 Doping degree, 641
DSC, 601 Dynamic recrystallization temp erature, 508
magnetoresistance, 603 DyP 3, 475
relative electric resistance, 60 I
resistance, 602
EDS analysis, 307
transport properties, 599
Effective dis tribution coefficient, 6 14
XRD,602
Effective stress, 513
Cu70%Fe30 % powder mixture, 569-574
Electric conduction
DSC thermogram, 57 1
of iron armo ur, 532
kinetic parameters, 573
of iron powder, 532, 534
specific electric resistivity, 572
of powder carbon, 532
XRD ,570
of steel, 534
Cu-rnatrix, 545
Electro n state
strengthening, 537-543
partial density of, 82
Cu-Ni-A u alloy, 6 18
total density of, 82
annealing of cold rolled sintered, 6 19
Electron structure, 8 1
electrical conductivity, 6 19
Electro spark alloying, 159-163
hardness, 6 18, 620-62 1
Energy dispersive ana lysis: see EDS analysis
Phkl texture facto r, 621
Epitaxial layer, 630
Cu-pow der
Expans ive cement clinker: see Sulphoa luminate
com pact, 49- 5 1
clinker
harden ing mechanisms, 545-550
Explosive conso lidation of AIN powder, 489-495
Cu-Ti alloys, 546
External field, 4
hardness, 548
microstructure, 547
Cu-Ti-TiSi 2 alloys , 546 Far infrared reflectivity, 385
hardness, 548 Fe, 527, 532
microstructure, 547 crystallite size, 560
CW67 alloy, 605 DSC,563
ductilit y values, 608 density, 567
micrograph, 607 electrical resistance, 567
yield stress, 608 enthalpy, 562
CW67 -SiC composite , 606-609 microhardness, 567
compressive characteristics, 607 powder, 557
ductility values, 608 propert ies of cold sintered, 566
effect of volume fraction , 608 relative density, 558-559
micro graph , 607 thermo-electro motor force, 567
yield stress, 608 FeS9.8NiI.5Si5.2B3Co.5 amorphous alloy
activation energy, 590
Deformation isothermal dependence, 590
co ld, 508, 5 11 specific elec tric resistance, 588- 589
during creep , 5 13 structure relaxation kinetic parameter s, 590
hot, 508, 5 11 Fep3,425,453
warm, 508, 5 11 diffractogram, 273
Deformation degree, 587 DSC diagram, 273
Deformation texture, 554 screen printed sample, 272
Dendrite arm spaci ng, 623 thick films of, 271-275
Densification, 58 , 137 Fe46 %-Pt54 % alloy, 634
Diamond-WC-Co, 125 Fer mi level, 64 1
Diffusion Fly ash, chemical co mposition of, 310
coefficient, 51-53 Fractal interpola tion, 399
time relat ion, 52 Fractals in ceramic structure, 397
interaction of so lid and liquid phases, 20 Fractal surface, 400
657
Fracture surface structure, 5 16 Liquid phase sintering, 19,22, 29, 55, 205-209,
Freeze-drying method, 143 594
Lithium ferrite, 453-458
GaAs, 630 ceramic structure, 454
Gas atomised powder, 547 microstructure, 455
Geguzin, equation of, 68 porosity histograms, 456
General thermodyna mic sintering model, 304 resistivity, 457
Glass, 337 saturation magnetization, 455, 457
crystallization kinetics, 339 Loading capacity, 633
nucleation curve, 338 LSGM-N iO: see L30.9Sro. IG30. sM ~.z03-NiO
X-ray powder diffraction pattern, 340
Glass sheet, 329 MA: see Mechanical alloying
mathemat ical model, 329 Magnetic transformation, 600
program algorithm, 330 Magnetoresistance, 599-600
process of drawing, 329-335 Matrix alloy, 484
simulation results, 331- 334 Matrix casing Al alloy stripes, 634
Gradient material s: see Multilayer materials Matrix composites, 484
Grain Matrix interface in bonding layer, 576
boundary migration, 34 Master sintering curve, 69
growth, 137,259 Mechanical activation, 167, 187, 193, 199, 205, 211,
inertia, 196 219
Mechanical alloying, 181
Mechanical properties, 507
HDS catalyst, 341; see also NiO-MoO/y-Al z0 3, Mechanically activated grains, 193-198
CoO-MoO/ y-Al z0 3 Mechanica l waves, 593
Heat conductivity, 641 Mechanochemical synthesis, 175
Heat transfer coefficie nt, 290 Melt spinning technique, 599
