Thermodynamic Modeling and Materials Data Engineering: P. Caliste A. Truyol H. Westbrook

J.- P. Caliste · A.
Truyol
J. H. Westbrook (Eds.)
Thermodynamic
Modeling and Materials
Data Engineering
With 150 Figures and 48 Tables
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Editors:
Dr. Jean-Pierre Caliste
Ministere de l'Economie, Finance et Industrie SQUALPI,
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Prof. Albert Truyol
47, Avenue du Clos Toutain, F-92420 Vaucresson, France
Dr. Jack H. Westbrook
Brookline Technologies, 5, Brookline Road, Ballstone Spa, NY 12020, USA
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ISSN 1431-2107
ISBN-13:978-3-642-72209-7
Library of Congress Cataloging-in-Pblication Data
Thermodynamic modeling and materials data engineering I J.-P. Caliste, A. Truyol,
J.H Westbrook (eds.).
p. cm. -- (Data and knowledge in a changing world)
Includes bibliographical references and index.
ISBN-13:978-3-642-72209-7 e-ISBN-13:978-3-642-72207-3
DOl: 10.1007/978-3-642-72207-3
1. Materials science--Computer simulation. 2. Thermodynamics. I. Caliste, J.-P., 1947-
II. Truyol, A., 1932- . III. Westbrook, J.H. (Jack Hall), 1924- . IV. Series.
TA403.6.T48 1998
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Data and Knowledge in a Changing World
Scientific Editorial Board

D. Abir (Israel) E. Fluck (Germany)
M. Chinnery (USA) A.S. Kolaskar (India)
J. Crease (UK) K.W. Reynard (UK)
J.-E. Dubois (France) J.H. Westbrook (USA)
Corresponding Members
M. Antoninetti (Italy) P. Masclet (France)

M. Attimonelli (Italy) J.C. Menaut (France)
C. Bardinet (France) B. Messabih (Algeria)
C. Bernard (France) P. Mezey (Canada)
H. Bestougeff (France) F. Murtagh (Germany)
Y. Bienvenu (France) G. Ostberg (Sweden)
F.A. Bisby (UK) W. Pillman (Austria)
L. Blaine (USA) J.R. Rodgers (Canada)
G. Blake (France) S.F. Rossouw (South Africa)
J.P. Caliste (France) J.J. Royer (France)
M. Chastrette (France) J. Rumble (USA)
E.R. Cohen (USA) S.K. Saxena (Sweden)
M.-T. Cohen-Adad (France) R. Sinding-Larsen (Norway)
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S. Iwata (Japan) A. Truyol (France)
J.G. Kaufman (USA) A. Tsugita (Japan)
H. Kehiaian (France) P. Uhlir (USA)
A.D. Kozlov (Russia) F. Webster (USA)
F. A. Kuznetsov (Russia) E.F. Westrum (USA)
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D. Lide (USA) Z. Xu (China)
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FOREWORD
J.-P. CALISTE, A. TRUYOL AND J. WESTBROOK
The Series, "Data and Knowledge in a Changing World", exemplifies CODATA's

primary purpose of collecting, from widely different fields, a wealth of information on
efficient exploitation of data for progress in science and technology and making that
information available to scientists and engineers. A separate and complementary
CODATA Reference Series will present Directories of compiled and evaluated data
and Glossaries of data-related terms.
The present book "Thermodynamic Modeling and Materials Data Engineering"

discusses thermodynamic, structural, systemic and heuristic approaches to the
modeling of complex materials behavior in condensed phases, both fluids and solids,
in order to evaluate their potential applications. Itwas inspired by the Symposium on
"Materials and Structural Properties" held during the 14th International CODATA
Conference in Chambery, France. The quality of the contributions to this Symposium
motivated us to present" a coherent book of interest to the field. Updated contributions
inspired by Symposium discussions and selections from other CODATA workshops
concerning material properties data and Computer Aided Design combine to highlight
the complexity of material data issues on experimental, theoretical and simulation
levels
Articles were selected for their pertinence in three areas.
Complex data leading to interesting developments and tools such as:

• new developments in state equations and their applications,
• prediction and validation of physical and energy data by group correlations for
pure compounds,
• modeling and prediction of mixture properties.
These topics reflect recent developments in calculating state equations enabling more
precise property prediction
2 Complex system dynamics and recent progress in:

• understanding the dynamics of complex biomolecular systems,
• the complexity of polyphase structures like: emulsions, gels, foams, micelles,
VI Foreword
• materials surfaces and interfaces,

• computer-aided design of composite materials.
For example, surface properties of multiphase structures often playa major role in
understanding and predicting physical and mechanical global properties of practical
engineering materials
3 Computer aided simulation as a conceptual and practical tool in such areas as:
• thermodynamics in metallurgical processes,
• the synthesis of new materials via: soft chemistry, powder processing and
molten salts,
• characterization of materials structures and behavior modeling,
• data capture and monitoring with intelligent materials and new micro-sensors.
The importance of design strategies that integrate various types of information, in

particular those dealing with dynamic aspects and time-controlled processes are
discussed.
Highlighted results are:

• new thermodynamic data capable of optimizing industrial processes,
• new routes of "soft chemistry" by which new metastable compounds or
materials can be obtained,
• micro-versus macro-structure modeling offering new developments in
understanding mechanical behavior,
• new physical and chemical components providing micro measurements
for more precise experiments.
Society's need for new products as well as concerns for the life cycles of products and
artifacts are examined in the light of the various constraints, technical and
environmental, that must be considered and evaluated as essential factors in
developing so-called "agile" industries.
The editors have sought to bring to the attention of concerned readers in the field work
contributing to the creation of valid and useful tools for data evaluation and for future
evolution.
Acknowledgements: We would like to thank all the authors of this book for their
contributions and for their continual cooperation. We would like to acknowledge the
hard work and dedication of Ms. Bernice DUBOIS in helping to shape this book and
the painstaking efforts of Dr. Karim FRAOUA in putting together the contributions of
authors from 13 different countries.
CONTENTS
CHAPTER 1: NEW DEVELOPMENTS IN STATE

EQUATIONS AND THEIR ApPLICATION
THE EXTENDED ApPLICATION OF A TENSG, VI. THEORETICAL METHOD FOR
CALCULATION OF GASEOUS HEAT CAPACITY
K. - W. Zhang (K. - W. Chang)
PVT MEASUREMENTS OF METHANOL AND ITS SPECIFIC EQUATION OF 11

STATE
Ch. Berro, H. Hocq, C. Rebufa and E. Rauzy
ENTHALPY OF VAPORIZATION OF N-ALKANES (FROM NONANE TO 21

PENTADECANE) EXPERIMENTAL RESULTS - CORRELATION.
C. Viton, M. Chavret and J. Jose
AIMS AND ACHIEVEMENTS OF THE SCIENTIFIC GROUP THERMODATA 33

EUROPE
I. Ansara
FIRST PRINCIPLES CALCULATIONS OF BINARY ALLOY PHASE DIAGRAMS 39

C. Colinet and A. Pasturel
EVALUATION OF EQUATIONS OF STATE AT HIGH PRESSURE FOR liGHT 53

HYDROCARBONS
J.-c. de Hemptinne, A. Barreau, P. Ungerer, E. Behar
CHAPTER 2: PREDICTIONS AND VALIDATION OF

PHYSICAL AND ENERGY DATA
THERMOCHEMICAL MIMICRY 71
J. F. Liebman and H. Afeefy
VllI Contents
COMPUTER-AIDED INORGANIC PROPERTIES ESTIMATION SYSTEM 79

J.-Y. Shen, G.-S. Huang, H. Wen and Z. Xu
ESTIMATION OF PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS. 85

A COMPARISON OF METHODS IN THE CASE OF VAPOR PRESSURE
ESTIMATION.
M. Chastrette and D. Cretin
MODEL FOR THE CRITICAL EVALUATION OF SOLUBILITY DATA IN SALT 95

SYSTEMS
R. Cohen-Adad, M.-Th. Cohen-Adad, D. Chehimi and A. Marrouche
ON THE EXPERT THERMODYNAMIC ANALYSIS OF POWER ENGINEERING 109

PROBLEMS
V. E. Alemasov, A. F. Dregalyn and R. R. Nazyrova
LIQUID-SOLID TRANSITIONS WITHIN MULTIPLE EMULSIONS. ENTHALPY AND 115

TEMPERATURE DATA ApPLIED TO MASS TRANSFER STUDIES.
D. Clausse, 1. Pezron, L. Potier and S. Raynal
CHAPTER 3: UNDERSTANDING COMPLEX SYSTEMS
INVESTIGATION OF THE STRUCTURAL AND ACIDIC PROPERTIES OF BULK 129

OFFRETITE USING FIRST PRINCIPLES MOLECULAR DYNAMICS
J. Weber, L. Campana, A. Sellon;, A. Pasquarello, I. Papa; and A. Goursot.
SURFACE THERMODYNAMICS OF SOLID MATERIALS BY INVERSE GAS 135

CHROMATOGRAPHY
M. M. Chehimi
DIFFERENTIAL SCANNING CALORIMETRY (DSC) AND TEMPERATURE 143

DEPENDENCE OF THE ELECTRICAL CONDUCTIVITY IN THE TERNARY SYSTEM:
WATER + CTAB + PHENOL
K. Busserolles, G. Roux-Desgranges and A. H. Roux
THERMODYNAMIC MODELS FOR MONITORING DEOXIDATION TREATMENTS 151

AND CONTROLLING INCLUSIONS IN STEELS
H. Gaye, C. Gatellier and J. Lehmann
A TECHNIQUE FOR STUDYING THE PARTICLE IMPACT PHENOMENA IN 161

PLASMA SPRAYING
A. Vardelle, M. Vardelle and P. Fauchais
THE ApPLICATION OF THERMODYNAMICS TO THE DEVELOPMENT OF 169

PROCESSES AND MATERIALS
P.J. Spencer, G. Eriksson, A. von Richthofen
Contents IX
CHAPTER 4: COMPUTER-AIDED-DESIGN AND NEW

MATERIALS
MATERIALS DATA FOR THE ERA OF AGILE MANUFACTURING 183
K. Preiss
MATERIALS DATA REQUIREMENTS FOR COMPUTER SIMULATION IN DESIGN 189

AND MANUFACTURING
D.R. Hayhurst
MICROCOMPUTER - AIDED - TOMOGRAPHY OF COMPOSITE MATERIALS 225

D. Wu, C. Batthias and F. Potter
MODELING OF THE VISCOELASTIC BEHAVIOR OF NON-HOMOGENEOUS MATERIALS 233

N. Alberola and P. Mele
MODELING STUDIES OF THE UNIAXIAL CREEP OF A BRITTLE MATRIX COMPOSITE 243

J L. Valles, M. Steen and F. Lamouroux
THE INTELLIGENT SELECTION OF MATERIALS FROM A DESIGN SPECIFICATION 251

A.C. Winstanley, s.P. Loughlin and F. J Smith
PHASE DIAGRAM CALCULATIONS AND THE OPTIMIZATION OF HIGH SPEED STEEL 255
COMPOSITIONS FOR ECONOMIC POWDER METALLURGY PROCESSING ROUTES.
I. A nsara, M. Durand-Charre; c.s. Wright, A. S. Wronski; J Mascarenhas,
M. Oliveira; E. Lemoisson, Y. Bienvenu.
THERMODYNAMIC ApPROACH TO THE DESIGN OF NEW CERMETS PROCESSED 263

BY LIQUID PHASE SINTERING
c.H. Allibert and H. Pastor
CHAPTER 5 : SYNTHESIS AND ApPLICATION OF NEW

MATERIALS
PREPARATION OF THIN FILMS USING A SOL-GEL METHOD 273
Jc. Plenet, C. Urlacher, F. Paille, C. Bovier, J Serughetti, J Dumas and
J Mugnier
AQUEOUS PREPARATION OF CHEMICALLY HOMOGENEOUS MUL TICOMPONENT 283

SILICATE PRECURSORS.
I. Jaymes and A. Douy
SYNTHESIS OF BARIUM TITANATE BY REACTION OF TITANIUM SALTS IN 289

MOLTEN ALKALI METAL SALTS OF OXOACIDS OF NITROGEN.
V. Harle, A. Aboujalil, F. Chassagneux, B. Durand and JP. Deloume
x Contents
NEW MATERIALS FOR (BIO)CHEMICAL RECOGNITION 293

N. Ja/frezic-Renault
IONIC RECOGNITON USING CONDUCTING CERAMICS 305

P. Fabry, H. Khireddine and M. Cretin
SYNTHESIS OF MACROCYCLIC LACTAMS IN ORGANIZED MEDIA 313

A. Caparros, E. Perez, I. Rico-Lattes and A. Lattes
SYNTHESIS OF CHROMIUM OXIDES FROM AQUEOUS SOLUTIONS 321

A. Bleuzen, P. Barbotix, F. Garcia and J. Livage
CHAPTER 6 : MATERIALS STRUCTURES AND BEHAVIOR

MODELING
DEFECT INTERACTIONS: ELECTRONIC TRANSPORT AND STATISTICAL 327
THERMODYNAMICS IN NONSTOICHIOMETRIC OXIDES
R. Tetot and G. Boureau
MECHANICAL RESPONSE OF AMORPHOUS POLYMERS: a+~ MECHANICAL 335

RELAXATIONS, PLASTIC DEFORMATION, CREEP TEST AND STRESS RELAXATION
J. Perez, L. Ladouce and R. Quinson
MODELING OF ANISOTROPIC COALESCENCE OF y' IN SUPERALLOYS 343

J.L. Valles and D. J. Arrell
DATABASE-RELATED STANDARDIZATION TO DESCRIBE EXPERIMENTAL 349

RESULTS OF THERMOPHYSICAL PROPERTIES OF SOLIDS
G.Jaroma-Weiland and G.Neuer
MATERIAL DATA OF THIN INTERLAYERS BY AN INVERSE METHOD: THE CASE 355

OF A CONSTITUTIVE LAW OF BRAZES
G. Lovato, F. Moret, G. Chaumat, G. Cailletaud and P. Pilvin
RELATIONS BETWEEN FRACTAL MODELS OF SOME OXIDE SURFACE SHAPES 363

AND THEIR OPTICAL PROPERTIES
L.Chagroune, G.Maurice, A. Thomas, Ph.Pigeat and B. Weber
TEMPERATURE DISTRIBUTIONS IN ADIABATIC SHEAR BANDS IN STEEL 371

V. Pina and P.Herve
SUBJECT INDEX 377
AUTHORS INDEX 383

Chapter 1
NEW DEVELOPMENTS IN STATE

EQUATIONS AND THEIR ApPLICATION
THE EXTENDED ApPLICATION OF A TENSG, VI.

THEORETICAL METHOD FOR CALCULATION OF
GASEOUS HEAT CAPACITY
Ke-Wu ZHANG (Ke-Wu CHANG)
Department o/Chemistry, Northeast Normal Universty, Changchun 130024,

China
ABSTRACT
The author has proposed a theoretical equation for the nonequilibrium state of gases
(TENSG), that is extended here to the theoretical calculation ofgaseous heat capacity.
Thus an equation of the heat capacity of gases at constant pressure is derived. This
equation applies to both polar and nonpolar gases, the average error from 2398
experimental values being 0.38 % based on 538 compounds. The method is far better
than all other published methods.
RESUME
L 'auteur propose une equation theorique pour les etats hors equilibre des gaz et
I'applique au calcul theorique de la capacite calorifique des gaz. On obtient ainsi une
equation donnant la capacite calorifique des gaz a pression constante. En appliquant
cette equation, a lafois au gaz polaires et non-polaires, on obtient un ecart, avec 2398
valeurs experimentales issues de 538 composes, de 0,38%. Cette methode est
nettement plus satisfaisante que celles publiees jusqu'a present.
J.-P. Caliste et al. (eds.), Thermodynamic Modeling and Materials Data Engineering
2 New Developments in State Equations ...
1 INTRODUCTION
Theoretical research and calculation of the heat capacity Cp of a real gas at constant
pressure are of great significance in developing chemical thermodynamics. Moreover,
calculation of Cp has also extensive applications to a great many engineering designs.
If Cp and the P-V-T relation for a gas are known, all important thermodynamic
properties can be derived from basic equations of thermodynamics. Scientists have
paid great attention to the fact that the study of heat capacity in early periods promoted
greatly the development of classical quantum theory. The theoretical formula for solid
heat capacity by Einstein and the T3 law by Debye are excellent examples. But there
are still many problems that need to be solved where these theoretical methods are
applied to the study of Cp, which involves the very difficult field of intermolecular
forces (IF). Therefore, tremendous research work is required in modem scientific
theory to explore a theoretical method which satisfies the technological demands in all
the three aspects of universality, applicability, over a wide range of temperature T, and
high accuracy. Till now authoritative engineering works all over the world still have to
use empirical formulae which are complex, inexplicit in physical meaning and
nonextrapolable. So far the theoretical values of Cp are usually determined by data of
vibration and rotation spectra and by structural data (moment of inertia and symmetric
number). But these theoretical methods fail for molecules which are IR spectra-
inactive and Raman-inactive.
2 BASIS OF THE PRESENT EQUATION
Knowledge of the various forms of intermolecular forces (VFIF) is the most important
factor in studying real gases. The VFIF are different for molecules of different
structural types which are the decisive factor in determining the macroscopic
properties of a substance. The energy of a gas molecule is a function of temperature,
T. As T increases or decreases, the state of motion of the micro-particles (e.g.
molecules, groups, electrons, nuclei, etc.) changes in the gas, resulting in a change of
Cp. The sum of the translation, rotation, and vibration energies possessed by the
micro-particles in a gas determines the value of Cp. Based on modem structural theory
and the rule of the spatial station of electrons in polyelectronic atoms (or molecules) as
clarified by quantum mechanics, the author has advanced the· hypothesis of using
gaseous argon as a model in studying the VFIF [1-8]. It is hypothesized that (I) the
field of force among argon molecules is spherically symmetrical, (2) the molecules are
nonpolar, and (3) the quantum effect can be neglected. The above hypotheses all
coincide with practical cases. Therefore, the mechanism of gaseous viscosity is further
clarified (see below) and a differential equation for the model of argon is derived as
2 2
[ -] r
4 1
Deff = D 1+ m W; -F(r)dr (I)
The Extended Application of a TENSG, VI 3
where Deff is the effective collisional D for argon molecules, F(r) is the IF for argon, r
1
is the intermolecular distance. Wr is the relative speed of molecules, - 2 is the mean
Wr
1
of - 2 ' and m is the mass of the molecule. The relationship
W-I
TX/ (2)
/-La /(T+G)
was obtained by using the gaseous theory, where /-L stands for the gaseous viscosity of
argon. In its derivation the only effect taken into consideration was the intermolecular
attraction. In order to remedy the influence of intermolecular repulsion, the Maxwell
model of a point center of inverse power repulsion was taken into consideration and
the above relation was improved and turned into
or (3)
where c, G, and ka are constants which depend on the molecular structure of argon.
They could also be obtained from the measured values of /-L of argon gas and they were
shown to be c=1.47, G=140 K and ka=23.42 x 10-7 Nsm- 1 K-0.47 The author has
clarified that:
(i) from a comprehensive view of the situation, there exist not only the VFIF (e.g.
electronic effect, chemical bond and molecular bond, etc) in gases, but also the
quantum effect which cannot be neglected:
(ii) the mutual repulsive and attractive forces in the translation, rotation and
vibration of the micro-particles in a gas are the unique origin of the internal friction
forces of gases. In terms of this general model, it may be concluded that argon gas
is identical with all other gases. Thus, it should obey the same fundamental
equation
(4)
where /-Li is the gas viscosity. Argon gas differs from all other gases in:
(a) the number of atoms.
(b) the presence of chemical bonds and molecular bonds.
(c) the quantum effect.
In essence, it is a problem of the rate of /-Li with T.

An important assumption in this development is that we introduce two parameters ko

and no into Eq (5) which can be written as the following:
I TI.47 JO (5)
Ili = kt T + 140
where ko and no are the coefficients and the power ofU, respectively. The assumption
is proven to be correct by using mathematical induction (MI), i.e. testing Eq 5 with
measured /li values of all different structural types (e.g. the polar and the nonpolar; the
normal and the quantized, etc.) of gases. The results are satisfactory and no discrepant
case has yet been discovered.
This method is evidently different in principle from empiric regression, because we

have used MI which is a rigorous theoretical method. Ref [2] emphasizes that the
phenomenon of gaseous diffusion should not be considered as a result of random heat
motion of the gas molecules alone. From the microcosmic view, the mutual repulsion
and attraction in translation, rotation, and vibration of the micro-particles in the gas are
the origins of gaseous diffusion. Viscosity, heat conduction and diffusion are referred
to as transport phenomena which are all in nonequilibrium states and have a similar
physical nature. And the pattern of mathematical equations describing these
phenomena with the same physical nature is just the same in principle. Thus the
gaseous transport phenomena can be described by a unified equation
where Ctran is the transport coefficient, k' and n' are the coefficient and the power of U.
Eq 6 can be applied to three nonequilibrium states of gases with different structural
forms. As shown by the last results, the average error from 1288 experimental values
is less than 1.2 %. It shows that Eq 6 has universal applicability with explicit physical
essence and can be applied over a wide range of T with high accuracy. That is why it
was named the "equation of nonequilibrium state of gases" by the author. Recently,
the author proved [1] that Eq 6 could be extended to liquids, and a theoretical equation
of thermal conductivity for liquids was derived. The author elucidated that the thermal
conductivity Ai of a gas must be related only to the translation, rotation and vibration
of micro-particles in a gas. Therefore
(7)
where n\ and k\ are the power and the coefficient in W / (m . Kl+0.47m) ofU.
Now comparing the mechanism for the thermal conductivity of a gas with the micro-
explanation of Cp , we find that the two theories are in agreement. The pattern of
The Extended Application ofa TENSG, VI 5
mathematical equations describing these phenomena with the same physical nature is
just the same in principle. Thus Cp can also be described by an equation analogous to
Eq 7, namely.
(8)
where nand kF are the power and the coefficient in J / (mol. Kl+0.47m) of Eq 8. The
values of kF and n are shown in Table 1.
Eq 8 was verified for 542 inorganic and organic compounds of various types of
structures. It is shown from 2398 experimental values [9-10] that the average error is
0.38 %, which is within the range of empirical allowable error (see Table 2). This is an
important breakthrough in basic research. The calculated values obtained from Eq 8
and the other well-known formulae recommended by [9] are compared with the data
selected from the work of Reid, et al. as listed in Table 1. % deviations between
calculated and experimental values are shown by the Ss.
3 THE RULES AND PHYSICAL ESSENCE
Rule 1. E=n - nt= f(Tm, Tb - Tm , T) = f(MS). As has been stated, the factors affecting n
are the number of atoms, the chemical bond, the molecular bond and the quantum
effect [1]. Chemical bonds and molecular bonds are the key factors, which
comprehensively reflect the molecular structures (MS) of gases. According to the
theory and practice of organic chemistry, the normal boiling point Tb of organic
compounds can reflect the characteristics of their molecular structures [11,12];
statistical physics indicates: the intervals between vibrational energy levels are much
bigger than those between rotational energy levels. In order to obtain enough
molecules with rather high vibration quantum states, high temperatures are needed. So
the Cp which is related to molecular vibration needs a high temperature, and the
saturation value needs a still higher temperature. It was under the guidance of this
theory, that selecting the difference between Tb and the melting point Tm of the
compound as a parameter, the author rationalized the changing regularity of the
difference E=(n - nt) between nt in the high temperature range and n in the other
temperature range (Table 2).
Rule 2. n is a constant for n-alkanes or mono-substituted n-alkyls. It has been proven

by experiments that n is not affected by the number of atoms A when A > 9 ( except
for ring compounds) and the quantum effect can be negligible when the molecular
weight M > 21 or T is high enough. So the values of n for a pure substance depend
only on the structure of the substituent group (chemical bond) and molecular bond. It
is known that the energy of a hydrocarbon molecule has a monotonic linear
relationship with the number of carbon atoms in the molecule [13,14].
According to this fact and the micro-explanation (mechanism) of Cp, one can see that
each group of n-alkanes has a nearly equal effect on n. In a certain homologue such as
RnOH (Rn = n-alkyl), the chemical bonds are the same, the effect on n is the same.
Because the inductive effect weakens sharply with distance, so the inductive effect can
be negligible due to the shelter effect. Hence rule 2 is correct under the discussed
conditions. It is experimentally true that, for example, for all n-alkanes starting from
n-butane, all l-enes from I-butene, all RnSH from n-CSHllSH, all RnOH from 1-
propanol with n of 1.06, 1.04, 1.04 and 1.02, respectively, which is in accordance with
the theoretical expectation.
The first, second and third items in the homologue series are exceptions, because, for
example, methane does not have a C-C bond, and the C-H bond has a different
environment from the following members in the series. Only with propane do the
molecules start to have a C-C bond which has a similar condition with the following
members in the series [4, 12, 13].
Compound T,K C*
p ~lt ~2* ~3*
Propane 298 73.94 0.22 0.9 1.1

n=1.08 KF =6.231 800 155.25 0.34 0.6 -0.4
n-Heptane 298 166.09 0.06 0.4 -0.2
1.06 14.63 800 340.93 -0.50 0.6 -0.2
2,2,3-Trimethylbutane 298 164.67 1.09 0.8 0.9
1.10 13.37 800 346.37 0.11 0.7 0.1
trans-2-Butene 298 87.88 -1.47 -1.8 -4.6
1.04 7.98 800 173.75 -0.26 -0.1 -0.3
2-Methyl-l,3-butadiene 298 104.7 0.59 0.7 -4.4
0.96 11.66 800 201.0 -0.01 0.5 -2.2
2-Pentyne 298 98.77 -0.44 -0.2 2.0
1.00 9.933 800 192.17 -0.01 0.8 0.7
P-Ethyltoluene 298 151.65 0 0.8 0.9
1.20 9.685 800 324.90 -0.07 0.5 0.3
cis-1,3- 298 134.56 0.72 -5.9 1.3
Dimethylcyclopentene
1.34 6.279 800 317.53 -0.14 -1.1 3.5
2-Butanol 298 113.38 -0.47 -0.8 -1.9
1.00 11.40 800 220.56 0.30 0.5 -0.1
P-Cresol 298 124.56 0.02 0.1 0.9
1.14 9.13 800 255.86 0.36 -0.1 0.1
Isopropyl ether 298 158.39 0 -0.8 0
1.00 16.00 800 311.46 -0.31 2.3 1.3
Table 1. Continued
P-Dioxane 298 94.l2 0 -1.0 -0.4

1.32 4.5645 800 218.34 -0.42 0 O.l
Methyl ethyl ketone 298 102.95 -0.44 -2.5 -5.1
0.94 11.88 800 192.93 0.02 -0.1 0.6
Ethyl acetate 298 113.71 0 -0.5 -0.4
0.93 13.48 800 213.57 -0.43 0.1 0.2
Trimethylamine 298 91.82 0.l4 0.3 0.2
1.08 7.765 800 191.00 -0.15 0.5 0.1
Propionitrile 298 73.10 -0.68 -1.4 1.9
0.92 8.81 800 134.56 0.22 2.1 0.8
2-Nitrobutane 298 123.55 0.23 1.0 2.0
1.10 9.90 800 248.86 -0.48 0.1 -0.3
3-Picoline 298 99.65 1.35 - 2.2
1.24 5.885 800 222.4 0.28 - -0.4
1,1-Difluoroethane 298 67.99 -0.21 -1.3 -0.5
0.94 7.864 800 124.3 0.11 0.6 0.3
Octafluorocyclobutane 298 156.25 0 -6.8 -12
0.74 28.645 800 245.56 0.54 5.5 -1.5
Bromobenzene 298 97.76 0.47 2.8 -0.1
1.12 7.535 800 200.05 -0.09 1.1 0
Butyl-methyl sulfide 298 140.84 -0.22 0.1 0.2
1.02 13.55 800 278.55 0.l7 -O.l -2.1
2-Methyl-2-butanethiol 298 143.51 -0.02 0.4 -1.5
0.98 15.18 800 277.5 0.l1 -0.2 -0.11
Propyl disulfide 298 185.48 -0.41 0.4 -0.2
0.92 22.60 800 350.44 0.08 0.4 -1.8
3-Methylthiophene 298 94.91 -0.24 0.3 1.8
1.16 6.627 800 192.38 0.82 2.5 1.0
t from this work I
Average Absolute
*given by Reid et al. (1987, Table 6-8) Error % 0.29 1.1 1.4
Table 1: Comparison of calculated and literature values ofCp (J.mor i . Ki)

Rule 3. kF is linearly related to the number of>CH1 in molecules for all n-alkenes, 1-
alkenes and one functional group substituted derivatives of n-alkyls. Logically, since
Cp depends only on the state of motion of micro-particles in a pure substance, in a
homologue such as RnSH with the terminal-CH 3, -SH are the same, and differ only in
the number of >CH2 • According to the dynamics theory, the states of motion are
controlled by >CH2 • Because >CH2 increases one by one, it must be a linear
relationship. This rule has been checked with Eq 8 which shows that the rule is
correct. For example, the following formula is accurate for all RnOH starting from n-
propanol.
kF = 8.343 + 2.25 (N - 3) (9)
where N = number of carbon atoms in RnOH.
This theoretical result is in good agreement with the experiments. Obviously the above
discoveries are very significant, since now Cp can be calculated based on the theory.
The present equations are of great significance in the development of statistical

physics and an important breakthrough in basic research.
Tm,K > 85 T105-174 I

>205 155-165 >205 I 166-204 I >205
Tb-Tm ring; 'anhydride I22 - 82 I
24 -89 1120-180 5-15 90-105 90-104 I 105-136 I105-119
T 600 - 650- 750- 850- 920 - 1040 600 -750 - 900 - 1040 650 - 800 -910 - 1040
E 0.008 I 0.010 I
0.Ql8 0.Q25I I
0.032 0.008 0.014 0.024 I 0.003 I 0.011 I 0.016
Tm,K 900 -200 201 -285 201 - 285 T > 285 > 85 11
Tb-Tm 150 -245 181-200 >201 I >220 > 95..1
T 700 800 900 1040 800 - 850 - 920 - 1040 800 - 850 - 910 - 1040 900 - 1040
E 0.002 I 0.008 I 0.013 I I
0.006 0.009 0.014 0.008 I0.010 0.015 0.007
6 except the left-listed All except the above- listed are « 0 »
Table 2 : Values ofE=n - nt (n=1 as reference, ifn=B, take value BxE)(a)
(a) We may take the average value of the values E from both sides of the end point, if
T is just the value ofthe end point. Substitute E=O.OI for E when E>0.01 or take
E=O when E<O.OI for an inorganic substance.
* When (1) hydrogen atoms of phenyl rings are substituted by over-two alkyls; (2)
fused (bridge or poly) rings, perhalogeno-cycle; 5-membered heterocycle which
contains two double bonds and (3) non-cyclic perhalide, then take the value times 0.7,
1.3 and 1.6 respectively.
4 CONCLUSION
1- This paper points out that there are still great limitations when the quantum theory
by Einstein and Debye et al. is applied to the study of Cp, because it involves the
very difficult field of intermolecular forces of gases.
2- The author has proposed an equation for the nonequilibrium state of gases which
can be derived from the differential equation for a model of argon gas,
(1)
and it can be extended to the calculation of Cpo A theoretical equation for calculation
of Cp is proposed as follows:
(8)
Eq 8 can be applied to both polar and nonpolar gases, the average error from 2398
experimental values being 0.38 % based on 542 organic and inorganic compounds. It
is far better than all other methods in the literature. The physical meaning of Eq 8 is
clear and definite.
The changing regularity of E (= n - ni) and two important rules are obtained by logical
reasoning. This paper solves one of the tremendous research tasks in statistical physics
and the achievement is an important breakthrough in basic research.
Practice shows that the argon model is of great significance in developing

technological sciences and engineering thermophysics.
KEYWORDS
heat capacity, non-equilibrium equation of state, theoretical calculation, polar gas,
nonpolar gas.
REFERENCES
[1] Zhang Ke-Wu, Science in China (Series A), 36, (1993), 346-354
[2] Zhang Ke-Wu, National Conference on Mass Transfer and Separation
Engineering (in Chinese), TianJin, (1986), p.1-1
[3] Zhang Ke-Wu, CODATA Bulletin, 24, 2, (1992), 85
[4] Zhang Ke-Wu, J. of Natural Science of HeilogJiang University, 11 (1994), 90
[5] Zhang Ke-Wu, Science in China (Series A), 3, (1992), 300
[6] Zhang Ke-Wu, National Conference on Chern. Eng. Thermodynamics (in

Chinese), Hangzhou, (1987), p. 17
[7] Zhang Ke-Wu, J. Jilin Institute of Chern. Technology (in Chinese), 3, (1988),
[8] Zhang Ke-Wu, National Conference on Chern. Eng. Thermodynamics (in
Chinese), (1993), p. 126
[9] Reid D.C. et ai., The Properties of Gases and Liquids, 4th ed. New York,
(1987), p. 196-197
[10] Still D.R., Westrum E.F., Jr., and Sinde, G.c., The Thermodynamics of
Organic Compounds, New York, (1969)
[11] Yama c.L., Thermodynamic and Physical Property Data, (1992)
[12] Zhang Ke-Wu, Acta Chimica Sinica, (in Chinese), 42, (1984), 1227
[13] Zhang Ke-Wu, Acta Chimica Sinica, (in Chinese), 40, (1982), 977
[14] Volkenshtein M.V., "Structure and Physical Properties of Molecules" (in
Russian), Izd. AN. SSSR, ch. II, (1955)
PVT MEASUREMENTS OF METHANOL AND ITS
SPECIFIC EQUATION OF STATE
Ch. BERRO, H. HOCQ, C. REBUFA and E. RAUZY
Laboratoire de Chimie-Physique, Faculte des Sciences de Luminy, 163 avo de

Luminy, 13288 Marseille Cedex 9.
ABSTRACT
The work presented deals with PVT data of methanol. A specific experimental
apparatus is described to measure liquid compressive densities. Results are in good
accordance with literature data.
RESUME
Le travail presente traite des donnees PVT du methanol. Un appareil experimental

specifique est decrit, qui mesure les densites liquides. Les resultats sont en bon accord
avec les donnees connues.
1 INTRODUCTION
The experimental apparatus is designed to obtain PVT data of a pure component or a

mixture over the temperature range 210 - 470 K and at pressures of 1 - 700 bars. We
present for methanol twelve isotherms from 242.54 to 450.97 K and at pressures of 5
to 600 bars, i.e. 184 PpT data. The results are correlated by means of two accurate
equations of state: the Goodwin equation and the bipolynomial equation of state.
2 EXPERIMENTAL
As details on the experimental procedure have recently been given elsewhere (Hocq,
1994; Hocq et al., 1994) only a short description of the apparatus is given here. Figure
1 shows schematically the main part of the apparatus. It consists of a windowed
equilibrium cell which includes a bellows whose volume varies between 30 and
150mL, a high pressure recirculation pump, a temperature-control, a section for
pressure and temperature measurements, and for volume measurement a micrometric
table. The experimental arrangement is drawn in Figure 2. The equilibrium cell is
placed in the air thermostat; it has a temperature range of operation between 230 and
470 K and the cell can withstand pressures up to 700 bar.
Sapphire windows
Stainless-sleel nlve
Fluid introduction
Internal iron kernel for the stirrer
Stirrer support
Stirrer
External iron kernel for the stirrer
t
J'
Copper cylinder
copper colUlTl1l
Bellow
Chamber
Copper rod
Thcnnocouple
i Column connecting the support of thc

external stirrer with the micrometric table
Low position of the stirrer
Copper mass for transferring the heating or

cooling fluid tGthe bottom of the bello,,"
Cooling cireuil
Entrance tube of the compression fluid
Cooling platfonn
Entrance of liquid nitrogen
Figure 1: Schematic diagram of measurement cell

PVT Measurements of Methanol 13
Temperature is measured with three platinum resistance thermometers with an

uncertainty of about 0.01 K. Pressure is measured by a pressure transducer and a
digital Heise gauge whose accuracy is within 0.1 bar. The bellows was calibrated by
means of two pure components, toluene and water, the liquid and vapor densities of
which are well known. Methanol was purchased from Prolabo with a minimum purity
of99%. It was used after purification on a 60 real plates Oldershaw column; the purity
was controlled within 99.90 mol %.
14
6
---,----~~--Q 15
16
(8,
----1,1
Figure 2. Schematic diagram of the flow apparatus.
1- Pressure fluid tank 9- Micrometric table

2- Filter 10- Temperature transducer
3- Plunger circulation pump 11- Temperature controller
4- OLAER pressure shock-absorber 12- Product introduction valve
5- Heise digital pressure transducer 13- Air bath
6- HBM absolute pressure transducer 14- Measurement cell with a
bellows
7- Breaking disc 15- Filled cell
8- Pressure regulation valve 16- CLEXTRAL vacuum pump
3 RESULTS
Experimental compressed densities of liquid methanol are reported in Table I. Nine

isotherms have been measured between 240 and 440 K, four of which are below
298.15 K. We also give in Table 2 vapor compressed densities measured at three
temperatures 422.15, 437.50 and 450.97 K. Literature PpT data are summarized in
Table 3. As can be seen, few direct measurements exist between 210 and 298 K.
The majority of the available data are those of Sun et al. which are derived from
measurements of speed of sound. They will be compared with the results of the
present work in the next section. At higher temperatures, and overlapping our data, we
shall consider those of Machado and Street (1983).
Pressure (Bar) Density (mol/L) Pressure (Bar) Density (mol/L)

T=242.54K
24.53 26.2265 92.58 26.3767
52.39 26.2865 106.95 26.3934
75.62 26.3485
T=257.18 K
26.91 25.8035 79.31 25.9364
55.39 25.8785 105.38 26.0098
T-272.28 K
27.09 25.3439 323.22 26.0941
59.38 25.4336 351.22 26.1579
75.22 25.4789 374.03 26.2107
99.91 25.5423 397.Q3 26.2591
124.58 25.6103 423.24 26.3170
151.I2 25.6783 449.24 26.3728
168.71 25.7206 475.85 26.4292
201.01 25.7990 502.65 26.4867
222.00 25.8536 532.06 26.5478
245.60 25.9090 564.67 26.6170
274.41 25.9803 587.07 26.6624
291.21 26.0172
T=292.70 K
28.01 24.7069 274.21 25.3902
55.56 24.7588 300.81 25.4580
69.22 24.8262 325.82 25.5194
99.49 24.9165 350.82 25.5818
125.36 24.9904 375.43 25.6397
157.92 25.0780 399.43 25.6923
175.85 25.1342 423.24 25.7513
199.53 25.2014 448.84 25.8140
223.20 25.2615 472.65 25.8676
251.20 25.3387 506.65 25.9413
Table1 Continued
Pressure (Bar) Density (mol/L) Pressure (Bar) Density (mollL)
T=323.57 K
18.04 23.7366 249.60 24.4793
49.28 23.8417 274.41 24.5512
72.08 23.9241 298.81 24.6198
106.75 24.0315 324.62 24.6883
124.24 24.0954 350.02 24.7571
150.62 24.1775 373.03 24.8210
174.65 24.2488 400.23 24.8929
200.32 24.3291 423.64 24.9526
225.20 24.4048 457.44 25.0687
T=352.33 K
27.43 22.9705 275.61 23.8702
54.74 23.0843 300.81 23.9489
75.26 23.1720 325.62 24.0259
99.05 23.2682 350.62 24.1006
124.88 23.3590 374.63 24.1722
149.14 23.4418 397.83 24.2364
174.51 23.5340 424.84 24.3245
197.51 23.6142 449.84 24.3904
225.40 23.7020 473.05 24.4518
251.80 23.7896
T=382.88 K
24.57 21.8949 225.20 22.8185
48.96 22.0222 250.40 22.9167
74.57 22.1517 275.41 23.0102
99.40 22.2740 300.01 23.1032
110.78 22.3314 325.22 23.1826
143.58 22.4744 349.42 23.2683
163.98 22.5642 374.23 23.3493
206.79 22.7506 396.23 23.4343
T=413.20 K
25.21 20.7409 250.20 22.0209
49.96 20.9096 272.81 22.1067
76.11 21.0838 297.oI 22.2127
100.21 21.2306 320.42 22.3074
118.23 21.3462 351.82 22.4357
148.38 21.5130 376.63 22.5060
168.68 21.6214 394.83 22.6273
196.87 21.7678 424.44 22.6996
222.40 21.8727 453.04 22.7755
T-442.16 K
25.95 19.3303 199.79 20.7423
34.86 19.4058 224.80 20.8926
50.56 19.5903 250.20 21.0373
76.21 19.8403 274.61 2l.l693
100.67 20.0522 299.81 21.3030
125.10 20.2425 324.22 21.4209
150.36 20.4222 353.22 21.5578
175.49 20.5888 376.23 21.6633
Table 1. Experimental values of pressure and vapor densities of liquid methanol at

different temperatures.
Pressure (Bar) Density (mol/L) Pressure (Bar) Density (mol/L)

T=422.15 K
4.69 0.1378 7.70 0.2421
4.89 0.1476 8.21 0.2607
5.21 0.1586 8.85 0.2820
5.51 0.1698 9.49 0.3087
5.84 0.1813 10.30 0.3387
6.09 0.1945 11.16 0.3722
6.71 0.2088 12.14 0.4139
7.09 0.2246 13.14 0.4645
T=437.50 K
4.89 0.1409 8.93 0.2696
5.23 0.1511 9.60 0.2931
5.55 0.1621 10.43 0.3202
5.89 0.1740 11.33 0.3517
6.13 0.1870 12.37 0.3884
6.68 0.2010 13.52 0.4343
7.17 0.2157 14.91 0.4918
7.67 0.2315 16.51 0.5677
8.33 0.2496 19.13 0.6769
T=450.97 K
17.73 0.5729 13.09 0.3852
15.87 0.4926 14.31 0.4326
11.67 0.3472 20.33 0.6832
10.77 0.3168 23.38 0.8608
9.23 0.2669 9.97 0.2898
Table 2. Experimental values of pressure and vapor densities of methanol at different

temperatures.
Authors Nb. of Temperature Pressure range Density range

points range /K /bar /mollL
Zubarev (1967) 187 413-573 4-210 0.1-20.4
Kudchaker (1968)* 211 298-473 0.05-34. 0.002-1.1
Finkelstein 162 473-573 86-690 6.2-21.0
(1970)**
Ledwig (1982)** 248 223-298 1-3000 24.6-30.1
Machado (1983) 163 298-488 5-1038 15.8-26.7
Isdale (1985)* 45 298-323 1-4000 15.8-29.0
Straty (1986) 222 413-573 4-210 2.1-22.1
Sun (1988)* 105 273-333 1-2800 23.5-29.2
Sun (1990)* 105 203-263 1-2800 25.6-30.6
Riembauer 71 183-213 1-3000 27.0-30.5
(1990)**
Vacek (1992) 29 227-300 4-513 24.6-27.4
Table 3. Literature PpT data. (* derived data ** smoothed data)

4 COMPARISON WITH Two ACCURATE EQUATIONS OF STATE
The experimental results are correlated using two equations of state.
- the Goodwin equation (1987)
This non-analytic equation is only reliable between 298 and 573 K for pressures up to
700 bar because measurements were scarce below 298 K before 1987 as mentioned
above. Its form is:
(1)
where the function F(p, T) consists of two temperature-dependent functions each with
a density-dependent coefficient.
Average relative deviations between calculated and measured liquid densities are
given for each isotherm in Table 4. The agreement is good.
T/K ~p/p%
242.54* 0.042
257.18* 0.024
272.28* 0.115
292.70* 0.156
323.57 0.277
352.33 0.153
382.88 0.143
413.20 0.298
442.16 0.467
Average 0.186
Table 4. Comparison between our experimental data and the values calculated from
the Goodwin equation. (* Outside validity domain)
- the bipolynomial equation of state
This empirical equation has been developed in our laboratory (Peneloux, 1993;
Rebufa, 1993). Its form is similar to the Angus equation (1976) for carbon dioxide and
enables calculating all thennodynamic properties by differentiation or integration. The

compressibility factor can be written as:
Z= PV =1+~ L:~:>ij
10 7 (
T, -1
)j-,(~-1)i-' (2)
RT p, i=' j=' T p,
where p ,= 9.05 mol L-' and T, = 512.58 K. The bij parameters, 19 of which are equal
to zero, have been fitted to numerous detenninations.
The details of the adjustment are described in the Rebufa thesis (1993). The proposed
equation of state allows one to represent accurately all thennodynamic properties of
methanol. Its validity domain is included between 203 K where pressure can reach to
2800 bar and 573 K where pressure is limited to 700 bar. Nevertheless a new equation
of state has been published recently by de Reuck and Craven (IUPAC, 1993).
The latter which contains exponential temperature tenns in order to account for the
association of the molecules in the gas phase, is very accurate and covers a great range
of temperature and pressure. Comparison of experimental liquid densities with values
calculated by the bipolynomial equation of state is given in Table 5.
TIK dP/p%
242.54 0.196
257.18 0.228
272.28 0.187
292.70 0.302
323.57 0.438
352.33 0.103
382.88 0.095
413.20 0.274
442.16 0.501
Average 0.258
Table 5. Comparison between our experimental data and values calculated from the
bipolynomial equation of state.
Table 6 reports the deviations obtained from the literature data which overlap our
measurements. A good agreement is observed for most of these. The measurements of
Ledwig and Wuflinger (1982) deviate systematically when the pressure increases.
Authors Temperature range (K) Ap/p%

Ledwig (1982) 223-298 0.53
Machado 298-488 0.13
(1983)
Isdale (1985) 298-323 0.14
Sun (1988) 273-333 0.05
Sun (1990) 203-263 0.04
Vacek (1992) 227-300 0.17
Our work 242-442 0.26
Table 6. Comparison between literature data and values calculated from the
bipolynomial equation of state.
5 CONCLUSION
Comparison of our results to those of the literature shows that the apparatus gives
reliable data. On the other hand while the. bipolynomial equation of state is less
accurate than the IUPAC equation to represent some thermodynamic properties such
as heat capacities, it can be used easily in computer programs.
KEYWORDS
experimental measurements, PVT data, methanol.
REFERENCES
[1] Angus, S., IUPAC Thermodynamic Tables Project Centre, Pergamon Press,
London, u.K., (1976).
[2] De Reuck, K.M. and Craven, RJ.B., IUPAC Thermodynamic Tables Project
Centre, Imperial College, London, U.K., (1993).
[3] Finkelstein, F.S. and Stiel, L.I., Chern. Eng. Prog. Symp. Ser., 98, (1970), 11-15.
[4] Goodwin, RoD., J. Phys. Chern. Ref. Data, 16, (1987), 799-892.
[5] Hocq, H., These de Doctorat es Sciences. Universite d' Aix-Marseille III.
Marseille, France, (1994).
[6] Hocq, H., Bur, Y. and Berro, Ch., Eldata, Int. Electron. 1. Phys. Chern. Data, 1,
(1995), 79-86
[7] Isdale, J.D., Easteal, AJ. and Woolf, L.A., Int. 1. Thermophys., 6, (1985), 439-
450.
[8] Kudchadker, A.P. and Eubank, P.T., J. Chern. Eng. Data, 15, (1970), 7-9.
[9] Ledwig, R. and Wurflinger, A., Z. Phys. Chern., Neue Folge, 132, (1982), 21-27.
[\0] Machado, J.R.S. and Streett, W.B., 1. Chern. Eng. Data, 28, (1983), 218-223.
[11] Peneloux, A., Private communication, (1993).
[12] Rebufa, C., These de Doctorat es Sciences. Universite d' Aix-Marseille III.
Marseille, France, (1993).
[l3] Riembauer; M., Schulte, L. and Wurflinger, A, Z. Phys. Chern., Neue Folge, 166,
(1990), 53-61.
[14] Straty, G.c. , Palavra, AM.F. and Bruno, T.J., lnt. J. Thermophys., 7, (1986),
1077-1088.
[15] Sun, T.H., Schouten, 1.A, Trappeniers, N.J. and Biswas, S.N., 1. Chern.
Thermodyn., 20, (1988), 1089-1096.
[16] Sun, T.H., Schouten, 1.A and Biswas, S.N., Ber. Bunsenges. Phys. Chern., 94,
(1990), 528-534.
[17] Vacek, V. and Hany, AM., Fluid Phase Equilibria, 76, (1992), 187-198.
[18] Zubarev, V.N. and Bagdonas, AV., Teploenergetika, 16:, (1967),88-91.
ENTHALPY OF VAPORIZATION OF N-ALKANES
(FROM NONANE TO PENTADECANE).
EXPERIMENTAL RESULTS - CORRELATION
C. VITON, M. CHAVRET and J. JOSE
Laboratoire de Chimie Analytique I (LICAS), Universite Claude Bernard (Lyon

1), 43 Boulevard du 11 Novembre 1918 69622 Villeurbanne Cedex, France
ABSTRACT
Measurements of enthalpy of vaporization of n-alkanes (from C9 to CI5), in the

temperature range 313-344 K were made by using a calorimeter equiped with an
original vaporization vessel. The experimental results have been compared with liter-
ature data and with values predicted by the equation of state developed by Coniglio
and Rauzy. This equation is derived from the Peng-Robinson equation and does not
require knowing the critical parameters. It is completely predictive.
RESUME
Des mesures d'enthalpie de vaporisation de n-alcanes (de C9 a CI5), dans Ie domaine
de temperature 313-344 K ont ete realisees a l'aide d'un calorimetre equipe d'une
cellule de vaporization originale. Les resultats experimentaux ont ete compares aux
donnees connues et aux valeurs fournies par l'application de l'equation d'etat de
Coniglio et Rauzy. Cette equation est derivee de celie de Peng-Robinson et ne
necessite pas la connaissance des parametres critiques. Elle est completement
predictive.
1 INTRODUCTION
The work we present has been perfonned within the framework of a research group in
charge of thennodynamics of reservoir fluids. This group consists of four companies
dealing with the petroleum and gas industry and five university laboratories. The
general theme is the development of predictive models in order to calculate the
properties of hydrocarbon mixtures that are representative of crude oils and natural
gases. Each laboratory is more directly concerned with a particular theme. Our own
topic is: Measurements of vapour pressure and enthalpy of vaporization. They are
important to enable the thennochemical properties in the gaseous state. For the heat of
vaporization, there is very little accurate data, except at the standard temperature of
298.15 K, available at the present time.
We have made an isothermal calorimetric determination of the heat of vaporization.