High temper ature synthesis, 182 Metal matrix co mposite, 605
n,o, 75, 242 mechanical properties of, 605
Hot deformed powder, 531 MgO-Al z0 3-SiO z system, 317
Hot pressed BaTi0 3, 408-410 density of sintered samples, 3I 8
Hot pressed ceramics, 409 phase composition, 318-320
Hydrodesulphu risation catalys t system: see HDS cat- Mica
alyst mechanical activation of, 2 11-2 17
Hydroxyapatite, 237-243 particle size
dense compact, 239 Gaussian distribution, 212-2 14
E-modulus,240 vibration and planetary mill, 215
SEM micrograph, 239 specific surface, 216
shear modulu s, 240 Microstructural characterization of BaTi0 3, 407
Microstructure, 58, 259
InGa eutectic, 638 development, 29
Ingot metallurg y, 484 gravity induced, 37- 38
InS, 497 microgravity induced, 37- 38
Integrated ceramics, 374-375 evolution, 90
1nterdigit al surface wave transducer, 629 formation, 55
Interface characterization, 575-580 quantitative analysis, 266
Ivensen, equation of, 68 of ZnO, 187
Mineralogical composition, 301
Minimum switching time, 629
Knee temperature: see Characteristic deformation
MLC: see Multilayer ceramic capacitor
temperature
MnCoFe,425
Mn doped SnOz, 437
Lao.sSro.zMnOr YSZ, 113-11 8 MnO, 425-426, 438
Lao.6Sro.4CoOrAIP3' 113-11 8 MnZn ferrite, 445
Lao 9Sro I G30 sM ~. PrN iO , 113-11 8 dilatation curves, 446-447
Layere d silicates, 337 electrical properties, 448-449
Lead zirconate titanate: see PZT linear dimensional change, 446
Least square method, 565 magnetic properties, 450-452
Lichtnecker formula, 423 shrinkage, 446
Lip , 445,453 Modelling, 29, 56, 6 1, 75, 89, 119, 565
Liquid nitrogen temperature, 630 of combustion-type interaction, 181
658
Modelling (co nt.) Packin g (CO Ilt.)
of compact sintered two-dimensional, 9 1
in the presence of liquid phase, 22 Particle
in solid state, 2 1 distribution
control of, 107 bi-modal, 92
grain boundary migration , 34 Gauss, 93
numerical, 32 uniform, 93
process, 32 unimodal, 92
simulation, 32 morphology, 107 , 115
sol ution-precipitation, 30 PbO , 413
Monolithic switch, 630 PbS, 497
Morph otrophic phase bound ary, 356 Pb(ZrTi)0 3, 374
MPB : see Morph otropic phase boundary PCTR effect, 413
Mult ilayer ceramic capacitor, 372 PdAg electrodes , 427
Multil ayer materials, 463 Pechini method , 356
Mult ilayered structure, 575 PEG: see Polyeth ylene alcohol
Peierls-Nabarro stress, 508, 510
Nanocrystalline zirconia based ceramics, sintering of, Phase co mposition, evolution of, 317- 320
137 Phenol novolac resin, 420
Nanophas e particle s, generation of, 105 Phenomenology, 67
Nanostructured material s, 97, 103, 125 Phosphogypsum, 323-328
preparati on of, 97-10 I SEM, 325
structure and properties, 99 TGA, 326
synthesis , structure, properties relationship , 104 X-ray diffractogram , 326
Natural gypsum, 323 Plasma, 159
NdP 3,475 Plasma spray pyrolysis, 225
Neck growth, 61 Plastic deformation, 507
kinetics, 62 co ld, 508
Ni, 575, 634 hot, 508
Ni-AIP 3 lamin ar composite, 575-580 warm, 508
load deflection curve, 578 Polarized BaTi0 3 ceramics , 408
SEM micrographs, 577 Polar materials, 14, 17
spinel phase, 578 Polyethylene glycol, 347
Ni45%-Fe55% alloy, 633 Polyol process , 46 1
Ni-doped W powder co mpact, 44-49 Polyurethane foam, 24 1
NiO-MoO/ y-AI20 3, 341 Polyvinyl alco hol, 347
average pore diameter, 343 Pore
pore size distributi on, 344 diffusion kinetics of, 17
pore volume, 343 equilibrium shape of, 14
surface area, 342, 344 Porosity, 532, 534
Non-isothermal heating, 41 of hot defor med powder, 532-533
Non-oxide cermets, 461 Porous sponge, 241- 242
Novolac,419 Portland cement, 30 1, 307
NTC thermi stors, 424 chemical model, 30 1
disk shape , 425 concentration gradie nt of sulphur, 310-314
resistivity vs. temper ature, 426 concrete corrosion, 307