The apparatus works on the principle of complete vaporization into a vacuum. After
calibration, the results we obtained were compared with those of the literature and
with values calculated from the vapor pressure and from estimation methods.
2 ApPARATUS AND TEST PROCEDURE
We have used a SETARAM BT 2.15 D calorimeter. It is more specially designed for

calorimetric applications at low and medium temperature (from 77.15 to 473.15 K).
We have used it in the range 309 to 374 K. It is a Calvet type calorimeter which works
according to the following principle: it consists of a thermostatted calorimetric block
containing the heat flow detectors.
IOmm
f ~:
± 3mm
H
5mm
80.8 mm
1.1 mm 60'
1.1 mm
Ilmm
Figure 1: Vaporization vessel
There are two symetrical parts: the measurement part and the reference part. The two
heat flow detectors are in opposition. There is nO vaporization vessel available for this
type of calorimeter so we had to conceive and build One (Figure 1). The vaporization
vessel is tightly fitted into the calorimeter unit. In order to eliminate condensation
phenomena we have overheated the tubings at 10 to 15 K above the experimental
temperature. The heating wire and sensor are wound around the external surface ofthe
tubings (Figure 2).
Enthalpy of Vaporization ofn-Alkanes 23
Control - rod
alPiratio n
tube
_ 'hudloss'
therma l
insuillio .
thre:!!!
Figure 2: Vaporization unit and « head loss» installation
The vaporization unit is placed in the measurement part. In the reference part we have
an identical but empty unit. The vaporization unit is connected to a two-stage primary
vacuum pump through a liquid nitrogen trap (Figure 3). The cell is always kept in the
calorimetric block.The vaporization unit is not removed for filling because we do not
want to modify the calibration. The operating method is simple: the liquid is
introduced into the cell by means of a specially equipped syringe.
In order to find out the exact mass we have to weigh the equipped syringe before and
after the insertion. After a steady state is obtained, characterized by constant heat leak,
vaporization is initiated by opening the control valve VI. Complete vaporization ofthe
liquid is indicated by a sudden change in the heating response and a constant heat leak
is soon re-established.
The amount of heat required for vaporization of the substance equals the difference
between the total amount of heat supplied and the correction for heat leak found prior
to and after the vaporization.
24 New Developments in State Equations .. .
connection R2 va lve V I
connection R3
connect ion RI liquid nitrogen trap
connection R4
valve V2
conn ection R5
sample vacuum gauge
{
Vessel reference valve V3
.. ~. ~~.~ tu b.~...
connection R6
connection R 7
Figure 3: Schematic diagram of the apparatus
The vaporization rate is determined by the drop in pressure through the top of the cell.
We have adjusted the diameter of the top hole of the cell so that the heat flow detector
is not saturated by using short steel tubes (<< head losses ») with different internal
diameters that are placed with the help of a left-hand threaded rod (Figure 2)
3 CALIBRATION
This equipment can not be used for a Joule effect, because it was too difficult to insert
a resistance wire. In order to calibrate the system we had to measure at different
temperatures the LlH's of some alkanes and compare them with Majer's and Svoboda's
data [5]. Then we determined the value of the calibration coefficient as a function of
temperature (Table I).
Vaporization into a vacuum is usually applied at low pressures where the ideal gas
equation of state holds for the vapour phase. Vaporization occurs under
nonequilibrium conditions because of the drop in pressure between the cell (pressure
Ps ) and the evacuated compartment. The vaporization doesn't occur at a constant
equilibrium pressure but against a pressure P neq < Ps
ao= +0.432196 10+2 0=0.10447 10+0

-I
al= +0.375868 10 0-=0.34403 10-2
-3
a2= -0.284242 10 0-=0.25635 10-4
t Kexp
(Kexp - Kcalc)xlOO
1°C IIlV/mW
Kcalc
35.95 44.1975 -0.014
36.35 44.2024 -0.018
45.73 44.3698 0.058
55.70 44.4021 -0.066
60.70 44.4801 0.059
80.70 44.4188 0.038
85.83 44.3133 -0.087
100.83 44.1326 0.029
..!.. tl(Kexp - Kcalc)xlOOI = 0.046

n 1 Kcalc I
Table 1: Calibration K = f(t)
The nonequilibrium heat of vaporization AH neq is always smaller than AH.
ps : pressure above the surface of the liquid

P neq : non-equilibrium pressure
V; : volume ofthe saturated gas

V~ : volume of the saturated liquid
We have measured the value of P neq in order to determine the exact value of AH.
4 COMPARISON WITH EXPERIMENTAL DATA
In order to compare the experimental results with the recommended data of Majer et al
[4], we have used three equations:
1 - Majer equation [5] : MI = A exp(-aTr )( 1- Tr ) 13
2 - Watson equation [10] : MI 2 = MI I

1- T
[ 1- ~
)n and n = 0.375
3- Somayajulu equation [6] :
ilH = A1(X/Tr ) +A 2XYs +A3XI% with X = (1- Tr)
The results we obtained are in good agreement with the literature (Table 2 to Table 8)
except for the dodecane (Table 5).
r - - - - - -1- - - - - - - - "l - - - - - - - - - - - - - - - - - -I
I
I
I
I.6.H
I
I
(dH exp -dHcalc ),100 I
I
I T I exp I lSHexp I
'1K: /kJ/mol: 2 3 I
313.75 I 46.08 1.68 1.01 1.66

313.75 I 46.19 I 1.91 1.24 1.90
313.75: 46.17 1.87 1.20 1.85
Itl(~Hexp-dH""C)Xlool= 1.82 1.15 1.80

n 1 ~H~",
Table 2:Experimental results ofnonane. Comparison with the recommended data of

Majer et al. [4] by means of three equations: 1 - Majer equation; 2 - Watson equation;
3 - Somayajulu equation
~
I
------:- ------- --- - :
I
~
I
-(~~
cxp
=~~
ca C
~;o~ ----: I
I T I .1.Hexp I tiHexp I
I IK /kJ/mol 2 3 I
n-Decane 313.75 I 50.64 I 0.98 I 0.35 I 0.99

313.75 I 50.79 I 1.28 I 0.64 I 1.28
I I I I
313.75 I 50.09 I -0.10 I -0.74 I -0.10
323.78 I 49.31 I -0.06 I -1.06 I -0.07
323.78 I 50.02 I 1.36 I 0.38 I 1.36
333.85 I 49.68 I 2.32 I 1.00 I
2.31
333.85 I 49.69 I 2.34 I 1.02 I 2.32
I
I I I I
333.85 I 49.53 I 2.02 I 0.70 I 2.01
ktl(~H.",-dH""c)Xlool= 1.31
I
I 0.74
I
I 1.30
I I
1 ~H~",
I I
Table 3:Experimental results of decane. Comparison with the recommended data of

Majer et al.[4] by means of three equations: 1 - Majer equation; 2 - Watson equation;
r - - - - - -1- - - - - - - - i - - - - - - - - - - - - ,
I J I ~ -6Hc.J ).100 J
I T I dHexp I AH;;q; C I
IK IkJ/mol 2 3
n-Undecane 313.75 I
55.30 J
-0.52 J
0.45
313.75 I 55.47 J -0.22 I 0.76
J I J
313.75 I 55.38 I -0.38 J 0.59
313.75 I
55.66 I
0.13 I
1.09
323.78 J 54.43 J -0.96 J 0.44
323.78 J 54.54 J -0.75 I 0.64
I J I
323.78 I 53.83 I -2.08 I -0.67
I J J
323.78 55.04 0.16 1.55
333.85 I 54.08 -0.37 J 1.38
333.85 J 54.07 -0.39 I 1.36
J J
333.85 I 53.72 -1.04 I 0.72
I J
333.85 I
53.41 -1.63 J
0.14
333.85 J 53.25 -1.93 J -0.16
I J
333.85 I 54.00 -0.52 I 1.23
343.88 J 53.00 -1.13 J 0.96
343.88 J 53.07 -1.00 J 1.09
I I
343.88 I 53.11 -0.92 J 1.16
I J
343.88 54.14 1.00 3.04
~ tl(81I"", -LlJIcalc)X1001 =
1 LlJI.'P I 0.84
I
J
I
0.97
Table 4:Experimental results of unde cane. Comparison with the recommended data of
r - - - - - -1- - - - - - - - "T - - - - - - - - - - - - ,
: : : (6H"", - 6H calJI00 :
T 6Hexp iSH"",
IK /kJ/mol 2 3
n-Dodecane 313.75 I
58.21 I
-3.95 I
-3.53
313.75 I 57.54 J -5.16 J -4.73
J I I
313.75 I 57.53 I -5.18 J -4.75
I I J
313.75 57.75 -4.78 -4.35
323.78 J 57.09 J -4.82 J -4.26
323.78 I 56.79 J -5.37 I -4.81
J I I
323.78 I 56.27 J -6.34 J -5.78
333.84 J 57.88 J -2.21 J -1.46
333.84 J 57.87 I -2.23 I -1.48
I J J
333.84 I 57.90 J -2.18 I -1.43
J J I
333.85 58.24 -1.58 -0.83
343.88 I 57.33 I -1.97 I -0.98
343.88 I 58.65 J 0.32 J 1.29
J I J
I
343.88 I 56.65 I -3.20 I -2.20
i71(~"'P~lc)X101=
J
3.52 J
2.99
J
Table 5:Experimental results of dodecane. Comparison with the recommended data of

r - - - - - -1- - - - - - - - ., - - - -,- - - - - - -, - - - - - -)
I I I \.l1H e),."p - .1HcalcJxI 00 I

I I i ' I
T Ll.Hexp liH,,,,, I
IK IkJlmol 2 3
n-Tridecane 313.75 I
64.82 I
-0.20 I
-1.25 I -0.20
313.75 I 64.77 I -0.27 I -1.33 I -0.28
I I I I
313.75 I 65.07 I 0.19 I -0.86 I 0.18
313.75 I
64.96 I
0.02 I
-1.03 I 0.02
323.78 I
64.44 I
0.70 I
-0.79 I 0.69
323.78 I 64.15 I 0.25 I -1.25 I 0.25
I I I I
323.78 I 64.01 I 0.03 I -1.47 I 0.03
323.78 I
I
63.99 I
I
0.00 I
I
-1.50 II 0.00
323.78 I 64.99 I 1.54 I 0.06 I 1.53
I I I
323.78 64.14 0.24 -1.26 I 0.23
,
333.81 I
63.49 I
0.73 I
-1.20 I 0.71
333.81 I 63.14 I 0.18 I -1.76 I 0.16
I I I I
333.81 I 63.26 I 0.37 I -1.56 I 0.35
333.81 I
63.07 I
0.07 I
-1.87 I 0.05
333.85 I 63.36 I
0.54 I
-1.39 I 0.52
333.85 I 63.41 I 0.61 I -1.31 I 0.59
I I I I
333.85 I 62.98 I -0.06 I -2.00 I -0.08
343.85 I 62.36 I
0.49 I
-1.88 I 0.45
343.85 I 62.35 I 0.47 I -1.89 I 0.43
I I I I
343.86 I 62.41 I 0.57 I -1.79 I 0.53
343.86 I
I
62.47 I
I
0.66 I
I
-1.70 II 0.63
343.86 I 62.29 I 0.38 I -1.99 I 0.34
I I I
343.86 I 62.81 I
1.20 I
-1.15 II 1.16
343.86 I 62.90 I 1.34 I -1.00 I 1.30
Iti(t.H"p -t.H",,,)XIOOi =
I I
I I
0.46 I 1.39 I 0.45
n 1 LlHc:..'P I I
Table 6:Experimental results oftridecane. Comparison with the recommended data of

r - - - - - -1- - - - - - - -., - - - ,- - - - - - - - - - - - --I
I I I \.6.H c.'I:p - LlHca1c).:.IOO I

I T I ~Hexp I LSOHexp I
IK IkJlmol 2 3
n-Tetradecane 323.78 I
69.05 I
-0.13 I
-1.30 I
-0.23
323.78 I 68.75 I -0.57 I -1.75 I -0.67
I I ! I
323.78 I 69.16 I 0.03 I -1.14 I -0.07
323.78 I
69.34 I 0.29 I -0.88 I 0.19
I I I I
323.78 I 69.26 I 0.17 I -1.00 I 0.D7
333.80 I 67.65 I
-0.94 I
-2.35 I
-0.97
333.80 I 67.67 I -0.91 I -2.32 I -0.94
I I I I
333.80 I 68.08 I -0.31 I -1.70 I -0.33
333.80 I
68.13 I -0.23 I
-1.63 I -0.26
I I I I
333.80 I 68.00 I -0.42 I -1.82 I -0.45
343.84 I 66.62 I
-1.21 I
-2.84 I
-1.12
343.84 I 66.66 I -1.15 I -2.78 I -1.06
I
I I I I
343.84 I 66.78 I -0.97 I -2.59 I -0.88
*ti(t.H,,~-t.Hoa")XlOOi = 0.57
I
I
1.85
I
I
0.56
1 ,
LlHc:..l'
I I
I
Table 7:Expenmental results oftetradecane. Companson WIth the recommended data

of Majer et al.[4] by means ofthree equations: 1- Majer equation; 2- Watson equation;
~ - - -- - -:- -- - -- - - ~ -- -- (;H::---L\H~JI00- - --:

: T : 8Hexp: dHexp :
I fK I /kJ/mol I I 2 3 I
n-Pentadecane 343.88 I 71.26 I

-0.16 I
-3.05 I
-0.16
343.88 I 71.67 I 0.41 I -2.46 I 0.41
I I I I
343.88 I 71.96 I 0.81 I -2.04 I 0.82
343.88 I 71.70 I
0.45 I
-2.41 I
0.46
Itl(AH",,-AHoa,o)XIOOI=
I
I I
0.46 I 2.49 I 0.46
n1 AH"" I I
Table 8: Experimental results of pentadecane. Comparison with the recommended

data of Majer et al.[4] by means of three equations: 1 - Majer equation; 2 - Watson
equation; 3 - Somayajulu equation
5 INDIRECT DETERMINATION OF 8H BY EXPERIMENTAL VAPOR

PRESSURE DATA
It is often difficult to trace the ongm of many "experimental" enthalpies of

vaporization. A few have been detennined from calorimetric measurements, but in a
large number of cases the so-called experimental value was obtained indirectly from
an analytical vapor pressure-temperature equation.
For many years, the principal activity of our laboratory has been the study of the
liquid-vapor equilibrium of pure compo\lnds. In a previous presentation we have
described a static device allowing measurements of vapor pressures within the range:
240.15 ~ T(K) ~ 468.15 [9].
The apparatus basically consists of a cell connected directly to a pressure gauge using
high vacuum technology. The gauge is calibrated with vapor pressure data of water.
Naphthalene and n-dodecane were chosen as test substances.
The enthalpies of vaporization were calculated from four equations :
1- Antoine equation with parameters detennined by smoothing our own

experimental vapor pressures.
2 - Previous equation with correction for non-ideal gas (compressibility factor)
3 - Gomez-Thodos equation [3].
4 - Vetere equation [8].
The results are given in Table 9. For most of them, we observe a good agreement with
the experimental data.
r--------i---------r-------T---------------------------,
: : : : Iti(liH,,,,,-liH"'k)XIOOi :
: : : : n 1 ~He.\p :
I I I I I
: T min : T max ' Nb pts '2: 3 : 4 :

I I J I I
I IK I IK I I I
n-Decane 313.75 I 333.88 I 8 I 0.79 I 0.93 I 1.03 I

I
0.96
I I I I I
I I I I I I
n-Undecane 313.75 I
I
343.88 I
I
18 I
I
1.30 I
I
1.44 I
I
0.74 I
I
1.20
I I I I I I
n-Dodecane 313.75 I
I
343.88 I
I
14 I
I
3.57 I
I
3.50 I 2.34 I
I
2.81
I I I I I
:
I
:
I
I
n-Tridecane 313.75 343.86 I
I
24 I
I
1.32 I
I 1.36 0.71 I 1.03
I I I I
I I I I
n-Tetradecane 323.78 343.84 I 13 I 0.43 I 0.45 I 0.30 I 0.75
I I I I I
i ,I ,
I I
,
I I
I
n-Pentadecane 343.88 I 343.88 I 4 I 0.54 I 0.55 I 0.38 I 0.43
,
I I
I
I
I
I
I
I
I
I
I
Table 9: ~H calculated by using vapor pressure. Comparison with experimental data

by means of four equations: 1 - Antoine equation; 2 - Antoine equation with
correction; 3 - Gomez-Thodos equation; 4 - Vetere equation
6 CORRELATION OF THE EXPERIMENTAL RESULTS
Results were also correlated with the equation of state of Carrier-Rogalski-Peneloux

[1] modified by Coniglio and Rauzy [2]. This is a cubic equation of the Peng-
Robinson type allowing the correlation and the prediction of vapor pressures for heavy
hydrocarbons. Besides simplicity, this equation has the advantage of not using critical
parameters. For a component the parameter m can be obtained by a group contribution
method developed by the authors, so this equation is completely predictive.
p
RT a
V - b V (V + y b)
and
~H
with: V + c = V and b + c = b
a(T)= a(Tb)exp illill -lTbJ{ ( r

T lX '1
j- (
ill2 1 - Tb
T )Y}
1 C 2 ill - YC I ill - xCI
0.4 and y = - , illi =
x = , ill2 =
x x C2 - Y x C2 - y
band m are calculated by a group contribution method.
V G and V L are the pseudo-molar volume of gas and liquids, and Tb: boiling point; c:
volume correction; C 1 and C2: constants; m b m2: parameters of the equation of state
- Svoboda and Dockalova [7] have proposed a group contribution method for
calculating the heat of vaporization of alkanes at an arbitrary temperature with high
accuracy. This method is based on the calculation of parameters of the relationship
between the temperature and heat of vaporization.
~H = A( 1- Tr) exp( -aTr )

whereTr : the reduced temperature and A,a : adjustable parameters
A = ~xjPj(A) and a = ~xljCa)

J J
Where Xj is the number of contributions, subscript j indicates the type of contribution
and Pj(A), Pj(a) are values of this contribution. The results are given in Table 10.
Tmin Tmax I Nb pts 2

IK , IK , , , ,
n-Nonane 313.75 ,, 313.75
,, 3 ,, 2.01 ,,
n-Decane 313.75 ,, 333.88
,, 8
,, 1.69
,, 1.22
, , ,
,,
n-Undecane 313.75 343.88 18 1.72 1.05
I , I
n-Dodecane 313.75 , 343.88 , 14 1.94 2.72

, I ,
I
,
I
n-Tridecane 313.75 343.86 , 24 , 2.33 1.65

,
I
, I
I
I
n-Tetradecane 323.78 343.84 , 13 , 2.51 , 1.02

,
I
I , I
n-Pentadecane 343.88 , 343.88 , 4 ,

,
2.99
,
I
1.22
I I
Table 10: ~H estimated by using group contribution methods. Comparison with

experimental data by means of two equations: 1 - Svoboda and Dockalova equation;
2 - Coniglio and Rauzy equation
The results we obtained are in rather good agreement with values estimated by these
two methods.
7 CONCLUSION
The vaporization unit we have built allows correct measurement of AH within the
range 309 K to 374 K.
We will have to modify the conception of the top of the cell in order to increase the
temperature range and to be able to do measurements at very low temperatures.
Our results are in good agreement with the estimation methods and particularly with
the prediction method of Coniglio and Rauzy based on equation of state.
KEYWORDS
enthalpy of vaporization, n-alkanes, Coniglio-Rauzy equation of state.
REFERENCES
[1] Carrier, B., Rogalski, M. and Peneloux, A., Correlation and prediction of physical
properties of hydrocarbons with the modified Peng-Robinson equation of state -
Representation of the vapor pressures and the molar volumes. Ind. Eng. Chern.
Res. ,29, (1990), 659.
[2] Coniglio, L., Berro, C., Rauzy, E., Representation and prediction of
thermophysical properties of n-heavy hydrocarbons. Fluid Phase equilibria. 87,
(1993)
[3] Gomez-Nieto, M. and Thodos, G., Ind. Eng. Chern. Fundam. 16, (1978), 254.
[4] Majer, V., Svoboda, V, Enthalpy of Vaporization of organic compounds. IUPAC
Chern. Data Series n032, (1985).
[5] Majer, V., Svoboda, V. and Pick, J., Heats of Vaporization of Fluids. Elsevier,
Amsterdam, (1989).
[6] Somayajulu, G.R., New equations for enthalpy of vaporization from the triple
point to the critical point. Int. J. Thermophys., 9, (1988), 567.
[7] Svoboda, V. and Dockalova, P., Extension of the group contribution method for
the calculation of the heat of vaporization. Fluid Phase Equilibria, 54, (1990),
293.
[8] Vetere, A., Predicting the vapor pressures of pure compounds by using the
Wagner equation. Fluid Phase Equilibria, 62, (1991), 1.
[9] Viton, C., Mokbel, I., Kasehgari, H. and Jose, J., Vapour-liquid equilibrium of
heavy n-alkanes. 13 th European Seminar on Applied Thermodynamics, Carry-Le-
Rouet, France, (1993).
[10] Watson, K.M., Thermodynamics of the liquid state. Ind. Eng. Chem.,35, (1943),
398.
AIMS AND ACHIEVEMENTS OF THE SCIENTIFIC
GROUP THERMODATA EUROPE
J.ANSARA
Laboratoire de Thermodynamique et de Physico-Chimie Metallurgiques, UMR,
ENSEEG, B.P. 75,38402 Saint-Martin d'Heres Cedex, France.
ABSTRACT
During the past fifteen years, the Scientific Group Thermodata Europe has been
involved in the compilation, critical evaluation and development of databases. They
contain assessed and self-consistent thermodynamic values for pure substances, metallic
alloys, slags and semi-conductor alloys. They are linked to application programes which
are developed by different members.
These applications concern calculation ofphase diagrams for multicomponent systems

of various sorts, metallic, superconductors, process development by modeling and
simulation, recycling and the environment.
RESUME
Pendant les quinze dernieres annees, Ie Groupe Scientifique Thermodata Europe s 'est
implique dans la compilation, l'evaluation critique et Ie developpement de bases de
donnees. Celles-ci contiennent des valeurs thermodynamiques evaluees et coherentes
pour des substances pures, des alliages metalliques, des laUiers et des alliages semi-
conducteurs. Elles sont utilisees par des programmes qui sont developpes par differents
membres du groupe.
Ces applications concernent Ie calcul des diagrammes de phase pour des systemes
multicomposants de diverses sortes, metalliques, supraconducteurs, Ie developpement de
procede par modelisation et simulation, Ie recyclage et l'environnement.
1 INTRODUCTION
The calculation of complex phase equilibria in chemical or metallurgical

thermochemistry requires the knowledge of reliable thermodynamic data which in the
case of systems containing solution phases, have also to be consistent with phase
diagram data. In this respect, computer data handling is a very convenient way for the
user to retrieve reliable assessed thermodynamic information from a data bank in order
to synthesize by calculation a selected multicomponent system for his specific needs
or as an aid in planning experimental work. Historically, many databases have been
initiated by small groups or individuals. But at present, and with increasing
experimental information on substances, mixtures or phase diagram data, the task of
assembling, compiling and collating data is enormous. That is why, the Scientific
Group Thermodata Europe (SGTE)*, a consortium of laboratories or research groups
belonging to different academic, industrial or public institutions, was founded in 1982
to develop databases. It is engaged in the critical assessment and compilation of
thermodynamic data for inorganic and metallurgical substances, and has great
experience and expertise in the thermodynamics of data for solution phases.
Its members are the following:

• Association Thermodata, Saint Martin d'Heres (France)
• Institut National Polytechnique, Grenoble (France)
• I.R.S.I.D., Maizieres-les-Metz (France)
• Max-Planck Institut, Stuttgart (Germany)
• National Physical Laboratory, Teddington (United Kingdom)
• Rheinisch Westfalische Technische Hochschule, Aachen (Germany)
• Royal Institute of Technology, Stockholm (Sweden)
• United Kingdom Atomic Energy Establishment, Harwell (United Kingdom)
The aims of SGTE are the following:

- provision, maintenance and expansion of high quality databases, that enable the user
to undertake calculations of complex equilibrium efficiently and reliably.
- cooperation in a broader international effort to unify thermodynamic data and
assessment methods; also to promote collaborative efforts.
In the development of a database, several requirements have to be fulfilled:

- The type of representation of the thermodynamic properties for elements and pure
substances has to be well defined, not only in their stable states but also in metastable
states.
- For solution phases, the thermodynamic behavior is generally represented by
different models of greater or less complexity. In order to describe higher-order
systems obtained by combining the thermodynamic properties of lower order ones, it
is necessary to use the same model or compatible models for the same phase in all
systems. In particular, the thermodynamic properties of molten salts, slags and
metallic liquids should be described with the same model.
- The information contained in the data bank has to be self-consistent. When several
groups are collaborating on a common database and assessing data for
multicomponent systems, it is necessary that the same data for substances and solution
phases for the lower order systems be used by the different evaluators.l
• Groupement d'Interet Economique, BP 42, 38402 Saint Martin d'Heres Cedex, France I
The Scientific Group Thennodata Europe 35
2 THERMODYNAMIC PROPERTIES
2.1 Elements.
The CODATA Key Values [1] for the elements in their condensed states and for the
gaseous species have been adopted by SGTE, and evaluations of the thermodynamic
properties of other substances are based upon these values. However, in the study of
phase stability of metallic systems taken as an example, dissolution of an element in a
phase of another element may extend the range of stability for the phase. This requires
that one must extrapolate the thermodynamic description of the phases of the pure
elements beyond the temperature range where each element is stable. As many
elements can dissolve in a phase which is not stable for that element itself (e.g. AI( fcc-
AI) in Ti(hcp-A3 or bcc-A2), it is necessary to estimate the thermodynamic properties
of elements in states which are metastable at all temperatures. Kaufman et al. [2]
presented sets of estimated parameters for the enthalpy and entropy differences
between the bcc-A2 and hcp-A3 and the fcc-AI and hcp-A3 structures of the transition
metals, applying Richard's rule for the entropy of melting. These values were derived
from high-pressure measurements or from the analysis of thermochemical data and
phase diagrams. However, these expressions implied that the heat capacities of the two
phases involved are the same at all temperatures. An interim solution adopted by
SGTE is to assume that the heat capacity of the liquid phase approaches that of the
most stable solid phase for temperatures below the melting point. In a similar way,
above that melting point, the heat capacity of the solid phases approaches that of the
liquid phase. In this assumption, the difference in heat capacities at the melting
temperature is taken into account. Dinsdale [3] has produced a database where the
Gibbs energy of a particular phase of an element, i, relative to the enthalpy of the
stable element at 298.I5K, H; (. 298.l5K), is presented in the form of a polynomial
in Tplus a TlnTterm. Many of these data are based on the study by Saunders et al. [4]
who evaluated the lattice stabilities for the metastable fcc-AI, bcc-A2 and hcp-A3
forms of the elements. Their results are based on assessed stable phase data, phase
boundary extrapolations from temperature-composition phase diagrams, extrapolations
from pressure-temperature phase diagrams, relationships between the crystal structure,
the entropy of fusion and the melting temperature, stacking fault energies and first
principle electronic energy calculations. Rather little work has been undertaken to
include the pressure dependence of the Gibbs energy of the pure elements. For Fe, Cr,
Mo, W, V and Zr, the selected values are those assessed by Anderson et al. [5] and
Fernandez Guillermet [6]. Magnetic contributions to the Gibbs energy of transition for
magnetic materials were not, until recently, treated explicitly. They were included in
the expression of the Gibbs energy with respect to temperature.
2.2 Compounds.
Since the last decade, there have been several compilations concerning the
thermodynamic properties of substances [7-16]. They contain the basic
thermodynamic properties, Hr (298.1SK), SO(298.15), C~, HO(298.1SK)-W(OK),

temperatures and enthalpies of transformations. The thermal functions are presented
either as equations or tabulations. Many of these compilations also present entropies,
Gibbs energies of formation, or equilibrium constants. These data were compared,
analyzed and discussed among members of the SGTE in order to select the data. In
addition, a great number of thermodynamic properties relative to substances have been
critically evaluated by the members. The heat capacity data were fitted and the
coefficients are stored in the database together with the room temperature data, the
temperature and enthalpies of transformations. Magnetic or pressure parameters are
also considered for those substances where data are available. At present the database
contains the thermodynamic descriptions of over 4000 substances.
2.3 Solutions
For solutions, a large variety of models exist to describe the thermodynamic properties
of mixing. But in the development of a database, it is necessary to use a formulation
ofthe excess properties which is suitable for a wide variety of solution phases. Indeed,
for many metallic or oxide systems, the liquid phase presents a tendency to chemical
ordering. Moreover, binary or higher-order systems also exhibit intermediate phases
with different crystalline structures and several sub lattices possibly with narrow
ranges of stoichiometry. These compounds are often assumed to be line compounds
when the range of non-stoichiometry is narrow. That is why the use of the sub lattice
model developed by Hillert et al. [17] based on Temkin's model for ionic solutions
[18] and extended by Sundman et al. [19] has been adopted. The solution phase is
represented by the general formula:
where Uj, Uj,'" and z, are the site fractions of the different constituents in a given sub-
lattice, withLVi = 1.
For solid phases, the number of sub lattices and the species (which may include
vacancies or ions) occupying them, is generally obtained from structural information.
The model can be applied to reciprocal salt systems (A+, B+)a (C-, D-h, III-V
compounds (AIII, BII~(CV, DV), interstitial solutions (Fe, Ni)a(C, N, O)b, ordered
phases i.e. L12 (AI, Ni);(Al, Ni), ionic liquid solutions (Al+ 3)p(O-2, Si044 , SiOg)q and
of course the simple cases of substitutional solutions (Ax,Bx2Cx3 .... ) or stoichiometric
compounds (A)a(C)b. The model parameters for the various phases forming a system
are generally obtained by means of optimization procedures which have been
developed by members of the SGTE. These procedures take into account
experimental thermodynamic information on compounds and solution phases such as
enthalpies of formation, activities, heat capacities, or phase diagram data. The
The Scientific Group Thermodata Europe 37
softwares in use are those developed by Lukas et a!. [20-22], "Parrot" developed by
Jansson [23] included in the Thermo-Calc package [24], and a module developed by
K6ningsberger [25] integrated in ChemSage [26].
3 ApPLICATIONS.
From these databases, sub-sets can be created for specific applications. The data
extracted from them provide users with a basic tool necessary to solve a wide
spectrum of problems arising in materials and process design and development.
Members of SGTE are currently involved in problems relevant to pyrometallurgy,
hydrometallurgy, waste processing, aqueous and high temperature corrosion, energy
conversion, alloy design, ceramics, safety assessment, pollution control, chemical
vapor deposition, crystal growth, electronic materials, joining (soldering, welding,
brazing), etc .... All these problems deal generally with many species and phases.
Sophisticated application software developed by the members and generally linked
with the databases to graphical packages are extremely efficient and are widely used to
solve these problems.
4 CONCLUSION
Critically-evaluated thermodynamic data of substances and solution phases are now

being generated in many countries. Many of these tasks are now being organized
among different groups on an international scale, for instance by the CODATA Task
Group on Thermochemical Tables (CTT), and the Alloy Phase Diagram International
Commission (APDIC), CALPHAD and other international endeavors where SGTE
members are contributing actively to the development of data.
KEYWORDS
SGTE, database, thermodynamic, substances, mixtures
REFERENCES
[I] "CODATA Key Values for Thermodynamics", Ed. J.D. Cox, D.D. Wagman,
V.A. Medvedev, Hemisphere Pub!. Corp., N.Y, U.S.A., (1989)
[2] L. Kaufman, and H. Bernstein, "Computer Calculation of Phase Diagrams",
Academic Press, N.Y (1970).
[3] AT Dinsdale, Calphad, 15,4 (199\).
[4] N. Saunders, A.P. Miodownik and A.T. Dinsdale, Calphad, 12,4 (1988) 35\-374.
[5] 1.-0. Andersson, A. Fernandez Guillermet and P. Gustafson, Calphad, 11,4
(1987) 36\-364.
[6] A Fernandez Guillermet and W. Huang, Z. Metallkde., 79, (1988) 88-95

[7] L.B. Pankratz, J.M. Stuve, and N.A Gokcen, "Thermodynamic Data for Mineral
Technology, Bull. 677, Bureau of Mines, U.S. Government Printing Off.,
Washington (USA), (1984).
[8] L.B. Pankratz, "Thermodynamic Properties of Halides", Bull. 677, Bureau of
Mines, U.S. Government Printing Off., Washington (USA), (1984).
[9] M.W Chase Jr., C.A. Davies, J.R. Downey Jr., D.J. Frurip, R.A McDonald, and
AN. Syverud, "JANAF Thermochemical Tables", 3rd. Ed., J. Phys. Chern. Ref.
Data, 14, (1985) Suppl.l
[10] E.H.P. Cordfunke, RJ.M. Konigs, P.E. Potter, J. Prins, and M.H. Rand,
"Thermochemical Data for Reactor Materials and Fission Products", Ed. E.H.P.
Cordfunke and RJ.M. Konigs, North-Holland, Amsterdam, (1990).
[11] L.V. Gurvich, L.Y Veyts, and C.B. Alcock, "Thermodynamic Properties of
Individual Substances", Vol. 1, Hemisphere Publ. Corp., N.Y., USA (1989).
[12] L.V. Gurvich, L.V. Veyts, and C.B. Alcock, "Thermodynamic Properties of
Individual Substances", Vol.2, Hemisphere Publ. Corp., N.Y., USA (1991).
[13] O. Knacke, O. Kubaschewski, and K. Hesselmann, "Thermochemical Properties
ofInorganic Substances", 2nd. Ed., Springer-Verlag, Frankfurt, (1991).
[14] L.V. Gurvich, L.V. Veyts, and C.B. Alcock, "Thermodynamic Properties of
Individual Substances", Vol. 3, CRC Press Inc., USA, (1993).
[15] O. Kubaschewski, c.B. Alcock, and PJ. Spencer, "Materials Thermochemistry",
6th. Ed., Pergamon Press, Oxford, (1993).
[16] I. Barin, "Thermochemical Data of Pure Substances", 2nd. Ed., V.C.H. Publ.,
(1992).
[17] M. Hillert and L.-I. Staffanson, Acta Chern. Scand., 24, (1970) 3618-3626.
[18] M. Temkin, Acta Phys. Chim., 20, (1945) 411-420.
[19] B. Sundman and J. Agren, J. Phys. Chern. Solids, 42, (1981) 297-301.
[20] H.L. Lukas, E.-Th. Henig and B. Zimmermann, Calphad, 1, 3, (1977) 225-236.
[21] H.L. Lukas, J. Weiss and E.-Th. Henig, Calphad, 6, 3, (1982) 229-251.
[22] H.L.Lukas and S. Fries, J. Phase Equil., 13 (5), (1992) 532-541.
[23] B. Jansson, Ph.D. Thesis, Div. Phys. Met., Royal Inst. Tech., Stockholm,
Sweden, (1984).
[24] B. Sundman, B. Jansson and J.O. Anderson, Calphad, 9, 2, (1985) 153-190.
[25] E. Koningsberger, Calphad, 15,1 (1991) 69-78.
[26] G. Eriksson, and K. Hack, Metall Trans., 2IB, (1990) 1013-1023.
FIRST PRINCIPLES CALCULATIONS OF BINARY
ALLOY PHASE DIAGRAMS
C. COL/NET and A. PASTUREL
Laboratoire de Thermodynamique et Physico-Chimie Mitallurgiques, INP. G.,

ENSEEG, BP 75, 38402 Saint Martin d'Heres Cedex, France.
ABSTRACT
In the past decade attempts to obtain a theoretical knowledge of thermodynamic data

and phase diagrams of alloys have been made by combining, at a high level of
accuracy, both quantum-mechanical and statistical-thermodynamical contributions.
These calculations have to take into account the local chemical environment in the
alloy which is important in determining both the internal energy and the entropy of
configuration. One of the most efficient methods for including short and long range
order is the cluster variation method. This method needs, as input the effective cluster
interactions which determine ordering or clustering reactions occurring in a given
lattice. These interactions can be derived from experimental data such as critical
temperatures or enthalpies of formation, but they can also be obtained within the
tightbinding framework or by using purely "ab-initio" methods such as the linear
muffin tin orbitals. These methods are presented and the results obtained in binary
metallic alloys are reported.
RESUME
Durant les dix dernieres annees des efforts pour obtenir une connaissance theorique des
donnees de thermodynamique et des diagrammes de phase des alliages ont ete menes en
combinant, avec une grande precision, a la fois la mecanique quantique et la
thermodynamique statistique. Ces calculs doivent prendre en compte l'environnement
chimique local dans l'alliage qui est important pour determiner conjointement l'energie
interne et l'entropie de la configuration. Une des methodes les plus efficaces pour tenir
compte de l'ordre a courte et longue distance est la methode variationnelle des amas.
Cette methode necessite en entree les interactions d'amas apparaissant. Ces interactions
peuvent etre derivees de donnees experimentales telles que la temperature critique ou
les enthalpies de formation, mais peuvent l'etre egalement en utilisant des methodes
purement "ab-initio".
40 New Developments III State Equations ...
1 INTRODUCTION
The study of phase diagrams, from both an experimental and a theoretical point of
view, is one of the most important subjects in material science. The important data for
phase diagram calculations are the Gibbs energies of the constituents (lattice
stabilities), the Gibbs energies of mixing of the solid and liquid solutions (from
constituents of same phase), and the Gibbs energies of formation of the compounds
(referred to the pure constituents). In recent years a considerable body of self-
consistent thermodynamic information has been built up that allows binary, ternary
and high-order phase diagrams, and associated thermodynamic properties, to be
calculated with success. The Gibbs energies are derived from direct experimental
information (such as calorimetry or vapour pressure or electromotive force
measurements).
Non-experimental Gibbs energies are derived with efficient computer programs of

optimisation from experimental thermodynamic information and phase diagram data.
This provides optimal Gibbs energies of formation and mixing (Calphad method).
Binary, ternary and higher order systems can be treated in this way. However, such an
approach needs knowledge or information concerning the considered system and is
unable to predict the existence of metastable phases or of intermetallic compounds if
not detected experimentally.
The purpose of this paper is to show the evolution of theoretical calculations of

enthalpies of formation and phase diagrams in binary alloys over the last twenty years.
2 THE FIRST DATABASES OF ENTHALPIES OF FORMATION OF

BINARY ALLOYS
The first attempts to predict enthalpies of formation of compounds or enthalpies of

mixing of solid and liquid solutions in metallic systems have been made by Miedema
and co-workers [9, 35] using a semi-empirical model. These predictions concern all
binary alloys. Concerning transition metal based alloys, numerous theoretical works
have been performed because the d-electrons can be treated in the tight binding
approximation. In 1979 Pettifor [14] proposed structural maps for binary transition
metal alloys. Later Watson and Bennett [16, 21] used a simple band theory model to
predict the enthalpy of formation of 276 transition metal alloys at the equiatomic
composition. Colinet et al. [22] also developed a tight binding model with a parabolic
d-band to predict the evolution of the enthalpy of formation with composition of 210
transition metal alloys. Later the same model was applied to transition metal-rare earth
metal alloys [33]. In these models, the input parameters, namely the bandwidth, the
Fermi level position, and the number of electrons in the band are allowed to vary,
within certain constraints, to closely approximate any known value of the enthalpy of
formation.
First Principles Calculations 41
However these databases give only the values of the enthalpies of formation. The
calculation of a phase diagram needs more information. For example, in the treatment
of an order-disorder transformation, the short range order and long range order in the
solid solution play a crucial role and then the use of more sophisticated models is
necessary. In recent years, the cluster variation method (CVM) [11] and the Monte
Carlo simulations [26] have proved to be highly effective. These methods need as
input the interaction parameters between the atoms (called cluster interactions).
In the following section we will focus our attention on the CVM and in sections 4 and
5 we will show how to get the values of the cluster interactions from theoretical
calculations.
3 THE CLUSTER VARIATION METHOD
The cluster variation method (CVM) was initiated by Kikuchi in 1951 [2,7, 11];
however, its applications to Gibbs energy and phase diagram calculations is far more
recent.
In the CVM the configurational entropy is expressed as a function of cluster

probabilities (points, pairs, triangles, tetrahedra, octaedra, etc.). Its expression depends
on the considered lattice (bcc, fcc or hcp). The choice of the maximum cluster depends
on the considered lattice and also on the cluster interactions which must be taken into
account. In a bcc lattice the maximum cluster usually considered is an irregular
tetrahedron including first and second neighbors; in this approximation the molar
entropy of a bcc disordered solution ( A2 ) is given by :
Sbcc = -R(6L WijkllnWijkl -12 Ltijk lntijk +3LYD 2) InYD2) +4LYl~ Iny~ - LXi lnxi)
~ ~ ij &
where Wijkl" tijk" YD2), Y~ and Xi respectively, denote the probability of finding
tetrahedra, triangles, second-neighbour pairs, first neighbour pairs and points in the
configuration given by their subscripts ( i represents A or B in a binary alloy), R is the
perfect gas constant.
In a fcc lattice two approximations may be used: the tetrahedron approximation when
the second neighbour pair interactions are negligible, and the tetrahedron-octaedron
approximation when the first and second neigbour pair interactions must be taken into
account. For the disordered fcc structure (AI) we have in the tetrahedron
approximation:
Sfcc = -R(2 L Wijkl ln Wijkl - 6Lyli) InYD 5L x i 1nxi)

1) -
ijkl ij i
For an ordered phase, the long range order is described by means of sublattices
reflecting the symmetry of the ordered structure. A given cluster may now have points
in the crystal belonging to different sub lattices and their probabilities have to be
distinguished accordingly (see the paper ofInden and Pitsch [44] for more details).
Liquid alloys may also display short range order, and it is essential to take it into
account in the determination of their thermodynamic data. The best way to perform
such calculations is to use a variational method with, as a reference system, a mixture
of hard spheres which all have the same diameter but different charges and which
interact through a screened Coulomb potential [24]. This reference system has been
found to describe well the structural and thermodynamic manifestations of short range
order in liquid alloys [21]. However Pasture I [49] has shown that the entropy of
configuration of a liquid phase can be approximated using a tetrahedron
approximation as in the disordered fcc structure.
The equilibrium state is obtained by minimization of the Gibbs energy: G = H - TS

with respect to the cluster probabilities using the natural iteration method [11] or with
respect to the correlation functions using the Newton-Raphson procedure. The
correlation functions are independent variables which can be easily expressed as a
function of the cluster probabilities. The enthalpy, H, is expressed as a function of the
correlation functions and of the cluster interactions.
In the following we will assume that the enthalpy is identical to the internal energy at
ordinary pressure for solid and liquid phases. The phase diagram is obtained by Gibbs
energy minimization provided that the Gibbs energy of each solid solution, of the
liquid phase and of the compounds are each referred to a same state which is indicated
in the following equations by G~f. and G~f. The Gibbs energy of a solid solution a
is then written as
where L'1mGu is the mixing Gibbs energy of the considered solid solution. G~' and
G~ are the Gibbs energies of A and B in the structure a. The formation Gibbs energy
(L'1 f GO) of a compound is usually referred to pure A and B in their standard states
(G ~ and G ~). Then the Gibbs energy of a compound is written:
When the CVM is used, it is more convenient to minimize the grand potentialQ given
by:
where !l * is called the effective chemical potential and is related to the chemical
potentials of A and B, !lA and !lB, in a binary system by :
The equilibrium phase diagram between two phases I and II is obtained when m =
011 for the same value of !l*.
The lattice stabilities of the constituents of an alloy are necessary to compute the phase
diagram. They can be taken from the compilation of Dinsdale [43] or, when ab initio
calculations are performed, they are derived from these calculations. However there is
still a "missing link" which is the difference in Gibbs energy between pure liquid and
the crystalline phases.
Although the density functional theory has made significant progress in the modeling
of liquids, application to the determination of the melting temperatures and enthalpies
does not yet appear possible. Therefore, we have chosen to use thermodynamic
compilations to obtain the Gibbs energy offusion [43].
The cluster interaction parameters may be fitted using thermodynamic and phase
diagram data, such as enthalpies of formation, enthalpies of ordering, temperatures of
order-disorder transformation, or from diffuse scattering data. These different
approaches and their applications have been reviewed by Inden and Pitsch [44]. An
important conclusion of these phenomenological calculations is that the atomic spatial
correlation, particularly the Cowley short range parameter (<Jk of the kth-coordination
shell) plays a crucial role in the details of equilibrium and metastable phase diagrams.
But the procedure can be misleading because the nature of the most important cluster
interactions (pairs, triplets, tetrahedra, etc.), their range and their composition
dependence are not known a priori.
For some years, several attempts were made to deduce the cluster interactions from
first principle calculations because of the necessity of developing a microscopic model
in order to have a clear insight into the nature of the pairs, and generally cluster
interactions appeared very clearly. Two methods will be developed in the next
sections: the tight binding approximation and the linear muffin tin orbitals method.
4 THE TIGHT BINDING ApPROXIMATION
The tight binding Hartree Hamiltonian can be divided into three terms:
H = HIe - He.., - Hion-ion.