thick film, 425 determinin g equ ilibrium composition, 304
NTC thermi stor layer, 427 fly ash, 308-3 15
NTC thermistor paste, 430 prognosis of mineralogical com position, 30 1-306
Nucleation , 175 raw materials used, 30 I
Nucleus confluence: see Coa lesce nce sintering model, 304-306
Positive temperature coefficient of resistiv ity: see
On-line method , 593 PCTR effect
Organic matrix, 419 Powder metallurgy materials, 507-5 18
Organic radicals, 357 Powder synthesis, 113
Oxide powder, 119, 143 Pressing
Oxide thermistors, 425 cold, 5 12
resistivity vs. geometry, 425-429 hot, 512, 546, 606
Packing warm, 5 12
ballistic, 9 1 Pressure working process, 507
three-dimensional, 9 1 Protective coverage, 159
659
PTC thermistor, 368 Si 3N4 (COllt.)
PYA: see Polyvinyl alcohol green density vs. additive amount , 206
PZT ceramics, 355 liquid phase sintering of, 205-206,
additives , 357 powder, 131-135
effect of Nb+s, 361-365 XRD,208
effect of Sr+z and B+z, 359-362 Single crystals, 576
lR bands, 358 Sinterab ility, 232-234
phase formation , 357 Sintered Cu, 581
piezoelectric material, 355 density, 58 1
reactivity, 357 electrical conductivity, 581
sintering, 355, 377 specific electric resistivity, 582
TO curves , 358 Sintered metal-graphite materials , 527-530
XRD data, 357 Sintering, 61, 237, 251, 283, 295, 317, 341,519,
617
Quantitative microstructure analysis, 266, 625 activated, 41
Quantum wires, 637 of BaTi0 3, 403
cold, 569
of composite materials, 527-530
Rearrangement, 25, 55 computer modelling of, 89
Receiver circuit diagram, 499 general thermodynamic model, 304
Recrystallization, 551 final stages of, 7, II
Recrystallization grain, 554 initial stages of, 5, 41
Recrystallization temperature, 617 isothermal, 259-263, 277
Rectangular preform, 329 liquid phase, 19,22,29,55,205-209,594
Refractory : see Alumina based refractory of MnZn ferrite, 445
Regime moving forces for, 20
cycling, 12-14 of powder metallurgy materials, 512-515
pulsing, 12-14 ofPZT ceramics, 355-366
Relative heat conduction, 532, 533 of SnO z doped with ZnO, 377-383
Relaxation parameters, calculation of, 9 solid state, 21, 594
Resin, 527 in vacuum, 225-229
Ristic -Jovanovic , equation of, 68 Sintering diagram , construction of, 245-246
Sintering kinetics, 41-53, 67,120,351
Sb doped Bi wires, 638 Si 3N4-TiN composite s, 475
longitudinal magnetoresistance, 639 microstructure development, 477--480
normalized resistivity, 639 SEM,478--480
thermopower, 640 sintering behaviour, 475--477
Sbz0 3 , 4 13 s.o, 167, 172,413
Screen printing technology, 272-274 Smart electroceramics, 372-374
SDC-NiO: see (CeOz)o.g(Sm0l.s)o.z-NiO SmCo s
Sectional bimagnetostri ctional element , 634 coercive force, 523
Sectional elements , 634 hysteresis curves, 522
Sharp shift devices, 633-635 magnetic properties, 519, 523-524
Shear stress, 514 microstructure , 523-524
Shock-wave treatment , 147 micro-X-ray analysis, 512
SHS : see High temperature synthesis SEM micrographs, 520
SiC, 167,483 volume fraction, 522-523
powder, 131-135 SmCo s magnets, 519
Silica aerogel, 277-281 Smz0 3, 475
bulk density, 281 Sn-Sb-Cu-O system, 251-257
IR spectra, 278, 280 ceramic properties, 253
Raman spectra , 279 phase composition , 252, 254
Silicon nitride based composites : see Si 3N4-TiN com- porosity, 256
posite quaternary system, 253
Simul ation , 61 shrinkage, 255
of liquid phase sintering , 29 SnOz, 377, 380,437--444
of neck growth, 61 doped with Mn, 437
process, 31 Ff-IR,439
Si 3N4 , 167,205 linear shrinkage curve, 441
content of p-phase, 208 SEM micrograph, 442
densification degree vs. sintering time, 207 XRD patterns, 440--442
660
SnO z (cont.i Therm o-mechani cal treatment, 515-517
doped with ZnO, 377- 383 Thermo-physical properties, 531-536