HIe is the one electron tight binding Hamiltonian, He-. is the electron-electron
interaction subtracted from the one electron Hamiltonian, since this interaction is
counted twice in HIe, and Hion-ion is the interaction between the ions. The one electron
Hamiltonian can still be written as:
where liJ.L> is the ket for the orbital J.l at site i, the on-site and hopping energies Eill and
till.iv give respectively the effective atomic energy of the J.l orbital on site i and its
coupling to the v orbital on site j.
When treating alloys of two transition metals such as the Ni-Ti system, we have
considered five d orbitals per lattice site. The calculation in the Ni-AI system includes
five d-like and one s-like orbitals for Ni metal and three p-like and one s-like orbitals
for Al metal. The density of states is given by :
N(E) = LNill (E)
where the local density of states Nij.1(E) is given in terms of a configurationally

averaged diagonal Green function Gij.1,i,lE) :
To calculate the electronic density of states of compounds we have used the recursion
method which constructs a new orthogonal basis from the linear combination of
atomic orbitals, orthogonal basis {liJ.L>}. The Green function of the tight binding
Hamiltonian is given by the continued fraction terminated in the usual way. The
calculations are repeated for all the nonequivalent sites of the structure of the studied
compound. Then the electronic density of states of the compound is given by the sum
of these local densities of states. To compute the electronic density of states of a solid
solution which can exhibit chemical short range order, two methods can be used: the
coherent potential approximation and the generalized perturbation method or cluster
Bethe lattice method.
In the coherent potential approximation ( CPA) only completely disordered alloys can
be studied. To analyze the ordering effects in solid solutions it is necessary to use the
generalized perturbation method (GPM), the ordering energy being expressed in terms
of pair and many body interactions using a perturbation expansion of the random CPA
energy in concentration fluctuations [8,10,25,31]. This technique has been studied
extensively in the tight-binding approximation and has been very valuable in
elucidating general trends in the alloying behavior of the transition metals. One of the
main results is that the alloy ordering energy is generally dominated by concentration
dependent, effective pair interactions [30,34,39,40].
The other method of calculating the configuration averaged Green function is the
cluster Bethe lattice method (CBLM) introduced by Kittler and Falicov [13] and by
Robbins and Falicov [17,20]. This method has been used by Hawkins et al. [23,27,38];
in its simplest version, a simple, single atom cluster, the real lattice is replaced by a
Bethe lattice, the coordination number and the near distribution of the nearest
neighbours being reproduced exactly. Despite the fact that the CBLM relies on a
topological approximation (it replaces the real lattice by a Bethe lattice) in comparison
with the CP A-GPM, it presents the advantage of including easily the off-diagonal
disorder part of the tight binding Hamiltonian and a self-consistent treatment of charge
transfer with the short range order. These two contributions have been shown to be
essential in order to achieve a good agreement between experimental and calculated
values of the enthalpy of formation in binary alloys.
To compute the electronic density of states of a liquid alloy which can also exhibit
chemical short range order, a scalar version of the cluster Bethe lattice method
(SCBLM ) can be used [28]
In the CPA-GPM treatment, the random energy of formation is deduced from the
CPA, and the effective pair interactions from the GPM for alloys of various
compositions. In the CBLM treatment, the random energy of formation is obtained
when the short range order is taken equal to zero, the effective pair interactions are
fitted from the energy variation with the short range order. The computation of the
thermodynamic data and of a phase diagram needs analytical expressions of the
energy of formation. The energy of formation of a solid solution A-B for a given
composition x (x is the A composition) and a given short range order cr is:
llfE=E(x,cr)-xE~ -(l-x)E~.
E~ and E~ are the total energies of pure A and B in the same structure as the
considered solid solution. The energy of formation is written as the sum of a non-
local energy term (associated with the random alloy) llrandE and a local ordering
energy contribution Eord which takes into account the contribution cr, due to short
range order:
llrandE is function only of the composition x or of the point correlation function SI =

2x- 1. llrandE can be expressed by the polynomial expression:
In term of effective pair interactions the ordering energy is written:

where Zk ,Vk and !;~ are respectively the coordination number, the effective pair
interaction and the pair correlation function of the kth-nearest neighbours. The
effective pair interactions, Vk, are composition dependent and may be written as a
polynomial function of the point correlation function!;t. The pair correlation function
can be expressed as function of the pair probabilities as:
For transition metal based alloys we have considered pair interactions between first
nearest neighbours in a fcc lattice and between first and second nearest neighbours in a
bcc lattice. The set of tight binding parameters necessary for the calculations are
deduced from Herman and Skillman [5] and Harrison [15] tables using the Slater-
Koster [3] parametrization scheme and the Shiba [6] approximation.
5 THE liNEAR MUFFIN TIN ORBITALS METHOD
An alternative approach which is now extensively used consists in performing ab

initio total energy calculations of perfectly ordered compounds in order to estimate the
value of limited, arbitrarily chosen sets of interactions. The ab initio methods
generally used are the ASW augmented spherical wave, the LAPW linearly
augmented plane wave, the LMTO linear muffin tin orbital. We have used the last
method and will report below the principal features of the calculations to achieve
phase diagram calculations.
The energies of stoichiometric compounds and pure components of various structures

in the A-B binary system are calculated using the all-electron total energy local
density formalism as carried out with the linear muffin tin orbital (LMTO) method
[19]. The LMTO calculations were made in the atomic sphere approximation but
including combined corrections, as developed in the code of van Schilfgaarde et al.
[51]. We have used the parametrization of the von Barth-Hedin exchange correlation
energy density given by Moruzzi et al. [12].
In the Brillouin zone integrals, a uniform mesh of sampling points is used with at least
16 divisions along each of the primitive vectors. With such a mesh, the convergence of
the absolute value of the total energy to 0.1 mRy is obtained. The same radius value is
taken for the Wigner-Seitz spheres of all the elements and the spherical harmonic up
to 1 = 2 (d orbitals) is included in constructing the basic functions [47].
For each structure, the total energies provided by the LMTO method are obtained for
different values of the volume. Moreover, the bulk modulus, which is related to the
curvature of the total energy with volume is obtained using a fit based on Birch
Murnaghan's equation of state [I]. The Debye temperature can be deduced from the
value of the bulk modulus.
The ground states at zero temperature are obtained by comparison of the energies at
equilibrium for the same composition and various structures. The stable state
corresponds to the n-minimum of the energy with respect to the volume.
The major difficulty is to derive the effective cluster interactions in a given lattice
from the values of the total energies of various configurations based on this lattice. In
the approach proposed by Connolly and Williams [18] the total energy for a given
configuration (x based on a given lattice (fcc or bcc or hcp ), is written in the form of
a cluster expansion:
Y = 0 is the empty cluster with which a value of one of the correlation functions is
associated. Vy is the multisite interaction associated with the multisite correlation
function ~~ defined as :
where ern takes the values + 1 or - 1 depending on the occupancy of site n by an A or

B atom.
~~ is the particular value of the multisite correlation functiony in the configuration a

(for more details of the definition of the correlation functions see the paper of Inden
and Pitsch [44]).
The interactions are determined by an inversion of the sum for a finite number of
configurations on the same lattice defined by the existence of a maximum clusterYmax
beyond which the multisite interactions vanish. Hence from a finite number of total
energies for ordered structures and by truncating the summation in the expression of
the total energy, a set of multisite interactions is obtained from:
for 0 < Y::;; Ymax

a
forY>Ymax
Of course, one performs total energy calculations of as many ordered structures as

there are unknown multisite interactions required by the truncation but it is clear that,
in this approach, this truncation leads to a non-uniqueness of the cluster interactions
[42]. However, if the concentration-independent multisite interactions decay rapidly,
one can expect this difficulty to become minor and then in practice, the interactions
can be uniquely computed.
As the total energy of each considered compound is a function of the lattice parameter,
or of the cell volume, the multisite interactions are also a function of the volume.
Three distinct approaches are used to obtain the cluster interactions
i) The "locally relaxed" treatment for which each cluster in the alloy is able to
relax to its preferred lattice constant; in this case the cluster interactions are
considered as volume independent and are obtained using the equilibrium
values of the energies of the various substructures.
ii) The "frozen lattice" treatment where each cluster is calculated at a fixed lattice
constant; in this case the effective cluster interactions depend on the volume.
iii) The c-G method proposed by Ferreira et al. [37]; In this method the energy of
formation is written as the sum of a chemical term and an elastic contribution.
Indeed the energy of formation of the phase x, in which the composition of the
element A is x and the equilibrium volume is V, is
~fE(a, V) = E(a, V)- xE(A, VA) -(1-x)E(B, VB)
This expression can also be written :
~fE( a, V) = E( a, V) - xE(A, V) - (1- x)E(B, V)

+x[E(A, V) - E(A, VA)]+(1- x)[E(B, V)- E(B, VB)]
the first term corresponds to the chemical effect on alloying and the second term is an
elastic contribution: the energy necessary to bring pure A and B from their respective
equilibrium volumes to the volume of the alloy. The chemical energy is written as a
cluster expansion, the chemical cluster interactions being considered as volume
independent. The elastic term can be calculated knowing the physical characteristics
of the pure constituents and of the alloy [37].
When we calculated the AI-Ni phase diagram [49], we used in the bcc and fcc solid
solutions the "locally relaxed" treatment of the lattice relaxation effects which is
considered to be more accurate than the "frozen lattice" treatment [32].
The disordered energy is obtained using the fact that the pair and higher order
correlations are given as products of the point correlations for the totally disordered
state. For the fcc and bcc based structures, all atomic positions are equivalent, and we
have:
where ny is the number of sites contained in the y cluster. The energy of the disordered
configuration is then given by:
Ymax
E~~~= LVY(~l)ny
Y
Cluster interactions from the Connolly-Williams expansion [18] and effective pair
interactions from GPM or CBLM can be compared using a resummation of the higher
order cluster interactions at fixed concentration, corresponding to a lowest order
expansion of the total energy in powers of the short range order parameters. Indeed
Carlsson [32] has shown that it is possible to convert multisite interactions into
concentration-dependent, effective pair interactions.
They are obtained by making a truncated approximation in the higher-order correlation

functions, using only the pair correlation function. Even, if this development suffers
from a loss of accuracy, the effective pair interactions present advantages in their ease
of interpretability and their practical usefulness. The same treatment was proposed by
Sluiter and Turchi [40] with more clusters in fcc phases and in bcc phases.
6 RESULTS
In a review paper, Inden and Pitsch [44] established a list of phase diagrams calculated
by the ab-initio methods or using a tight binding approximation until 1990. Since this
time a large number of new investigations have been performed in this area, Turchi
[52] has done a review of these investigations until 1992.
The first calculations we performed concerned bcc transition metal alloys. The
enthalpies and entropies of formation of Cr-Mo, Cr-W, Mo-W, Mo-Ta, Mo-Nb and
Ta-W alloys have been calculated using a tight binding Hamiltonian and the Bethe
lattice method [36]. The miscibility gaps displayed in the Cr-Mo, Cr-W, and Mo-W
systems have also been calculated [36]. Later Colinet et al. [41, 48] and Le et al.
[45,46] presented calculations of the enthalpies of formation and phase diagrams
respectively in Ni-AI and Ni-Ti systems using the CBLM. The Ni-Ti system was also
studied in the CPA-GPM formalism [53]. Our first attempt to compute a phase
diagram using LMTO total energies calculations concerns the AI-Ni system [49].
All these calculations have been performed assuming a rigid lattice, assuming that the
configurational entropy of the stoechiometric compounds is equal to zero, neglecting
the electronic entropy term, and also the vibrational contribution to the Gibbs energy
of formation. Recently we calculated the Au-Ni phase diagram from LMTO
calculations; in this case we introduced the relaxation of the lattice, and took into
account the vibration contribution in the Debye-Grilneisen approximation [54].
7 CONCLUSION
We have shown that the contributions of relaxation dominate the behavior of the
configurational energy whereas the contribution of the vibrational modes lowers the
miscibility gap at its maximum temperature by approximately 200 K. We believe that
our results show that first principle studies of phase equilibrium may now be
considered feasible. We are presently studying other systems using the LMTO
method. The major point of discussion is now the level of truncation of the energy as a
function of the cluster interactions to obtain reliable values of these cluster
interactions. Preliminary calculations have also shown the importance of various
contributions: relaxation, vibration of the lattice and electronic entropy.
KEYWORDS
cluster variation method, CPA-GPM, CBLM, LMTO
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EVALUATION OF EQUATIONS OF STATE AT HIGH
PRESSURE FOR LIGHT HYDROCARBONS
J.-c. DE HEMPTINNE, A. BARREAU, P. UNGERER, E.

BEHAR
IFP, 1&4 Av. de Bois-Preau, F-92506 Rueil Malmaison Cedex, France
ABSTRACT
Equations of state are used for predicting reservoir fluid properties in a large range of
pressures and temperatures. The choice of an equation depends on the type of
component, the pressure and temperature ranges and the property to be computed. In
this work, four equations are tested (Peng-Robinson, Simonet-Behar Rauzy, Lee and
Kesler, Chain of Rotators) for three different thermodynamic properties (molar
volumes, isobaric and isochoric residual heat capacities). The accuracy of the
calculations for alkanes from methane up to n-butane are expressed as deviation maps
in (P, T) coordinates. The analysis is mainly focused on the behavior in the high
pressure and high temperature regions. The modified version of the Lee & Kesler
method provides good density results for hydrocarbons up to n-butane, but is not to be
used for heavier components
RESUME
Des equations d'etat permettent de predire les proprietes des fluides de reservoirs
(petroliers) dans une large gamme de press ions et de temperatures. Le choix d'une
equation depend du type de fluide, des intervalles de pression et de temperature et de
la grandeur aprevoir. Dans Ie travail presente, quatre equations ont ete testees (Peng-
Robinson, Simonet-Behar Rauzy, Lee et Kesler, Chain of Rotators) pour trois
differentes proprietes thermodynamiques (volume molaire, capacites calorifiques
residuelles isobares et isochores). La precision des cafculs pour les alkanes depuis Ie
methane jusqu'au n-butane est presentee sur des cartes de deviation en coordonnees
pression et temperature. L'analyse a porte principalement sur Ie comportement devant
les hautes press ions et les hautes temperatures. La version modifiee de la methode de
Lee et Kesler, fournit de bons resultats pour fa densite des hydrocarbures jusqu'au n-
butane mais ne convient pas pour des composes plus lourds.
S4 New Developments in State Equations ...
1 INTRODUCTION
According to the phase rule, the behavior of a mixture is entirely determined once
\f'=2+n-IT
state variables are known (n is the number of components in the system and IT is the
number of phases). For many engineering applications, it is important to know one or
several thermodynamic properties of a given mixture. Properties that are most
commonly looked for are densities or molar volumes, enthalpies, fugacities to
determine phase equilibria and heat capacities. Usually no reliable experimental data
can readily be found for a particular need (i.e. enthalpy, fugacity, ... ), so that models
must be used to compute the property of interest.
All thermodynamic properties can be computed from the knowledge of two

relationships:
• The ideal gas heat capacity for each component, as a function of the absolute
tem perature:
C~i = f(T)
• An equation of state (eos) relating pressure, volume, temperature and composition.
Most commonly, it is explicit in pressure:
P = g(v,T,N1, ... ,N n)
where n is the number of components and Nj the amount (in moles) of
component i present in the mixture.
Hereafter we will evaluate the accuracy of various equations of state in calculating the
most important properties. The criteria for a proper selection among the very large
number of equations is based on:
• The composition of the mixture to be modelled. It is clear that self-associating

liquids require a different approach than polymers. In this paper, we only consider
pure light hydrocarbons, and in particular methane, ethane, propane and n-butane.
• The computation time and the availability of a computer program is often a crucial
reason for eliminating some equations that may be very accurate otherwise.
• The pressure and temperature ranges. At very low pressures, all substances tend to
the ideal gas behavior. Very simple (virial) equations are accurate enough. At high
pressures, some equations may yield better results in the liquid region (low
reduced temperatures), others in the supercritical region (high reduced
temperatures). Generally, analytical equations have the most difficulty in modeling
correctly the region surrounding the critical point.
• Depending on the property to be modelled, different calculations must be carried
out with the equation of state:
Evaluation of Equations of State at High Pressure 55
* If the molar volume is needed, an iterative technique directly yields the

roots of the equation.
* When phase equilibrium conditions must be determined (generally called

flash calculations), the component fugacities are evaluated by means of:
RTln f~ = ((-~l
Pi aNI TN.
+ RT]dV_RTln(PV)
V RT
(1)
, J'v
A correct calculation of the molar volumes as a function of pressure is
needed.
* If enthalpic information is needed, the residual enthalpy is calculated as

follows:
h""(P, T) ~ hlP, T) - h# (P, T) ~ r: ( :IT -

v T:UdV (2)
It thus requires the evaluation of two different derivatives. The change of

ideal gas enthalpy with temperature must also be computed using the ideal
gas heat capacity. The evaluation of the possible equations for this property
(see for instance Aly and Lee, [2] falls outside the scope of this paper.
* The isochoric and isobaric heat capacities are split into two parts:
and
cp -- c#p + Cpres (4)

Only the residual part of these properties can be computed from equations of
state:
A second derivative is needed here. The calculation of the residual isobaric heat
capacity first requires the calculation of Cvres(T,v):
Cres(T P)
p'
= Cres(T
v'
v) _ ) ~J
8PI (6)
OvT
In this last equation (6), the third term (ratio of first derivatives of the equation of state)
is much larger than Cvres , except perhaps for high temperatures and low pressures. In
this latter region, however, the residual properties are negligible compared to the ideal
gas properties and the error is of little significance. The reliability in the calculation of
the residual isobaric heat capacity depends therefore essentially On the capacity of the
equation of state to describe correctly the first derivatives versus temperature and
volume.
The purpose of this paper is to evaluate the ability of a number of equations of state to
reproduce well some important physical properties of pure fluids. We chose three
properties: molar volume, residual isochoric heat capacity and residual isobaric heat
capacity.
• All calculations require a correct estimation of the molar volume. This property is
therefore of crucial importance.
• As mentioned above, the calculation of the residual isobaric heat capacity allows a
test of the calculation of the first derivatives of the equations of state.
• The residual isochoric heat capacity calculation is a very stringent test for an
equation of state as it requires, along an isochore, an excellent description of the
second derivative of the equation versus the temperature.
2 THE EQUATIONS OF STATE STUDIED
In this work, we have tested four equations of state very different in their structure: the
well-known Peng-Robinson equation as a representative of the cubic equations of
state; the Simonet-Behar-Rauzy-Jullian (SRBJ) equation of state developed at the
Institut Franyais du Petrole which provides a good description of hydrocarbon
volumetric properties; the Chain-of-Rotators equation of state based on statistical
mechanical considerations and the Lee-Kesler method using the corresponding state
principle.
2.1 The Peng-Robinson equation of state
The cubic equation of state of Peng-Robinson [16] can be expressed in the general
form:
with
b=b+c v=v+c
v is the calculated volume before correction and c is the translation term proposed by
Peneloux [15]. The volume translation c has been selected so that the correct molar
volume is obtained for the saturated liquid at atmospheric pressure, which is

determined from Reid et al. [17] density data.
2.2 The equation of state of Simonet, Behar, Rauzy and Jullian
The SBRJ equation of state (Jullian et aI., [13]) is a modification of the non-cubic
equation of state SBR (Simonet, 1978, Behar et al.[5,6]). They both have the following
form :
P =RT
--- a b b2 J
( l-y-+<>- (8)
v- b (v (v + b) v v2
The SBRJ equation of state contains four parameters which vary with the temperature.
This dependence is expressed through the corresponding state law using methane as a
reference component. The only values that are needed in order to apply this equation of
state are the critical coordinates (Tc' Pc) and the acentric factor.
2.3 The Chain-of-Rotators equation of state
A number of equations are based on a more theoretical approach: PHCT, BACK, COR,
SAFT, .... Following the recommendation of Solimando [20], we chose to investigate
the Chain-of-Rotators equation of state. This equation of state proposed by Chien [9] is
based on a modification of the repulsion term. It includes a term developed by
Carnahan and Starling [7] for hard spheres and a term that takes into account the shape
of the molecules. The attractive term is based on the theory of Alder et al. [1].
Z = 1 + 4y-2y2 + 05 '( '1)3Y+3a'y2_(a'+l)y3

. C a- + (9)
(l_y)3 (l_y)3
with: y = Jr/2 (v */6vJ = 0.7405 v*/v
The parameters Ank and Bi are universal. The value of a', which is related to the
length of the carbon-carbon bond, is fixed at 1.078.
Three parameters are enough to characterize a pure substance: v *, T* and c '. This last
parameter corresponds to the number of "extemal" rotational degrees of freedom. The
parameters used in this work are taken from the publication of Chien et al. [9].
2.4 The Lee-Kesler method
The method developed by Lee and Kesler [14] is based on the principle of
corresponding states. The compressibility factor of two substances (C1 and C8) can be
expressed very accurately by using a reference equation of state. In order to calculate
this property for any other substance, a simple interpolation formula is used, based on
the acentric factor :
(10)
where:
and Pc and Tc are the critical constants of the component of interest. For mixtures,
mixing rules must be used. The reference equation used to express the reference
compressibility factors Z1 and Z8 is the Benedict-Webb-Rubin (BWR) equation found
in the original publication (Lee & Kesler, [14]). The pure component parameters, Tc '
Pc and m are taken from Reid et al. [17].
3 REFERENCE DATA
In order to compute deviations on a grid with very narrow pressure and temperature
intervals, we would need either a complete set of consistent, high-quality experimental
data covering the whole pressure and temperature range desired for the component
considered, or specific equations of state whose volumetric calculations lie within the
uncertainty range of experimental measurements. In the present work, two types of
reference equations of state are used:
1) The modified Benedict-Webb-Rubin (BWR) (Jacobsen and Stewart, 1972) equation

is a 32 parameter equation containing a polynomial in the density,p, and terms with an
exponential function of _(p/pc>2.
19 19
P = pRT + I GiprjTSj + I GiprjTSj exp(-(p/ Pc)2 (11)
i=l i=l
where Pc is the critical density ofthe fluid, T the temperature and P the pressure.
The parameters Gi with the exponents ri and si are calculated so as to best approximate
the experimental data. This equation has been adapted to the light hydrocarbons by
Younglove and Ely ([22]. The range of validity of this equation as proposed by these
authors is shown in Table 1.
Compound P Tmax(K)
max (Mpa)
Methane 200 600
Ethane 70 600
Propane 100 600
Isobutane 35 600
Normal butane 70 500
Table 1: Validity range of the equation proposed by Younglove and Ely [22]. The
minimum temperature is the triple point temperature.
The uncertainties on molar volumes and heat capacities calculated by these equations
are given in Table 2.
Property Liquid Gas Fluid Critical

belowT BelowT AboveT Region
c c c
Methane
Molar volume 0.2 0.3 0.1 5
Isobaric Heat Capacity C 5 5 2 10
P
Isochoric Heat Capacity C 5 5 2 10
v
Ethane
Molar volume 0.5 2 0.2 0.2 5
P
Isochoric Heat Capacity C 1 1 10
v
Propane
Molar volume 0.1 0.04 1.5 1.5
P
v
Normal butane
Molar volume 0.05 0.4 0.06 3
P
v
Table 2: Uncertainties (%) for the properties calculated with the equation proposed by
Younglove and Ely [22]
2) The Schmidt and Wagner [18] equation of state is similar to the previous equation,
except for the presence of an exponential function of -(pi pC)4. It is derived from an
expression given for the residual part of the Helmholtz energy :
A-A# 13 24
<D res = RT =I GipqTs i + I GiPriTsi exp(-(p/pc)2)
i=l i=14
12
The pressure explicit equation is obtained from:
8~r
p=-( -8A) =RTp(1+p-) (13)
8V T 8p
Regarding the rather large uncertainties on the molar volume near the critical region
with the modified Benedict-Webb-Rubin equation, we chose to use the Schmidt and
Wagner equation as the reference equation for computing the "experimental" molar
volumes of methane and ethane. All other reference data were obtained with the
modified BWR equation, as proposed by Younglove and Ely [22].
These authors usually do not guarantee the same low uncertainty in extrapolation
above the highest pressure limit given in Table 1. Where experimental data could be
found, the equations have been tested with molar volumes up to 3000 bar. For ethane
(data from Tsiklis et aI, [21]), the deviations did not exceed 2%; for propane (data from
Babb and Robertson, [3]) they remained below 0.5%. For heat capacity determinations,
the upper pressure limit of the equation was not exceeded.
4 DEVIATION MAps
The deviation maps presented in this work show the relative deviation F versus
pressure and temperature, for a selected set of properties, components and equations of
state. Deviation is defined as:
F = lOO(Xcal(T, P) - Xref(T, P») (14)

Xref(T, P)
where Xcal(T,P) is the property (density, isochoric or isobaric residual heat capacity)
computed from the equation of state considered, and Xref(T,P) is the property obtained
from the reference equation of state. For density calculations, only the absolute value
ofF is considered.
The detailed results with all deviations charts cannot be given within the scope of this
talk. We therefore refer the reader to the two following more complete publications
(Barreau et aI, [4] and de Hemptinne and Ungerer, [10])
4.1 Volumetric results
For each component, the density deviation between the reference equation and the four
equations of state investigated has been calculated in the range of 1 to 2000 bars, 150
to 500K. An illustration of these deviation maps is presented in Figure 1 (methane).
c. Chai n-or-R otators equa tion d. Lee· Kesler melhod
1$. 2Of) l SO .\1)1] .lSI) ~uo 21MI 250 "HI .IS. $'HI
Tempcraturc (K) Temperature (K)
Figure 1: Error maps on density for methane
For each equation of state, the deviation patterns obtained for different components
tend to show a common shape, simply shifted by the critical point of the component.
For instance, the low temperature domain on the methane deviation map corresponds
to the high temperature domain of the n-butane map. This may be summarized by the
following statement: for a given equation of state, the density inaccuracies of most
equations of state seem to obey the principle of corresponding states. Along the
saturation line, deviations may result from two different causes:
1) inaccurate vapour pressure calculation, which results in an erroneous phase

prediction (vapour instead of liquid, or the opposite), 2) inaccuracy in the calculation
of the density. In case 1, a narrow zone of large deviations is observed. In case 2,
moderate deviations are evidenced but in a wider zone. The quality of the equations is
evaluated in four different regions and summarized in Table 3. The results for methane
have been separated from the other light hydrocarbons as its critical temperature is so
small that the liquid region is insignificant compared to the supercritical region.
The vapour region is very well represented by all equations as the fluids tend to the
ideal gas behavior. Second comes the liquid phase, where the Peng-Robinson equation
has the largest errors. There, the Chain of Rotators equations show the best results,
especially for the heavier hydrocarbons.
Methane
Phase Close to
liquid Supercritical vapour critical point
Peng-Robinson + ++ +++ --
S.B.R + - ++ +
Chain-of-Rotators ++ - ++ -
Lee-Kesler + ++ +++ ++
Ethane, Propane, Normal butane
Peng-Robinson + + +++ --
S.B.R ++ + ++ +
Chain-of-Rotators +++ + + -
Lee-Kesler ++ ++ +++ +
very bad (>10%) + average (2 to 5%)
bad (5 to 10%) ++ good (1 to 2%)
+++ excellent «1%)
Table 3: General evaluation of the ability of equations of state to calculate the molar
densities
In the supercritical region, the differences are more noticeable from one component to
the other than from one equation to another. The exception is the Lee and Kesler
method that provides good results in that area. The Peng-Robinson equation also yields
very good results for methane, but deteriorates for higher molecular weight
components. The SBR and COR equations, on the other hand, are bad for methane and
improve with increasing molecular weight. The critical area is the most difficult to
model correctly. The Peng-Robinson equation clearly provides the worst results in that
area, while the Lee-Kesler method is the most accurate. The modifications to the cubic
equations implemented in the SBR equation are most appreciated there.
4.2 Results on residual isobaric heat capacities
The magnitude of the residual isobaric heat capacity is strongly dependent on the
situation on the "pressure/temperature-map". Approaching the critical point, the heat
capacity goes to infinity because the isothermal compressibility goes to zero. In the
liquid phase, the residual heat capacity is always considerable, while it vanishes in the
vapour phase, except close to the vapour pressure curve at reduced temperatures above
about 0.85. Thus, when testing equations of state, it must be strongly emphasized that
the absolute error in some areas is insignificant, although the relative error seems
rather large. In these areas, other types of equations of state will probably be better.
The four selected equations of state were tested for their ability to calculate the residual
isobaric heat capacity of methane, ethane, propane, iso-butane and n-butane. For each
component, error maps were drawn in a domain of pressure up to 300 bars and
temperature up to 450K. For methane and propane additional maps were drawn at
higher temperatures and pressures (methane : P up to 2000 bars and T up to 600K,
propane : P up to 1000 bars and T up to 600K). All error maps can not be shown within
the limited scope of this presentation. However, Figure 2 illustrates, for methane, the
results obtained for the four different equations. Table 4 summarizes the results for all
components. Methane has again been set apart as the behavior of the equations is
somewhat different when applied to this substance.
uoo
.,
'i:'
e
§ 1000
'qj
"'.."
Po.
500
500
-
200 300 400 600 eoo 200 300 400 000
Temperature (X) Temperature (X)
_ Above 50.0 -2.0 - 0.0

20.0 - 50.0 -5.0 - -2.0
C~"' (EOS) - C~"'( E ·Y ) x 100 10.0 - 20.0 -to.O - -5.0
Cp "'(E.Y) 5.0 - 10.0 -20.0 - -to.O
0 2.0 - 5.0 -50.0 - -20.0
D 0 .0 - 2 .0 Be low -50.0
Figure 2: Residual isobaric heat capacity. Comparison error maps for methane (high
pressure) (see also colour plate on page 391)
Methane
Phase Close to
liquid supercritical vapour critical point
Peng-Robinson + + - -
S.B.R +++ + - +
Chain-of-Rotators + - - -
Lee-Kesler ++ +++ ++ ++
Ethane, Propane, Isobutane, Normal butane

Peng-Robinson + + - -
S.B.R - + - +
Chain-of-Rotators +++ + - -
Lee-Kesler ++ ++ +++ +

bad (20 to 50%) ++ good (5 to 10%)
+++ excellent «5%)
Table 4: General evaluation of the ability of equations of state to calculate the residual
isobaric heat capacity
The Peng-Robinson equation of state is not accurate in its description of the residual
heat capacity. In fact, , it is not really reliable in any area for any of the components. In
the liquid phase, the Cpres is underestimated for reduced temperatures lower than 0.74,
and overestimated for higher temperatures.
The SBRJ equation of state has a structure similar to the Peng-Robinson equation but
with an additional density dependent term which allows an improved description of the
PVT properties at high densities. On the other hand, it does not obey the constraints at
the critical point (first and second derivatives of the pressure versus volume are zero at
Tc and Pc).
These two characteristics of the SBRJ equation of state cause the following
particularities. Near the critical point, the "large error" zone is quite small compared to
the other equations of state, and there is only one "error lobe" which is negative and
situated in the vapour-like part of the supercritical zone. This gives a good description
of Cpres in the area with pressures close to the critical pressure and temperatures above
the critical temperature. The additional repulsion term intervening at high densities in
the COR equation seems beneficial for the desciption of the liquid phase. Although the
Aij constants were fitted to experimental data of methane, the COR does not describe
the Cpres of methane very well. It is bad in the liquid phase close to the critical point
and also in the vapour phase and in the supercritical region except at low pressures. For
the other components, the C pres in the liquid phase is very well described by COR. The
prediction is improved close to the critical point for higher chain length components
while the supercritical phase is rather poorly described.
The Lee and Kesler method clearly gives the best results. For all components, the
errors are smaller than 10% in the whole pressure-temperature domain. The
supercritical phase is very well described compared to the other equations except close
to the critical point. In the vapour phase, the Lee-Kesler equation is the only equation
able to give reasonable values ofC pres . At very high pressures, the results are also very
good except at very low temperatures.
4.3 Results on residual isochoric heat capacities
As stated earlier, the residual isochoric heat capacity is a very stringent test for an
equation of state. Figure 3 represents the error maps of ethane for this property. We
can see that none of the selected equations of state is able to calculate C/es reliably.
For PR, SBRJ and COR, the error maps are very similar. In the vapour phase and the
vapour-like supercritical phase, the errors are strongly negative. In the liquid phase and
the liquid-like supercritical phase, the errors are extremely positive. For the three
equations, there exists a narrow zone where the C/es prediction is good. For the LK
equation, the results are slightly better but the error sign is reversed. Table 5
summarizes the above observations.
Ethane
Phase Close to
Liquid supercritical vapour critical point
Peng-Robinson - - -- --
S.B.R -- - -- --
Chain-of-Rotators - + -- --
Lee-Kesler - + - -
bad (20 to 50%) ++ good (5 to 10%)
+++ excellent «5%)
Table 5: General evaluation of the ability of equations of state to calculate the residual
isochoric heat capacity
66 New Developments in State Equations .. .
Temperature (K)
AbQv(' 50.0 -2.0 - 0.0

20.0 - 50.0 -5.0 - -2.0
Cv''' (EOS ) - Cv'''(E-Y) x 100 10.0 - 20.0 -10.0 - -5.0
Cv"' (E-Y) 5.0 - 10.0 -20.0 - -10.0
2.0 - 5.0 -50.0 - -20.0
0.0 - 2.0 Below -50.0
Figure 3: Residual isochoric heat capacity. Comparison error maps for ethane
(see also colour plate on page 392)
5 CONCLUSION
In this work, we have tested the ability of four equations of state, very different in their
structure, to compute three different physical properties requiring different types of
calculations on the equation. The molar volume is obtained by solving the equation of
state with an iterative procedure, the residual isobaric heat capacity is calculated using
first derivatives of the equation, in addition to the isochoric heat capacity, which itself
is computed with a second derivative. These tests have been performed with the four
lighter hydrocarbons. The error maps have been obtained by comparing the properties
calculated by these equations of state with the "experimental" values obtained with a
reference equation of state.
The following conclusions can be drawn:
• It appears, as expected, that the more the equation of state must be

mathematically manipulated, the worse the modeling result becomes. Thus, the
inaccuracies on the residual isobaric heat capacities, essentially based on the first
derivatives of the pressure versus temperature and volume, are greater than for the
molar densities that are obtained by simple root-finding techniques. Residual
isochoric heat capacities that require a second derivative are thus the worst
represented.
• For all properties, the most difficult area to represent is that surrounding the
critical point. Second, for the residual heat capacities, comes the vapor phase, for
which, on the contrary, the molar volume is very well represented. Note,
however, that for vapor, the residual heat capacity is very small compared to the
ideal gas heat capacity.
• The Lee-Kesler equation of state is the best of the four for the three properties
tested. There is no domain in which its predictions are unrealistic. This is
certainly due to the fact that both the Lee-Kesler and Ely-Younglove equations of
state are based on a BWR equation of state. This kind of equation computes the
fluid properties very well but it includes a great number of parameters.
• Depending on the P-T area of interest, the second best equation to use is the
COR equation (at high pressures) or the SBR equation (close to the critical point).
If isochoric heat capacities are needed, it is best to avoid the use of the SBR
equation.
• In general, the Peng-Robinson equation of state gives the worst performance. Its
major advantages, however, are its simplicity of use and its availability in
numerous computer applications.
Notations
a Parameter of the Van der Waals type of equation of state
A Helmholtz energy
Ank Universal parameters in the COR equation of state
b Parameter of the Van der Waals type of equation of state
BO,Bl, B2 Universal parameters in the COR equation of state
c Volume correction ofPeneloux [15]
c' Parameter in the COR equation of state
Cp Isobaric heat capacity
Cv Isochoric heat capacity
Gi Parameter in the modified BWR equation of state
fi Fugacity of component i
F Deviation as plotted on the deviation maps
h Molar enthalpy
n Number of components in a mixture
P Pressure
ri Parameter in the modified BWR equation of state
R Ideal gas constant
si Parameter in the modified BWR equation of state
T Temperature
T* Parameter in the COR equation of state
v Molar volume
v* Parameters in the COR equation of state
Molar volume before volume correction
x Any selected property
y Compacity term in the COR equation
Z Compressibility factor
a' Fixed parameter in the COR equation of state
Parameter in the SBR equation of state
Parameter in the SBR equation of state
Number of phases in the phase rule
Residual part of the Helmholtz energy
Degrees of freedom in the phase rule
Density
Acentric factor
Superscripts:
# ideal gas
res residual value
Subscripts
I Methane in the Lee-Kesler method

8 n-octane in the Lee-Kesler method
c At the critical point
cal Calculated value
Refers to constituent i
r Reduced value of pressure or temperature
ref Value obtained by a reference equation
KEYWORDS
equation of state, reservoir oil, fluid propagation, heat capacity, molar volume, high
pressure, high temperature, density
REFERENCES
[1] Alder BJ., D.A. Young and M.A.Mark, "Studies in molecular dynamics. X.
Corrections to the augmented Van der Waals Theory for the square well fluid" J.
Chem.Phys., 56, W6, (1972), 3013-3029
[2] Aly F.A. and L.L. Lee, "Self-consistent equations for calculating the ideal gas
heat capacity, enthalpy and entropy" Fluid Phase Eq., 6, (1981), 169-179
[3] Babb S.E. and S.L. Robertson, "Isotherms of ethylene and propane to 10000 bar",
J. Chern. Phys., 53, N°3, (1970),1097
[4] Barreau A., 1. Vidal and J. Mogensen, "Isobaric heat capacity calculation of light
hydrocarbons by means of equations of state" Revue de I'Institut Fraw;:ais du
Petrole, 48, N°5, (1993), 515-525
[5] Behar E., R. Simonet and E.Rauzy, "A new non-cubic equation of state", Fluid
Phase Eq., 21, (1985), 237-255
[6] Behar E., R. Simonet and E.Rauzy, "A new non-cubic equation of state,
ERRATUM", Fluid Phase Eq., 31, (1986), 319
[7] Carnahan N.F. and K.E. Starling, ""Intermolecular Repulsions and the Equation
of State for Fluids" AIChE. J., 18, W6, (1972),1184-1189
[8] Chapman W.G., K.E. Gubbins, G. Jackson and M. Radosz, "New reference
equation of state for associating fluids" Ind. Eng. Chern. Res.,29, (1990), 1709-
1721
[9] Chien C.H., R.A.Greenkorn, K.c. Chao, "Chain-of-rotators equation of state",
AIChE. J., 291 W4, (1983), 560-571
[10] de Hemptinne J., P. Ungerer, "Accuracy of the volumetric predictions of some
important equations of state, including a modified version of the Lee and Kesler
method" Fluid Phase Eq. submitted for publication
[11] Friend D.G., J.F. Ely and HIngham: "Thermophysical properties of methane", J.
Phys. Chern. Ref. Data, 18, W2, (1989), 583
[12] Friend D.G., H. Ingham and 1.F. Ely, "Thermophysical properties of ethane", J.
Phys. Chern. Ref. Data, 20, W2, (1991), 275
[13] Jullian S., A. Barreau, E. Behar and J. Vidal, "Application of the SBR equation to
high molecular weight hydrocarbons", Chern. Eng. Sci., 44, N°4, (1989), 1001-
1004
[14] Lee B.I and M.G. Kesler, "A generalized thermodynamic correlation based on
three-parameter corresponding states", AIChE. 1., 21, N°3, (1975), 510
[15] Peneloux A., E. Rauzy and R. Freze, "A consistent correction for Redlich-
Kwong-Soave volumes", Fluid Phase Eq., 8, (1982), 7-23
[16] Peng D-Y and D.B. Robinson, "A new two-constant equation of state", Ind. Eng.
Chern. Fundam., 15, (1976),59-64
[17] Reid R.C., J.M. Prausnitz and T.K. Sherwood, "The properties of gases and
liquids", 3rd edition, Mc Graw Hill Book Comp., (1977)
[18] Schmidt Rand W. Wagner, "A new form of the equation of state for pure
substances and its application to oxygen", Fluid Phase Eq., 19, (1985), 175-200
[19] Solimando R, "Equations d'etat susceptibles de representer les fluides petroliers",

Ph.D. Thesis, Universite de droit, d'economie et des sciences d' Aix-Marseille
(1991 )
[20] Solimando R., M. Rogalski and L. Coniglio, "Heat capacity estimations using
equations of state", Thermochimica Acta, 211, (1992), 1-11
[21] Tsiklis D.S., A.I. Semenova, S.S. Tsimmerman and E.A. Emel'yanova,
"Compressibility and thermodynamic properties of Ethane at ultrahigh pressures
and high temperatures", Russ. J. Phys. Chern., 46, N° 11, (1972), 1677
[22] Younglove B.A. and 1.F. Ely, "Thermophysical properties of fluids II. Methane,
ethane, propane, isobutane and normal butane", 1. Phys. Chell. Ref. Data, 16,
W4, (1987), 577
Chapter 2
PREDICTIONS AND VALIDATION OF

PHYSICAL AND ENERGY DATA
THERMOCHEMICAL MIMICRY
Joel F. LIEBMAN1 * and Hussein AFEEFY,
Department of Chemistry and Biochemistry, University of Maryland, Baltimore

County Campus, Baltimore, MD 21250 (USA).
ABSTRACT
Thermochemical mimicry is defined and applied to the enthalpies of formation of

organic and inorganic derivatives of the halogens and the alkali metals.
RESUME
Le "mimetisme" en thermochimie est defini et applique aux enthalpies de formation
des derives organiques et inorganiques des haloglmes et des meraux alcalins.
1 INTRODUCTION
We commence this study with a definition, an acknowledgment, and a confession.

Thennochemical mimicry of the group X by the group Y is defined by a constant
1 Permanent address: Chemistry Department, Mansoura University, Mansoura (EGYPT).
72 Predictions and Validation of Physical and Energy Data
difference for some thermochemical property ofRX and RY that is independent of the
choice of R. That is, for some property P, then thermochemical mimicry for X and Y
means
P[RX] - P[RY] = P[R'X] - P[R'Y] (EQ.l)
for any choice of Rand R'. In the text that follows, P is always an energy or enthalpy
term: most often we will consider enthalpies of fomlation, implicitly (and
colloquially) at "25°C (298K) and 1 atm". We acknowledge that if the principle of
group additivity [1,2,3] were strictly valid, then essentially any X and Y could serve
as the mimic for the other. Equivalently, mimicry would become a trivial property not
unlike conservation of mass, charge and atom-type for isodesmic, homodesmic,
exchange or transfer reactions of the type
RX + R'Y ---+ RY + R'X (EQ.2)
We would then write: P[RX] + P[R'Y] = P[RY] + P[R'X] (EQ.3)
which is but an algebraic rewriting of equation 1. However, since group additivity is

never strictly valid for any thermochemical property, then there are no absolutely
realized cases of mimicry. This latter statement of contrition, of course, is somewhat
disingenuous because if we strictly meant "never" and "no", we would never have
started this project and there would have been no conference presentation or
associated publication. What we mean in practice is that discrepancies of a "few" kJ
mol- l must be tolerated. Whether these deviations are ascribed to some structural
feature that earlier had been neglected, to inaccuracies in a measurement, or impurities
in a sample, is less the issue than the utilitarian approach of offering simple predictive
estimation methodologies for the experimental chemist to use, extend or delimit, and
for the theoretical chemist to rationalize or explain. Deviations must be tolerated:
whereas there are some ten million known compounds, two major archival sources for
enthalpies of formation contain but ca. 6000 inorganic [4] and 3,000 organic [5]
compounds respectively. By writing Rand R', we may seem to limit our attention to
organic chemistry and then further limit it to the study of derivatives of the relatively
simple alkyl groups. Not so, because Rand R' may be taken from the inorganic
vocabulary as well. However broad the scope of this study, the examples to be
discussed below will be related to our own studies.
2 EXAMPLES
2.1 Example of F and OH
Benson [6] introduced the concept of "isothermal pair" for this choice of X and Y
because the enthalpies of formation of numerous sulfur - fluorine and the
Thermochemical Mimicry 73
corresponding sulfur - hydroxy species are nearly identical, e.g. iltHm °(Na+FS03-, s)
= -1122.1 kJmol- i and iltHm (Na+HOS03-, s) = -1125.5 kJmol- i . We do not ask for
near identity: it suffices for us that the differences are nearly constant. That aside,
extension for the application to more general fluoro- and hydroxy- compounds
throughout the periodic table were made[6], including a revised rule that also spoke of
a nearly constant ca. 25 kJmol- i difference for corresponding organic compounds
taken in their gaseous state[8,9], e.g iltHmO(iPrF, g) = -293.5 ± 1.5 kJmol- i ,
iltHm O(iPrOH, g) = -272.8 ± 0.5 kJmol- i , iltHm0= -22.1 ± 1.6 kJmol- i . It is clear, at
least a posteriori, that a constant difference (in any phase) cannot be universally true:
the enthalpies of formation of alkali metal fluorides and hydroxides are significantly
different, e.g. iltHm °(NaF, s) = -573.6 kJmol- i and iltHm °(NaOH, s) = -425.6 kJmoti,
i.e. iltHmo= -148.0 kJmol- i . Significant difference is also found for the fluorides and
hydroxides of the more electronegative elements, e.g. iltHm 0(F2 , g) = 0.0 kJmol- i ,
iltHm O(HOF, g) = -98 kJmol- i [10], iltHmO(H202, g) = -136.3 kJmol- i , with iltHm
0= 98 and 38 kJmol- i respectively. The differences of enthalpies of formation of the
corresponding fluoro-, and hydroxy- compounds are opposite in sign for the two
cases, and this suggests an electronegativity dependent difference for the enthalpies of
formation of the fluoro and hydroxy derivatives. A semi-empirical quantum
chemical/formal electronegativity based study [11] of a variety of these species
confirmed this dependence and the fortuity of the near equality for carbon and sulfur-
containing species. The organic chemist may give a sigh of relief, but it must be
acknowledged that there is but one aliphatic (" sp3 ") monofluoride, 1-AdPh2CF, for
which there is a modem combustion calorimetric measurement of its enthalpy of
formation [12] (-120.5 ± 2.5 kJmol- i ), but there are no thermochemical data for its
corresponding alcohol. Indeed, while use of earlier data shows general success, that of
the most scrutinized organic case [13] is for CH3F and CH30H with enthalpies of
formation, -225.4 and -201.5 ± 0.3 kJ mol-I, respectively, and we recall methyl is an
atypical alkyl group [14]. If we consider fluorine mimicked by hydroxy, what then
mimics the other halogens?
We have studied mimicry involving chlorine twice, once in an organic and once in an
inorganic "motif': true generality evades us. With regards to organic mimicry [9], it is
seen that gas phase alkyl chlorides and their corresponding nitro compounds enjoy a
quite constant -7 ± 3 kJmol- i enthalpy of formation difference. Nearly the same
difference is seen for R=Me, Et, iPr and tBu, namely -7.6 ± 0.6, -9.8 ± 1.3, -5.9 ± 1.6
and -5.1 ± 4.0 kJmol- i . Compounds with multiple chloro groups fail to show the same
difference for their analogs with multiple nitro groups (per group, of course). For
example, for R = >C<, the difference is 42.5 ± 0.8 kJ mol-i. It might be thought that
steric effects involving CI and N02 are quite different, yet they are not [13].
Electronic effects for CI and N02 are quite different when these groups are bonded to
an unsaturated or n-framework. As evidenced by benzene substitution reasoning, the
former is weakly electron-donating and the latter quite strongly electron-withdrawing.
74 Predictions and Validation ofPhysicai and Energy Data
Furthermore, the oxyanion OCI- has enhanced nucleophilicity relative to OH- while
ON02- (a.k.a. N03 -) is considerably less nucleophilic. However, neither difference
seems particularly relevant for the aforementioned multiple substitution on saturated
carbon.
2.2 Example of cr and CN-
With regards to inorganic mimicry, it was observed [15] that the gas phase anions, CI-
and CN- show considerable similarity with respect to clustering and complexation
energies. That is, the formal (L, L') exchange reaction
CI-.L + CN-.L' -+ CI-.L' + CN-.L (EQ.4)
IS essentially thermoneutral. Likewise, formal ligand exchange reactions are also