linear shrinkage of, 379 Therm o-plastic deformati on, 507
SEM micro graph s, 381 Three point bending test, 579
SnO z based ceramics: see Sn-Sb-Cu-O system TiC, 465
SnS ,497 mechanochem ical synthesis of, 175-179
Sol-gel method, 347 X-ray diffraction patterns, 178-179
Solid oxide fuel cell, 113 TiC-MozC-Ni cermets, 466
Solid ification proces s, 611 effect of binder of TiC, 468
Solidification rate, 611 effect of TiN co ntent, 467
Solution precipitation modell ing, 30 microstructure, 466
Spatial configuration of grains, 399 Ti-Mg production waste, 131
Specific relati ve electri c conduction, 532, 534 TiN, 99- 10 1, 475
Spray drying process, 463 TiO z, 413,437,453
Spray pyrolysis, 113, 153; see also ultrasonic spray Titanium carbonitride based cermets, 464
pyrolysi s, aerosol spray pyrolysis, plasma applications, 470
spray pyrolysis microstructure, 466-470
SrTi0 3, 364,371 propertie s, 466-470
Stoichiometric network analysis, 75 sintering, 465
Stokes' law settlin g, 34-36 Titanium diboride based cermets, 470-472
Structural configuration model of BaTi03, 397 propertie s, 470
Stru ctural relaxation, 587 sintering, 470
Structure of sintered material s, 515 Topochemi cal reaction, 175
Sulph oaluminate clinker, 295-299 Transmitter circuit diag ram, 499
microph otograph , 298 Tungsten, 125
participation of phases, 298 Tungsten monocarbide based cermets, 461
sintering of, 297 20 co mputer model , 55
X-ray diagram, 299
Supercondu cting powder : see Bi-Pb-Sr-Ca-Cu oxide Ultradisperse materials, 125
powder Ultrafine powder, 461
Supercondu cting switch, 629-631 sintering of, 137
Surface adsorpt ion , 231-235 Ultraso nic spray pyrolysis, 106- 110
Surface area, 234 UOz, 67-72, 23 1-235
Synthe sis, 119; see also aeroso l synthesis sinterability, 232-234
of films, 109
of particles, 105
Vacuum sintering, 225-229
Sy nthetic diamond powder
Varistor, 369, 37 1
electron structure of, 147-151
Vertical Bridgman system, 6 12
EPR signal, 150
Viscous force, 56
X-ray spectra, 149
Volume changes
effect of additive concentration on, 26
effect of temperature on, 26
Tamrnan 's equati on , 329
effects of porosity on, 26
Thick films : see Fep3' MnCoFe
Volume fraction, 605
Thermal contacts, 638
Therm al expansion. 588-589
Thermal recovery, 569 Waste, 323; see also Ti-Mg producti on waste
Thermal shock, 289 carbidization of, 133
Thermal stress, 289 nitriding of, 135
Thermi stor, 368, 37 1 WC-Co cermets, 461
with negative temperature coefficient of resistance WC-Ni-Fe-Co alloys, 465
(NTCR), 369 WC powder production, 462
with posit ive temperature coeffic ient of resistance Weertman 's model, 513
(PTC R),368 W-Ni, sintering of, 37-38
Therm istor resistivity W-Ni-Fe compact, 593
disc, 428 acoustic emission signal, 596
interdi gitated,428 sintering of, 596
multilayer, 428
rectangular, 428 YBaZCu30 7_/S' 629-630
sandwich, 428 YNizPz co mpound, 8 1-86
segmented, 428 X-ray emission band , 84
66 1
YNi 2Si 2 compound, 81-86 ZnO, 107, 109,245,371 ,380,413
X-ray emission band, 83 compact relative density, 191
Y203,476 depolarisation factors, 190
Y-TZP ceramics, 225-229 IR spectra, 189
bending strength, 228 microstructure evolution, 187
fracture surface monoclinic content , 227 particle shape parameters, 190
fracture toughness, 227 relative density, 191
synthesis by plasma spray pyrolysis, 225-226 SEM microphotograph, 145-146
TEM micrograph, 226 sintering diagram, 247
synthesis by freeze-drying, 143-146
ZA27 alloy, 483 ZnO-Sn0 2 system
microstructure, 485-486 dislocation density, 221
yield strength, 487 mechanical activation of, 219-222
ZA27-7wt%SiC composites, 483-488 specific surface, 221
yield strength, 487 XRD,220
Zirconia based ceramics, 225 ZrNb 20 7, 364
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ADVANCED SCIENCE AND

Maria Vesna Nikolic

Springer Science+Business Media, LLC

Advanced science and technology of sintering/edited by Biljana D. Stojanovic, Valery

1. Sintering. I. Stojanovic, Biljana D. II. Skorokhod, V. V. (Valerii Vladimirovich) III.

TN697.17 A38 1999

ISBN 978-1-4613-4661-6 ISBN 978-1-4419-8666-5 (eBook)

1999 Springer Science+Business Media New York

All rights reserved

This volume entitled Advanced Science and Technology of Sintering,

Influence of External Fields on Sintering 3

Liquid-Phase Sintering of the Systems with Interacting Components . . . . . . . . . . . . . 19

Simulation of Two-Dimensional Microstructural Development During Liquid Phase

Sintering Kinetic Analysis by Dilatometric Data Obtained at Different Heating

Computer Study of Microstructure Formation by Rearrangement During Liquid

Computer Simulation of Neck Growth During Sintering Process . . . . . . . . . . . . . . . . 61

Phenomenology of Sintering Kinetics Using UOz as a Model 67

Contraction of the Complex Models by the Stoichiometric Network Analysis 75

Scientific and Technological Problems in Nanostructured Materials Science . . . . . . . 97

Aerosol Synthesis of Nanostructured Materials 103

Preparation of Fine, Spherical, Composite Powder by Spray Pyrolysis II3

Synthesis of Submicronic Oxide Powders by Aerosol Spray Pyrolysis: Modeling

Nanostructure Composition of Diamond-WC-Co . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125

Pecularities of Fine-Dispersion SiC and Si 3N4 Powders Obtained from

Sintering of Nanocrystalline Zirconia-Based Ceramics 137

Analysis of Thermal Treatment of ZnO Derived by the Freeze-Drying Method 143

The Effect of Shock-Wave Treatment on the Structural Characteristics of Synthetic

Structural Properties of Ultradispersed Bi-Pb-Sr-Ca-Cu-O Particles Synthesized

Mechanical Activation of BaC03-AIP3-Si02 167

Mathematical Modeling of Combu stion-Type Interaction During Mechanical

Evolution of the Micro structure of Disperse ZnO During Mechanical Activation

Physical Properties of Mechanically Activated Grains 193

Change of the Physical-Chemical Characteristics of the Materials by Mechanical

Mechanically Activated BaC03-AIP3-Si02 Mixture as an Additive for Liquid

Mechanical Activation of Mica 211

The Influence of Mechanical Treatment on Activation of the ZnO-Sn0 2 System 219

Vacuum Sintering of Zirconia Based Ceramic s 225

A Study of Reactivity and Sinterability of Uranium Dioxide Powder through

Sintering and Creation of Porous Structure of Bioactive Ceramics 237

Ceramic Properties of the Sintered Materials in the Sn-Sb-Cu-O System 251

Grain Growth in System CdO-BiP3 259

Characterization of Thick Films of Fe.O, Obtained by Chemical Deposition 27 I

Evolution of the Surface and Internal Structure of Silica Aerogels During

Sintering Conditions and Hydraulic Activity of 4CaO . 3AlP3 . S03 283

Thermal Shock Behavior of Sintered Alumina Based Refractories . . . . . . . . . . . . . .. 289

Sintering of Sulphoaluminate Clinker . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 295

Prognosis of the Mineralogical Composition of Sintered Portland Cement

EDS Analysis of Sintered Material Degradation in an Aggressive Environment . . . . 307

Evolution of the Phase Composition During Sintering of the MgO-Al 203-Si02

Experiences in the Chemical Gypsum-Phosphogypsum Preparation from the Triad

Crystallisation Kinetics of Layered Silicates in Glass 337

The Effect of Atmosphere on HDS Catalyst Sintering 341

The Stability of Porous Alumina Catalyst Support against Sintering 347

Synthesis and Sintering of PZT Ceramics 355

Advances in Sintered Electronic Materials 367

Sintering of ZnO Doped Sn02 377

Far Infrared Properties of BaTi03 Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 385

Characterization of Domain Structure in BaTi0 3 Based Ceramics by Scanning

Fractals in Ceramic Structure 397

The Influence of Heating Rate on Sintering Process of BaTi0 3 Ceramics 403

Microstructural Characterization BaTi03-Composite Ceramics 407

Semiconducting Properties of Doped Barium-Lead-Titanate Ceramics . . . . . . . . . . . . 413

Synthesis and Dielectric Properties of BaTi0 3-Novolac Composite 419