nearly thermoneutral. For example, in that the clustering enthalpies ofCI- and CN-
with HCN are 87 ± 4 and 92 ± 4 kJ mol-I, reaction 4 with L = HCN and L'= "zilch" is
but 5 ± 6 kJ mol- I endothermic.
The lattice energies and enthalpies of solution of alkali metal chlorides and related
cyanides are comparable as well, e.g. the difference of the two enthalpies
~tHm°(NaCI, s) and ~tHm°(NaCN, s) and that of the enthalpies ~tH°(NaCI, aq) and
~tH°(NaCN, aq)is less than 3 kJ mol-I. Equivalently, the formal reaction
NaCI(s) + NaCN(aq) -+ NaCI(aq) + NaCN(s) (EQ.5)
differs from thermoneutrality by less than 3 kJ mol-I. This does not mean that the
enthalpies of formation of any of the four species in equation 5 are the same: e.g.
those of solid NaCI and NaCN differ by some 320 kJ mol-I, where the precise (within
3 kJ mol-I) difference depends on the crystal form of the cyanide. The difference
generally decreases as the cation G becomes more electronegative and/or the species
GCI and GCN become more covalent, e.g. it is reduced to 286 kJ mol- I for gaseous
NaCI and NaCN (- 176.65 - (+ 109)), to 155 ± 15 kJ mol- I per CI or CN as one
considers gaseous NCCN and CICN (306.7 - 137.8) or 138 KJ mor1for CICN and CI2
(137.8 - 0.0). It is to be admitted that we have changed the names and symbols for
what is attached to the CI and CN. We are not consistent in the use of the terms
groups and ligands, nor in the symbols R, L, and G (and any "primed" varieties). This
lack of consistency betrays the lack of uniformity in nomenclature amongst organic,
inorganic and physical chemists: we have made no attempts at remedying this or even
attempting to enforce a subdiscipline-wide uniformity on ourselves. We may
admittedly almost disingenuously include a brief "biochemical" disclaimer: CN- and
Cl- are certainly not mimics in this realm. We are convinced that no individual,
however extremely stricken with hypertension, would ever conclude that NaCN was
toxic because of its "sodium content", nor however bland the diet, would that
individual decide to add NaCN to flavor the food.
2.3 Examples of Br and NH2, Br and SH, I and CH3
What about mimicry for bromine? The organic chemistry-based mimicry of Br and
NH2 [9], I and CH3 works surprisingly well: differences [9] of -13 ± 3 and 100 ± 5 kJ
mol- I successfully traverse R = Me, Et, iPr and tBu. For example, the difference of
enthalpies of formation of gas phases MeBr and MeNH2 is -12.5 ± 1.2 kJ mol- I while
for iPrBr and iPrNH2, the difference is -15.6 ± 2.8 kJ mol-I. Errors in describing the
thermochemistry of multiple-substituted species has not been a particular problem for
these mimics -- but then again there are almost no relevant enthalpy of formation data
with which to make the desired comparison. Yet it is obvious that these mimicry
relations cannot be universally valid. After all, numerous metal bromides are known
and are generally stable. Few amide salts are known, much less thermochemically
characterized. Only for those salts of the alkali metals and the more electropositive
alkaline earths, Sr and Ba, are there the desired archival data. Loss of ammonia, and
also nitrogen, is quite common. For example, iron forms the thermochemically
characterized FeBr2 and FeBr3. By contrast, there are no enthalpy of formation data
for the formally corresponding Fe(NH2h and Fe(NH2h nor the corresponding nitrides
Fe3N 2 and FeN. Instead, we have data for F e4N. For reference, the difference of the
enthalpies of formation of two of the very few relevant inorganic bromide/amide
pairs, solid NaBr and NaNH2, is -237.3 kJ mol-I. Indeed, this difference is very
different from the organic cases, as well as from the other salts: for 1/2[Sr] and Cs, the
differences are -185.1 and -281.4 kJ mol-I respectively. Br and NH, are hardly mimics
in the ionic inorganic realm. We now recall the earlier comparison [6] of Br and SH.
The difference of the enthalpies of formation of two of the even fewer relevant
inorganic bromide/hydrosulfide pairs, solid NaBr and NaSH, -123.83 kJ mol- I is
encouragingly close to that for the Cs case, -130.3 kJ mol-I. Does it follow that SH is
a better mimic for Br than NH2 is? For inorganic species, maybe, but for organic
compounds, the difference of the enthalpies of formation ofMeBr and MeSH is found
to be -12,6 ± 1.3 kJ mol- I while for iPrBr and iPrSH the difference is -23.2 ± 2.6 kJ
mol-I. For organic compounds, SH mimics Br more poorly than NH2. Let us briefly
turn to iodine. The organic mimicry of I and CH3 with a suggested [9] difference for
~tBm O(g) of 100 ± 5 kJ mol- I works quite well, e.g. for EtI and EtMe, the difference
is 97.2 ± 1.8 kJ moLl while for tbul and tBuMe, the difference is 96.1 ± 3.4 kJ mol-I.
We lack experimentally determined data for the comparison of inorganic derivatives
of! and CH3. Yet, the comparison of these RI and RCH3 compounds is clearly belied
here as well. Iodide salts are neutral, water soluble, and show some tendency to
oxidize on standing. "Methide" salts are archetypical organometallic compounds --
highly basic and readily destroyed by the presence of water and oxygen.
2.4 Examples of Alkali metals
So far all of our discussion of mimicry has dealt with derivatives of comparatively
electronegative elements. For example, what are the mimics of the electropositive
alkali metals? The simplest answer is the alkali metals themselves. Letting M and M'
be two different alkali metals, we do not expect a constant difference between the
enthalpies of formation of MX and M'X, i.e. that are thermochemical mimics of the
other. However, the "triple mimicry" relation for three alkali metals [16]
L'.tHm O(MX,s) = a L'.tHm O(M'X,s) + (I-a) L'.tHm O(M"X,s) +b (EQ.6)
is accurate to better than 8 kJ mol-I, e.g. with M = Na, M' = K, M" = Li, a = 0.639, b =
21.3. NH4+ is often considered among the alkali metals, and there is the related
parameter set: M = NH4, M'= K, M" = Na, a = 0.502, b = 108. Indeed, the simpler
identification of K+ and NH4 + as mimics has been seen [17] in such diverse realms as
enthalpy of formation of salts; ion clustering, lattice and solvation energies; electrolyte
solution conductance; and even some key biochemical interactions. Yet even here it is
clear that the mimicry is not complete. After all, should X = some "hydrocarbyl
group", R, and M = K, we again encounter water and air labile organometaIIics for
which enthalpy of formation data are essentially nonexistent: even for the much better
characterized organolithium species, the data are sparse and often suspect [18]. These
data are also essentially nonexistent for their ammonium counterparts as well, That is
because these compounds are essentially nonexistent as well: "intramolecular", but
interionic proton transfer almost invariably results in the covalent NH3 + RH.
2.5 Examples of Alkanes and derivatives
The mention of RH brings us back to alkanes, particularly n-alkanes and thus simple
n-alkyl derivatives. For these species, there is the long-studied thermochemical
mimicry of Z and CH2Z for whatever Z we choose. That is, there is an essentially
constant enthalpy of formation difference of gas-phase RZ and RCH2Z, and by
induction, R(CH2)nZ and R(CH2)n+IZ. More precisely, the series MeZ, EtZ, nPrZ,
nBuZ constitute a homologous series that defines the "universal methylene increment"
[19,20]. This universality may be expected to be more universal than any of the above
mimics in this text. For numerous Z there are ample data to test the approach to
constancy, and then to note that n is often disappointingly large before ca. kJ.mol- 1
constancy is achieved [20]. Not surprisingly, the methyl compound is deviant. The
deviation from constancy for "small n" seems to relate to the electronegativity of Z
[13,14]) but there is a notable absence of thermochemical data for alkyl fluorides with
their high-electronegativity Z = F and for organoalkalis with their low
electronegativity Z = M. Even for n-alkyl derivatives, this most simple class of
species, much remains to be learned.
3 CONCLUSION
We close with a generality and a caveat about thermochemical mImIcry. The

generality is that thermochemical mimicry is never general, but is often a very
powerful method for making reliable enthalpy of formation estimations. The caveat is
that one must have a sense of when it may be applied. This means the species are
most meaningfully compared in the same phase: e.g. it is clearly wrong to contrast
(amine and/or ether) solvated and/or solid, (C .. LLC) associated methyl lithium,
gaseous methyl fluoride and liquid (O .. H..O) associated methanol. It is not adequate to
merely write CH3Li, CH3F, CH30H and then commence a thermochemical mimicry
analysis. It also means that the compounds must be comparable. For example, as part
of the fluorolhydroxy comparison cited above, the same purported constant difference
for AtHm O(R-F) and AtHm O(R-OH) is assumed to be valid for gem-disubstituted-
species, i.e. for 112 [AtHmO(RF2)] and is tacitly 112 [AtHm O(R(OHh)]. In addition, the
enthalpy offormation of the diol R(OHh equated with the carbonyl-containing R=O +
H20. This equivalence was successfully used in interrelating the enthalpies of
formation of polyvinylidene fluoride [6] with that of acetylacetone or pentane-2,4-
dione, where explicitly the "CH3COCH2COCH3" tautomer was meant and not the
intramolecularly hydrogen bonded enol - it was recognized that the majority
component of the CSHS02 isomer [21] generally goes by the -dicarbonyl name, and
not (Z)-4-oxo-2-penten-2-01 nor (Z)-4-hydroxy-3-penten-2-one, despite its
CH3C(OH)=CHCOCH3 structure.
KEYWORDS
thermochemical mImICry, formation enthalpy, standard entropy, heat capacity,

halogen, alkali metals
REFERENCES
[1] Benson, S. W., Buss, J. H., J. Chern. Phys., 29 (1958),546.

[2] Benson, S. W., Cruickshank, F. R, Golden, D. M,. Haugen, G. R., O'Neal, H.
E., Rodgers, A. S., Shaw, R., Walsh, R., Chern. Rev., 69 (1969), 279.
[3] Cohen, N., Benson, S. W., Chern. Rev., 93 (1993), 2419.
[4] Wagman, D. D., Evans, W. H., Parker, V. B., Schumm, R. H., Halow, I.;
Bailey, S. M., Chumey, K. L., "The NBS Tables of Chemical Thermodynamic
Properties: selected values for inorganic and CI and C2 organic substances in
SI units," 1. Phys. Chern. Ref. Data, 11 (1982), supplement 2. All
unreferenced thermochemical data for inorganic compounds in our study come
implicitly from this source.
[5] Pedley, J. B., Naylor, R. D., Kirby, S.P., "Thermochemical Data of Organic
Compounds (2nd ed. Chapman & Hall, London, 1986). All unreferenced
thermochemical data for organic compounds in our study come implicitly from
this source.
[6] Benson, S. W., Chern. Rev., 78 (1978), 23.
[7] Woolf, A. A., Adv. Inorg. Chern. Radiochem., 20 (1980), 1; J. Fluor. Chern.,
11 (1978), 307; 20(1982), 627; 32 (1986), 453.
[8] Liebman, J. F., in "Fluorine-Containing Molecules: Structure, Reactivity,
Synthesis and Applications", eds. J. F. Liebman, A. Greenberg and W. R.
Dolbier, Jr., YCH, New York, (1988).
[9] Slayden, S.W., Liebman, J. F., Mallard, W. G. in "The Chemistry of
Functional Groups, Supplement D: The Chemistry of Halides, Pseudo-Halides
and Azides" Yol. 2, eds. S. Patai and Z. Rappoport, John Wiley & Sons,
Chichester. (1995).
[10] Berkowitz, J., Appelman, E. H., Chupka, W. A., J. Chern. Phys., 58 (1973),
1950.
[11] Kunkel, D. L., Fant, A. D., Liebman, J. F., J. Mol. Struct., 300 (1993),509.
[12] Schaffer, F., Beckhaus, H.-D., Rieger, H,-J., Ruechardt, C., Chern. Ber., 127
(1994),557.
[13] Liebman, J. F., Martinho Simoes, J. A., Slayden, S. W., Struct. Chern., 6,
(1995),65
[14] Montgomery, R, L., Rossini, F, D., J. Chern, Thermodyn., 10 (1977), 471.
[15] Mautner M., Cybulski, S. M., Scheiner, S., Liebman, J. F., J. Phys.Chem., 92
(1988), 2736.
[16] Hisham, M. W. M., Benson, S. W. in "From Atoms to Polymers: lsoelectronic
Analogies", ed. J. F. Liebman and A. Greenberg, YCH, New York, (1989).
[17] Liebman, J. F., Romm, M. J., Meot-Ner (Mautner), M., Cybulski, S. M.,
Scheiner, S., 1. Phys. Chern., 95 (1991), 1112.
[18] Liebman, J. F., Martinho Simoes, J. A., Slayden, S. W., in "Lithium
Chemistry: A Theoretical and Experimental Overview", ed. A.-M. Sapse and
P. v. R. Schleyer, John Wiley & Sons, New York, (1995.)
[19] Cox, J. D., Pilcher, G., "Thermochemistry of Organic and Organometallic
Compounds", Academic Press, New York, (1970).
[20] Liebman, J. F., Crawford, K. S. K., Slayden, S. W. in "The Chemistry of
Functional Groups, Supplement S: The Chemistry of Sulphur-Containing
Functional Groups", eds. S. Patai and Z. Rappoport, John Wiley & Sons,
Chichester, (1993).
[21] Hacking, J. M., Pilcher, G., J. Chern. Thermodyn., 11 (1979), 1015.
COMPUTER-AIDED INORGANIC PROPERTIES
ESTIMATION SYSTEM
Jian-yun SHEN, Guo-sheng HUANG, Hao WEN and Zhi-hong

XU
Laboratory of Computer Chemistry (LCC), Academia Sinica, Beijing 100080
ABSTRACT
The main approaches for estimating the fUndamental thermodynamic properties H~98'
S~98' G~98 and Cp are discussed, including the Bonding Model developed
298
recently in our laboratory. This model is successfUl for estimating S~98 and Cp of
298
the compounds with less ionic character, where the simple additivity scheme is not
appropriate. A software program, Inorganic Properties Estimation System (IPES), is
presented. IPES can give the above estimated values when experimental data are not
available. It can also consult a thermo-data bank to see if the data desired already
exist and output both the experimental and estimated values for evaluating the
estimation methods.
RESUME
Les voies principales pour estimer les proprietes thermodynamiques de base H~98'
S~98' G~98 et C p sont discutees, y compris le Modlde de Lien developpe

298
recemment dans notre laboratoire. Ce modl!le a reussi it estimer S~98 et C p des

298
composes avec moindre caractere ionique OU le schema simple d'additivite n'est pas
approprie. Un logiciel appele le systeme d'Estimation des Proprietes Inorganiques
(IPES) est presente. IPES va donner les valeurs estimees en cas de manque des
donnees expirimentales. Il est lie avec un data bank, et peut donc sortir les valeurs
experimentales si elles existent et celles estimees pour evaluer les methodes
d'estimation.
1 INTRODUCTION
Thermodynamic calculation is an important step in process simulation and materials

design for developing and optimizing metallurgical and chemical processes and new
materials. The shortage of the thermodynamic data is often the main difficulty which
troubles research workers, especially in the ever-widening field of new technology.
So it is one of the functions of the experienced thermochemist to estimate the missing
data with reasonable accuracy. But it is not an easy work and this problem is being
pushed forward at present because the calculation is readily performed automatically
by computer. A software program, Inorganic Properties Estimation and Evaluation
System (IPES), is developed in our laboratory, Lee. The aim of the software is to
supply estimated values of properties for inorganic substances when the experimental
values are not available. The first part of IPES is the estimation of thermodynamic
properties at 298 K: H~98' S~98' G~98 and C p . These values are the fundamental
298
data in thermodynamic calculations.
2 MAIN ApPROACH OF ESTIMATION PROCEDURES IN IPES
In order to understand this software better, we shall first review the main approaches
used for estimating these properties.
2.1 Standard heat of formation
It is well known that the most famous approach to estimate heat of formation LlH~,298
of simple salts is Pauling's formula [1] which uses electronegativity as the correlation
parameter.
LlH~,298 = -95.6(XB - X A )2 + 232nN + 109no (1)
This estimation is too rough although it reveals an important regularity in heat of
formation. So there are some modified methods based on this approach which
achieve acceptable results[2,3,4] for different types of compounds. For the polyvalent
binary compounds MX, there are several empirical correlations where the charge of
the cation and the number of anions are used as parameters, such as:
N
LlH~ 298
= a + bz [5] (2)
LlH~,298 = az+ bz2 [6] (3)
LlH~ 298
log N =a+bz [6] (4)
Computer-Aided Inorganic Properties of Organic Compound 81
Each has its best estimation precIsion for different series of polyvalent binary
compounds, and IPES can recommend the more convenient approach for specified
compounds. For complex oxides, Erdos's approach [7] improved by others [8], can be
widely used. In this method, the H of complex oxides is separated into two parts. One
is the sum of the H of the simple compounds which constitute these complex oxides.
The other is the so called standard heat of reaction. Thus we can write
LlH~,298 = LLlH~,298,i + LlH~ (5)
The formula used for estimating LlH~ is similar to that of Pauling, but the exponent
here it is not a fixed value.
Where Ki and Aj are parameters of the cation and anion respectively, c is an empirical
exponent which has its characteristic value for different anions. Generally the three
parameters are obtained by the least-squares method from the available data of the
formation of heat. Chen Nianyi et al.[9] proposed a semi-empirical approach to
estimate them, where the concept of a screening parameter is used. For the
intermetallic compounds, the well known approach is Miedema's phenomenological
macroscopic Atom Model [10] . But this model is successful only for binary
intermetallic compounds, in which at least one of the constituents is a transition metal.
The Pair Potential Model of Mach lin [11] can be used for some compounds without a
transition metal, but this model is generally suitable for the AB type intermetallic
compounds. Beside the main approaches mentioned above, many empirical methods
for correlating the heat of formation with various parameters are incorporated in IPES
for different types of compounds.
2.2 Standard entropy and heat capacity
For the thermochemical properties of S~98 and Cp ,the results from additivity
298
schemes [12] have good accuracy for those compounds with predominantly ionic
character. In this approach S~98 or Cp of the compounds are estimated by simply
298
adding the ionic entropy or ionic heat capacity of the constituents. That is to say, the
interaction between the two ions has no significant effect on these two properties. This
consideration is not sufficient for compounds with less ionic character. A Bonding
Model [13-14] has been developed in our laboratory for countering the drawback of
the simple additivity approach. In this model, there is a correlation term in addition to
the sum of the ionic terms. So for a compound Ax,B y,
~S~98 = xScation + ySanion + Sr (7)
Cpo298 = xC p catIOn
. + y C panIOn
. + C pr (8)
where Sr and Cpr are the interaction entropy and interaction heat capacity, which are
correlated with the number of pairs of atoms m, the electron distribution and the
character of the bond I. They are expressed as
(9) (10)
where is correlated with the charge and the principle quantum number, and I is
correlated with the difference of the electronegativity between the two constituents,
cis a modifying factor for heat capacity, which is
lxy
c=--- (11)
2x+y
The estimation accuracy has been obviously improved by adding this correction term,
both for standard entropy and heat capacity. IPES includes several other approaches
for estimating the two fundamental thermochemical properties of complex
compounds, intermetallic compounds, etc.
2.3 Standard Gibbs free energy
As to the standard Gibbs energy ~G~98' generally it can be calculated from the basic
thermodynamic relation
~G~98 = ~H~98 - T~S~98 (12)
So ~G~98 can be indirectly estimated by estimating ~H~98 and ~S~98. There are also
some direct approaches such as that of Tardy for complex oxides[15] which correlates
~G~98 of hydroxides, oxides and gaseous ions, that of Lau[16] which uses the
thermodynamic functions and the stability principle, etc. The direct estimation of
~G~98 can be made in two ways: one is to obtain a predicted value if the estimation
approaches for both ~H~98 and ~S~98 are not available. The other is to verify the
thermodynamic consistency of the values of H~98' S~98 and G~98 if all of them can
be estimated directly.
Computer-Aided Inorganic Properties of Organic Compound 83
3 FUNCTION OF IPES
In the software program IPES there is a retrieval system to classify the substance
according to its molecular formula for finding the appropriate estimation method for
it, a subprogram bank including all the relatively facile estimation methods available,
a sub-databank where various structure parameters such as ion radius,
electronegativity, bond energy and polarizability, etc. are well organized. IPES can
conveniently read the data bank ITDB [17] (Inorganic Thermochemistry Data Base) to
see if the desired data already exist. ITDB is another piece of software developed in
our laboratory which collects the literature on thermodynamic data of inorganic
compounds. So IPES has four main functions:
1. To recommend a suitable estimation method according to the constituent species

input by the user. This function of IPES is based on the work of summing up and
evaluating systematically all the estimation methods by comparing their calculation
results with the data available. Thus the methods collected are well classified by their
precision for various types of compounds. Once the formula of a species is input into
the computer, IPES can rapidly separate this formula into its constituents and find
their positions in the periodic table. As the estimation methods are keyed to the
reliability for various types of compounds, the software program can find the most
suitable method promptly.
2. To give the estimated value using the recommended method. The parameters used
in all the methods are collected and well organized in the software. After a method is
selected, the program can perform the calculation with suitable parameters and show
the estimated values on screen. The results are also stored in an assigned data file.
3. To list the literature values if they exist in the data bank ITDB. As the methods
incorporated in IPES, either semi-empirical or empirical, are not rigorous, the values
obtained may not be very exact. The program will first look up ITDB and show such
literature data on the screen if they exist. This function of IPES can have two uses: 1)
to retrieve the literature data available in the data bank; 2) to give an idea of the
precision of estimation by comparing the results for similar substances for which the
properties are in the data bank.
4. To list the results with all the possible estimation methods if the user requires this.
Thus the user himself can select a method by comparing the results for similar species
with the different methods.
4. RUNNING OF IPES
IPES can accept the request of the user in two ways. The first is to read on screen the
molecular formula of the compound and the thermodynamic properties to be
estimated. The second is to read an input file prepared before calculation. In the input
file, the first line is the number of compounds for which the thermodynamic properties
are to be estimated, and then their molecular formula should be listed. In the second
case IPES will execute the estimations in succession and output the values of the four
thermodynamic properties. The latter is more convenient for connecting chemical or
phase equilibrium calculation where a series of compounds are studied and the four
properties are all needed. The estimated results will be output on the screen and
organized in a assigned output data file. As IPES also has the function of consulting
the data bank ITDB, it will output the reference data if they exist in ITDB.
5 CONCLUSION
The software package IPES is based on the work of collecting and evaluating the
existing methods for estimating the fundamental properties of inorganic compounds. It
can provide the data missed in data banks with reasonable accuracy. The search for
rules of estimating properties from basic parameters leads us to further understand the
relationship between properties and structure and to develop a new approach for
improving the estimation system. This software will be a useful tool in the research
work of metallurgy, chemical processes and material science.
KEYWORDS
Thermodynamic properties, inorganic compounds, estimation, computer software.
REFERENCES
[1] L. Pauling, The Structure of the Chemical Bond, Cornell University Press(1960)
[2] H.W. Anderson, L.A.Bromley, 1. Phys. Chern., 63, (1959), 1115
[3] D.E. Wilcox, L.A. Bromley, I&EC, 55, (1963), 32
[4] S. Aronson, 1. Nuclear Mater., 107, (1982), 343
[5] Han Tianyou, Chinese Chern. Bull., 3, (1966), 60
[6] M.W.M. Hisham, S.W. Benson, 1. Phys. Chern., 91, (1987), 5998
[7] E. Erdos, 1.NucI.Mater., 107, (1982), 343
[8] K. Schwitzgebel et aI., 1. Chern. Eng. Data., 16, (1971), 418
[9] Chen Nianyi, Wen Yuankai, Acta Metal. Sinica, 15(3), (1979), 85
[10] A.K. Niessen, A.R. Miedema et aI., Calphad, 7, (1983),51
[11] E.S. Machlin, Calphad, 5, (1981),1
[12] O. Kubaschewski, C.B. Alcock, Metallurgical Thermochemistry, 5th ed.(1972)
[13] Huang Guosheng, Xu Zhihong, Thermochem. Acta, 136, (1988), 133
[14] Huang Guosheng, Xu Zhihong, Thermochem. Acta, 145, (1989), 363
[15] Y. Tardy,L. Gartner, Contrib. Mineral Petrol,. 63, (1977),89
[16] S.K. Lau, 1. Material Sci. Lett., 2(4), (1983),137
[17] Wang Leshan, Xu Zhihong, Inorganic Thermochemistry Data Bank (1981)
ESTIMATION OF PHYSICAL PROPERTIES OF
ORGANIC COMPOUNDS. A COMPARISON OF
METHODS IN THE CASE OF VAPOR PRESSURE
ESTIMATION.
Maurice CHASTRETTE and Dominique CRETIN
Laboratoire de Chimie Organique Physique et Synthetique, URA 463, Universite

Claude Bernard, 43 bd du 11 Novembre 1918,69622 Villeurbanne Cedex.
ABSTRACT
Physical properties of organic compounds, needed to estimate various bioactivities,

have to be estimated in many cases, due to insufficient literature data. A brief survey
of several methods, used in various fields, is presented: group contribution methods
like UNIFAC, topological methods like DARC, autocorrelation methods like the
Moreau contribution. An advanced multifunctional autocorrelation method, MAM, is
compared, for 186 compounds comprising hydrocarbons and alcohols, with the two
others types of methods. MAM then was tested on 66 other oxygenated compounds.
RESUME
Les proprietes physiques des composes organiques, necessaires pour estimer leur
bioactivite, doivent etre estimees dans de nombreux cas, du fait de l'insuffisance de
donnees. Une breve revue de plusieurs methodes, utilisees dans des domaines varies,
est presentee: des methodes de contribution de groupes telle UNIFAC, des methodes
topologiques telle DARC, des methodes d'autocorrelation telle celle de Moreau. Une
methode d'autocorrelation amelioree multifonctionnelle MAM, est comparee, sur 186
composes comprenant hydrocarbures et alcools, avec les deux autres types de
methodes. La methode a eM ensuite testee sur 66 composes oxygenes.
1 INTRODUCTION
Vapor pressure is an important physical property in the description of the

environmental behavior of pure compounds, but its values are available only for a
finite number of compounds, generating a need for estimation methods. Among

methods actually used to estimate vapor pressure those based on suitable descriptions
of the molecule have proved very useful. Two principal types of descriptions are used
: group contributions and topological indices.
In group contribution methods, the contributions are fixed once and for all before the
calculation. Similarities and differences between these methods are illustrated in the
five following examples.
- in the AMP [1] method, based on the kinetic theory of gases, the
fundamental equation is:
In Pv = A + BIT + Cln T + DT + ET2
Coefficients A to E are obtained from three structural variables: Vw, sand EoIR. V w is
the Van der Waals volume of the molecule; s depends on shape, size and flexibility of
molecules ; Eo reflects intermolecular forces, it is the enthalpy of vaporization of an
hypothetic liquid at T = O. These three parameters are calculated by group
contributions.
Vw = Lnivwi
i
s= Lni Si
i
~ ~ ~ni(E~i)
Vwi, Sj, EOi are contributions of group i; ni: number of group i in the molecule.
The disadvantage of this method is that it doesn't take into consideration interactions
between the groups.
- Amidon and Anik [2] calculated free energies ~G of compounds like aliphatic,
aromatic and alkyl aromatic hydrocarbons, by regression on Hermann [3] surfaces of
these compounds. They calculated the vapor pressure using the equation:
LlG vap
InP(atm) =---
RT
No interactions were considered and the following groups were used:
o ArC = aromatic carbons.
o ArH = aromatic hydrogens.
o AIOV = aliphatic overlap for carbon atoms in ex position to the aromatic ring.
Estimation of Physical Properties of Organic Compound 87
OReAl = remaining aliphatic, for groups attached to the first carbon atom that
doesn't belong to an aromatic nucleus.
The following three methods use specific contributions to describe some interactions.
- UNIFAC [4]: Vapor pressure can be calculated by UNIFAC with the equation:
N
RTln(q>S ,ps) = Lnk ~gk + RTLnk lnrk
k=l
Llgk: difference between Gibbs energy of group k and reference energy of the same
group: Llgk = gk - gOk. This parameter is calculated by group contributions, that
reflect groups alone but also some specific interactions.
cps: fugacity coefficient.
hUk: term calculated from the residual part of UNIFAC. Parameters reflecting the
surface areas of different groups and interactions between the groups are used in the
calculation of this term.
The first term of this equation accounts for specific interactions and the second term
considers all the interactions.
- Hoshino [5] used a group contribution method to calculate coefficients of the

Antoine equation for substituted benzenes. Group contributions were calculated for
six groups. Differences due to different positions of substituents in the cycle were
represented by increments.
- Ad hoc descriptors used by Dravnieks [6] are particular group contributions,

calculated and adjusted directly from the property under study. They represent both
the nature of groups and the interactions.
Topological methods consider the molecule as a graph where atoms are nodes.
Topological indices are not adjustable and not specifically linked to vapor pressure.
Wiener [7] or Balaban [8,9] indices do not take into account the nature of groups, but
only the distances between them. Kier [10,11] indices also represent interactions, the
nature of the groups being represented by connectivity. Autocorrelation methods are
intermediate to these two kinds of methods. They are based on the graph of the
molecule, like topological indices, and use descriptors analogous to group
contributions.
- Moreau's Autocorrelation: Moreau [12] used an autocorrelation method to solve

problems of structure-activity relationships. Their method derives from the
autocorrelation function used in mathematical problems of periodicity or
pseudo-periodicity of an f(t) function. There is periodicity iff(t) and f(t + L) (where L
is the lag) are well correlated. That is expressed by the autocorrelation function F(L):
F(L) = iB f(t) * f(t + L)dt
For discrete values the relation becomes:

k
F(L) = Lf(t)*f(t+L)dt
i=1
Moreau considered the molecule as a graph, where the nodes are the atoms (hydrogen
atoms are not taken into account), connected by bonds. Properties Pi of atoms
(electronegativity, volume, surface, ... ) were defined on every node of the graph and
are analogous to f(t). The components Pk of an autocorrelation vector P,
corresponding to that property, were calculated as:
Pk = LPi *Pj d=k

j>1
d = k : topological distance between atoms.
- O.5MAM method (Multifunctional Autocorrelation Method): Chastrette et al.

[13,14,15] modified Moreau's autocorrelation method by introducing two important
improvements:
).>- The notion of expanded atoms: e.g. instead of having one type of carbon atom,
four types were considered, thus taking into account hydrogen atoms.
).>- The use of functions f(Pi) instead of the properties Pi. The components Pk of
autocorrelation vector P were then calculated as:
Pk = Lf(Pi)*f(pj) d=k
j >1
This relation is often used with f(Pi) = (Pi)O.5 and in this case the method is called
O.5MAM. The advantage of o.5MAM is that it takes into account both the nature of
the groups (by the group properties) and the interactions (by the calculation of the
vector components). The o.5MAM method was previously used for molar volume,
molar refraction, molar, surface, aqueous solubility and partition coefficients [13-16].
o.5MAM is used here to estimate vapor pressures of alkanes and alcohols. Its
efficiency was tested and compared to some of the methods cited above.
2 MATERIALS AND METHODS
2.1 Data
A set of 142 alkanes (linear or branched from C5 to C15) was first studied.
LogVP(mm Hg) values at 25°C were calculated from constants of the Antoine
equation, given in the "Research Project 44" [17]. A set of 44 alcohols (linear and
branched from Cl to C12) was also studied. Constants of Riedel-Plank-Miller [18] or
Wagner [19] equations were used, except for nine alcohols, obtained from the API
project. A global set containing the 142 alkanes and the 44 alcohols was then studied.
Three other sets of oxygenated compounds were also studied: a set of 21 ketones, a set
of 12 ethers and a set of 33 esters. Values of log VP of ketones were calculated from
the coefficients of the Antoine equation given in the "Research Project 44" [17] and
by Boublik [20]. For ethers, constants were taken from Boublik. For esters, they were
taken from Boublik [20] and Billot [21].
2.2 Methods
The 0.5 MAM method was used here with the surface area as property P, because the
surface is generally a good molecular descriptor (e.g. Hoshino's method or UNIFAC
used surfaces, which were also used with the O.5MAM method to calculate octanol-
water partition coefficients or water solubility).
Bondi's surface areas si [6] were used to calculate the autocorrelation vector
components Sk, obtained (for alkanes) for each topological distance k in the molecule
as:
Sk = '~:>1/2 *s~12 d=k
j>l
For functionalized compounds, the Surface vector was decomposed into one
Lipophilic Surface vector (SL), calculated as the S vector but with sf= 0 (sf= surface
of the function), and one Functional Surface vector (SF). SF aims to take into account
the function using the relation:
d=k
i
si is the surface of the ith carbon atom placed at the distance k from the hydroxyl.
Values of Sf for ketones, ethers and esters are respectively: 1.605, 0.74 and 2.345.
Pertinent components of the autocorrelation vector were selected by multiple
regression on the experimental 10gVP values. The quality of the correlation was
estimated by the correlation coefficient r, the standard error s and the F test.
3 RESULTS AND DISCUSSION
3.1 Alkanes
Comparisons among different methods for the set of 142 alkanes are given in Table I.
They show that good results may be obtained in very different ways. A good
correlation was obtained with two autocorrelation variables only, and a slightly better
relation was found using five MAM variables:
log Pv = - 0.39 So - 0.037 SI + 0.015 S2 + 0.017 S4 + 0.023 Ss + 6.21

n=142 r=0.998 s=0.045 F=7288
Gore's [21], contributions showed that So contributed in an important way (65.4 %) to

log VP. SI contributed less (16 %) and the other components had contributions
between 3.8 % and 7.9 % meaning that branching was accounted for by several
components. Results similar to those of other methods were obtained with fewer
variables. Ad hoc method gave the same results as MAM with five variables, and
Wiener's method with d Wand dP gave better results.
Methods varnb r s
Wiener (W,P) 2 0.971 0.18
Topological Indices Wiener (dW/n2, M)* 2 0.981 0.03
Kier (oX, IX) 2 0.992 0.09
UNIFAC 2 0.993 0.08
Group Contributions AMP 5 0.989 0.11
ad hoc (n, nCH3' d(33)3, d(33)4, d(32)3)** 5 0.998 0.04
So 1 0.968 0.19
Autocorrelation So, SI 2 0.992 0.09
MAM Sj (i=0, 1,2,4,5) 5 0.998 0.04
Table 1: Comparison of methods to calculate log Pv of the alkanes
* d W et dP are differences between Wand P Wiener indices for a branched

compound and the linear compound with the same formula. The calculation is
carried out on corresponding dlog VP.
** n: number of carbon atoms, nCH3: number of CH3 groups, d(xy)z: number of
interactions between groups x and y at z distance.
3.2 Alcohols
The results obtained for the set of 44 alcohols are shown in Table 2. Four MAM
variables gave a correct correlation:
log Pv = - 0.28 SLo - 0.071 SLI - 0.50 SFI + 0.071 SF3 + 3.54
n=44 r=0.996 s=O.11 F=113
An ad hoc method gave the same statistical quality, but the other methods were not so
good as MAM or ad hoc. With three more variables, MAM gave even better results
(r=0.999, s=0.055).
Methods varnb r s
Wiener (W,P) 2 0.941 0.39
Topological Indices Wiener (~W/n2)*.*** 1 0.884 0.17
Kier (OX, IX) 2 0.981 0.22
Group UNIFAC 2 0.985 0.19
Contributions ad hoc (n, nCH3'class of alcohol)** 3 0.996 0.10
So, SJ, S3, S4 4 0.986 0.19
Autocorrelation MAM SLo, SLI, SF J, SF3 4 0.996 0.11
SLo, SLI, SL4, SFI, SF2, SF3, SF4 7 0.999 0.05
Table 2: Comparison of methods for calculation of logP v of alcohols.
* and ** : see Table 1 notes

*** ~P was not significant
3.3 Global set
For the set containing both alkanes and alcohols (Table 3) 0.5MAM gave good
correlations. With only five variables, the results were satisfactory and better than
those obtained with all other methods:
log Pv = - 1.29 SFo - 0.52 SF I + 0.08 SF3 - 0.31 SLo - 0.058 SLI+ 5.6
n=186 r=0.994 s=0.10 F=2792
Statistical tests could be improved by adding other variables (with eight variables: r =
0.996. s = 0.067).
Among the other methods, only UNIFAC gave comparably correct results. Ad hoc
descriptors were less efficient than for alkanes and alcohols taken separately, and
simple topological indices were relatively inefficient.
Methods varnb r s
Topological Wiener (W,P) 1 0.792 0.54
Indices Kier (OX, IX) 2 0.721 0.61
Group UNIFAC 2 0.989 0.13
Contributions ad hoc (n, nCH3,d(33)3, d(33)4, class of 5 0.918 0.35
alcohol)**
Autocorrelation SLo, SL}, SFo, SF}, SF3, 5 0.994 0.10
MAM SLo, SL}, SL2, SL4, SL5, SFo, SF}, SF3, 8 0.996 0.07
Table 3: Comparison of methods for calculation of logPvof alkanes and alcohols.

** : see Table 1 notes.
3.4 Other oxygenated compounds
The results obtained for the sets of 21 ketones, 12 ethers and 33 esters are shown in
Table 4.
Set Variables varnb r s

SLo, SF I 2 0.994 0.11
Ketones SLo, SF2, SF3 3 0.995 0.10
SLo, SL I , SF2, SF 3 8 0.996 0.066
Ethers SLo,SF I 2 0.999 0.049
Esters SLo, SL 1, SF I 3 0.998 0.064
Table 4: Quality of regressions of logPv on components of SL and SF vectors for

oxygenated compounds.
For ketones, SLo had a contribution of 76.5 %. Interactions between the carbonyl
function and carbon atoms in the molecule were represented by SF2 and SF 3, with
contributions of 15.6 % and 7.9 % respectively. The addition of SL I improved the
results and showed the influence of branching. For ethers, only the type of carbon
linked to the oxygen atom (represented by SF I) was important (SF I had a
contribution of 20.9 %). For esters, SLo had a contribution of 58.5 %. Interactions at
distance 1 were represented by SL I and SF 1. These three variables gave good results.
4 CONCLUSION
For alkanes, methods like AMP that don't take into consideration the interactions gave
nearly correct results, but other methods gave better results. O.5MAM is one of the
best, along with Kier indices, UNIF AC or ad hoc. For alcohols, the methods had to be
more selective. The best estimations were given by O.5MAM and the ad hoc method.
The relatively low efficiency of UNIFAC could be due to the fact that this method
takes into account too large a number of interactions and not only pertinent
interactions. For the global set, the ad hoc method was no longer as efficient as
o.5MAM, more ad hoc variables would be necessary to obtain good results. These
three sets showed that o.5MAM method was particularly efficient in the case of sets
containing different families of compounds. It was able to selectively represent
interactions, contrary to the other methods that involve too many interactions
(UNIFAC) or only a part of the important interactions (ad hoc). o.5MAM also gave
good results with 66 oxygenated compounds, and could be expanded to aromatic
compounds.
KEYWORDS
organic compounds, vapor pressure, UNIF AC group contribution method, topological

method, autocorrelation method, MAM.
REFERENCES
[I] D.S. Abrams, H.A. Massaldi, J.M. Prausnitz, Vapor Pressure of Liquids as a Function
of Temperature. Two-Parameter Equation Based on Kinetic Theory of Fluids, Ind.
Eng. Chern. Fundam., 13,3, (1974), p.259-262.
[2] G.L. Amidon, S.A. Anik, Application of the surface area approach to the correlation
and estimation of aqueous solubility and vapor pressure. Alkyl aromatic hydrocarbons,
J. Chern. Eng. Data, 26, (1981), p.28-33.
[3] R.B. Hermann, Theory of hydrophobic bonding - II - The correlation of hydrocarbon
solubility in water with solvent cavity surface area, J. Phys. Chern., 76, (1972), p.2754-
2759.
[4] T. Jensen, A. Fredenslund, P. Rasmussen, Pure-components vapor pressure using
UNIFAC group contribution, Ind. Eng. Chern. Fundam., 20, (1981), p.239-246.
[5] D. Hoshino, X.R. Zhu, K. Nagahama, M. Hirata, Prediction of vapor pressures for
substituted benzenes by a group contribution method, Ind. Eng. Chern. Fundam., 24, I,
(1985), p.112-114.
[6] A. Dravnieks, Correlation of odor intensities and vapor pressures with structural
properties of odorants, Am. Chern. Soc. Symp. Ser., 51, (1977), p.II-28.
[7] H. Wiener, Vapor pressure-temperature relationships among the branched paraffm
hydrocarbons, J. Phys. Chern., 52, 5, (1948), p.425-430.
[8] A.T. Balaban, V. Feroiu, Correlation between structure and critical data of vapor
pressure of alkanes by means of topological indices, Reports Molec. Theory, 1, (1990),
p.133-139.
[9] A.T. Balaban, Highly discriminating distance-based topological index, Chern. Phys.
Let., 89, 5, (1982), p.399-404.
[10] a) L.B. Kier, L.H. Hall, W.J. Murray and M. Randic, Molecular connectivity.- 1-
Relationship to non-specific local anaesthesia,. J. Pharm. Sci., 64, (1975), p.1971-
1973.
b) L.H. Hall, L.B. Kier and W.1. Murray, Molecular connectivity - 11- Relationship to
water solubility and boiling point, J. Pharm. Sci., 64, (1975), p.1974-1977.
c) ) W.J. Murray, L.H. Hall and L.B. Kier, Molecular connectivity - III- Relationship
to partition coefficients, J. Pharm. Sci., 64, (1975), p.1978-1981.
[II] L.B. Kier, L.H. Hall, Molecular Connectivity VII : Specific treatment of heteroatoms,
J. Pharm. Sci., 65,12, (1976), p.1806-1809.
[12] G. Moreau, P. Broto, The autocorrelation of a topological structure: a new molecular
descriptor, Nouv. J. Chim., 4, (1980), p.359.
[13] M. Chastrette, F. Tiyal, Relations structure-proprietes. Determination de la solubilite
de composes organiques dans l'eau a l'aide de la methode d'autocorrelation modifiee
(MAM), C.R. Acad. Sci. Paris, t.310, Serie II, (1990), p.511-514.
[14] M. Chastrette, F. Tiyal, J.F. Peyraud, Relations structure- proprietes : Determination du
coefficient de partage octanolleau des composes organiques a l'aide de la methode
d'autocorrelation modifiee (MAM), C. R. Acad. Sci. Paris, t.311, Serie II, (1990),
p.1057-1060.
[15] M. Chastrette, D. Cretin, F. Tiyal, Relations structure- proprietes : determination de la
pression de vapeur des hydrocarbures satures et des alcools a l'aide de la methode
d'autocorrelation multifonctionnelle « MAM », C.R. Acad. Sci. Paris, t.318, Serie II,
(1994), p.1059-1065.
[16] D. Zakarya, F. Tiyal, M. Chastrette, Use of the multifunctional autocorrelation method
to estimate molar volumes of alkanes and oxygenated compounds. Comparison
between components of autocorrelation vectors and topological indices, 1. Phys. Org.
Chern., 6, (1993), p.574-582.
[17] American Petroleum Institute (API), Research Project 44, Values of the properties of
hydrocarbons and related compounds, Thermodynamics Research Center, Texas A &
M University, Vol III, (1968).
[18] D.G. Miller, Derivation of two equations for the estimation of vapor pressures, 1. Phys.
Chern., 68, 6, (1964), p.1399-l408.
[19] W. Wagner, New vapor pressure measurements for argon and nitrogen and a new
method for establishing rational vapor pressure equations, Cryogenics, 13, 8, (1973),
p.470-482.
[20] T. Boublik, V. Fried, E. Hala, The vapor pressure of pure substances, Elsevier,
Amsterdam, (1984).
[21] M. BILL aT, Am. Perf. and Cosm., (1965).
[22] A. Bondi, Van der Waals volumes and radii, 1. Phys. Chern., 68, 3, (1964), p.441-45 1.
[23] W.L. GORE, Statistical methods for chemical experimentation, Interscience, New
York, (1952), p.141.
MODEL FOR THE CRITICAL EVALUATION OF
SOLUBILITY DATA IN SALT SYSTEMS
R. COHEN-ADAD*, M-Th COHEN-ADAD*, D. CHEHIMI**

and A. MARROUCHE***
*Physicochimie Minerale II, Laboratoire de Physicochimie des materiaux

luminescents URA 442, Universite Claude Bernard Lyon I
**Institut Superieur de I'Education et de la Formation Continue,
Universite de Tunis, 43 rue de la Liberti, Le Bardo, Tunisie
***Laboratoire de Chimie Minerale Appliquee et de Genie des Procedes
Universite Ibnou Zohr, Agadir, Maroc
ABSTRACT
A rational exploitation of salt systems, for industrial or fundamental application,

requires reliable solubility data and the determination of the sequence of
crystallization during evaporation or cooling of a brine, the calculation of yield,
recycling etc. It is based on convenient fitting equations allowing the calculation of
solubilities in a large range of temperature and composition. The water-salt systems
involving stoichiometric solid phases can be described in totality with a semi-
empirical model deriving from the thermodynamic conditions of equilibrium. The
model complies with all thermodynamic constraints of the system and requires a small
number of adjustable coefficients. The same procedure can be used for the calculation
of a complex system and included sub-systems (binary, ternary...). The model is
applied to the ternary system NaCI-KCI-H2o.
RESUME
L 'exploitation rationnelle d'un systeme salin, afinalite industrielle ou fondamentale,
necessite l'utilisation de donnees fiables et la determination de la sequence de
cristallisation d'une saumure au cours d'une evaporation ou d'un refroidissement, Ie
calcul des rendements, des recyclages etc. Elle est basee sur l'utilisation d'equations
de lissage permettant Ie calcul des solubilitis dans un domaine etendu de temperature
et de composition. Les systemes eau-sels faisant intervenir des phases
stoechiometriques peuvent etre decrits en totalite apartir d'un modelesemi-empirique
traduisant les conditions thermodynamiques de /'equilibre. Le modele, qui respecte

les contraintes thermodynamiques est applique au systeme ternaire NaCI-KCI-H20
1 INTRODUCTION
Progress in Science and Technology is essentially based on former publications

concerning the considered topics and related subjects, but the data are in everlasting
expansion and this is an unsolvable problem for scientists. For example, as shown in
Figure 1, the number of scientific reviews has increased in an exponential way from
10 in 1750 to 225000 in 1972. The numerical data are increasing at the same rate and
they constitute the major part of information required in academic or industrial
research. Unfortunately their collection is not easy since a great number of data are
published in unavailable foreign publications or in confidential reports; collecting
such data is expensive and requires a lot of time.
200000
L.
iii
,Q
E
~
z
100000
1750 1800 1850 1900 1970 1972

Year
Figure 1: Increase of the number of scientific reviews between 1750 and 1972
Moreover, a lot of data cannot be used as they are presented in publications:
• they are often expressed in various units,

• great discrepancies are often observed between the results of different authors,
• in spite of their great number, a lot of data are still missing and must be calculated
or extrapolated to the required range oftemperature, pressure and composition.
Model for the Critical Evaluation of Solubility Data 97
For these reasons the work of collecting and selecting reliable data cannot always be
done by the users. The present study has been developed in the frame of the Solubility
Data Project (S.D.P.) of the International Union of Pure and Applied Chemistry. This
project had been initiated by the late Professor Steven Kertes. Its main purpose is the
collection and critical evaluation of solubility data, the selection of best values, the
calculation of solubilities for rounded values of temperature and consequently the
calculation of solubility phase diagrams.
2 TREATMENT OF NUMERICAL DATA
A rational treatment of data is summarized in the flow chart presented in Figure 2. It

implies first a conversion of raw solubility data and a graphic selection in order to
separate the aberrant values which are set aside for further treatment. The adjustable
coefficients of the fitting equation are then calculated. A statistical evaluation of the
reliability of data, based on appropriate models, is performed as well as an
exploitation of the phase diagram (calculation of the solubility for a given temperature
etc).
Figure 2: Treatment of data (flow chart)

3 CHOICE OF A MODEL
As already stated in a previous publication concerning the critical evaluation of binary

systems [1], the models used for the description of salt systems must comply with
several constraints:
• The aqueous solution is a strong electrolyte

• The solid phases (ice, salt, hydrates) are stoichiometric
• The fitting equations of solubility surfaces must never be in contradiction
with thermodynamic laws
• The model must be able to describe any simple or reciprocal system and
all included sub-systems
• The model can be extended to systems presenting an associate liquid
phase
Several models have been proposed in the literature for the description of phase
diagrams, and, in particular, Pitzer's model [2] has been successfully applied for the
description of isothermal sections of salt systems. The selected model presented in this
paper is based on the presentation of solubility surfaces of the system and seems very
convenient for the critical evaluation of polythermal salt systems.
4 EQUATION OF A LIQUIDUS SURFACE
This equation is obtained, in a multi component system, from the expression of phase
equilibrium:
• At constant pressure, for each component (ion or molecule) of a phase
(I)
where IlF is the chemical potential, h?Cl is the molar enthalpy in the reference state
and aF is the activity of i in phase a .
• Two phases, a and ~ are in mutual equilibrium along the solubility surface
{~J~{~J (2)
The activity product of the solid phase ApBqC r (H20)n of the system, where A, B, C
can be ions or molecules, is deduced:
(3)
AH = LVi(hi13 - hill) Is the phase change enthalpy of the compound i, where i =

A, B, C, H20 and the superscripts concern the reference
i
states of liquid and solid.
The relation (3) can be written after integration:
Y-Ym=Z-Zm (4)
The subscript m concerns the coordinates of a particular point on the solubility

surface, taken as a limit of integration. Y is the natural logarithm of an activity
product, expressed for any stoichiometric solid phase ApBqCr.nH20 of the system, by:
(5)
S is a solubility product and f is related to a mean activity coefficient:
(6)
Z is a function of temperature:
rr
Z-Zm = -T_ --2 dT
AH (7)
mRT
The congruent melting point of the solid phase involved in solid-liquid equilibrium is
taken as the reference for activity measurements and as a limit of integration, so that
f m = 0 and the equation of the solubility surface becomes:
S - Sm = Z - Zm - In(f) (8)
5 FITTING EQUATION
5.1 Expression of 8 - 8 m for simple systems
The first member of equation (8) can be easily expressed as a function of the
composition of the liquid phase. If we consider, for example, the ternary systemNaCl,
KCl, H20 where the mole fractions of salts and water are respectively Xl, x2, l-XI-X2,
the values of S - Sm for the solid phases of the system are given in Table I.
Solid phase S-Sm

NaCI·2H20 In [64 x I (x 1+x2) (I-x I-X2)2 J (1 +XI +x2 )4]
NaCI In [4 XI (Xl+X2) J (l+Xl+X2)2]
KCI In [4 X2 (Xl+x2) J (1+XI+X2)2]
Ice In [(1-xI-X2) J (1+xI+X2)]
Table 1: Values ofS - Sm

Ternary system NaCI-KCI-H20
These expressions can easily be extended to the systems where all ions have not the
same electric charge.
5.2 Expression of S - Sm for reciprocal systems
The solubility product can be derived from the expression of composition variables.
Let us consider, for example, the reciprocal quaternary system K+, Rb+JCI-, Br-/J
H20. If nj is the number of moles of a component i (ion or molecule) in a mixture:
nK + nRb = nCI + nBr = 8 (9)
The composition co-ordinates are:
nCI
y= - (10)
8 '
and for the solubility product of KCI, for example becomes:
X(l- V))
S-Sm = In( 4 2 (11)
(2+Z)
5.3 Expression of Z - Zm and Ln(r)
When the enthalpy of phase change and its variation with temperature are known (this
is the situation for the solubility surface of ice), Z - Zm can be evaluated but, in a
general way, the term related to activity coefficient is not known so that it is expanded
in a series and relation (5) becomes at last:
A 2
S-Sm == -+Bln(T)+ C+DT + ET + ... (12)
T
Equation 12 is a semi-empirical fitting equation smce it involves the adjustable

coefficients A, B, C, etc.
6 EVALUATION OF THE ADJUSTABLE COEFFICIENTS
6.1 Binary system
At constant pressure the adjustable coefficients are determined from experimental

solubility data by linear regression. However all available thermodynamic information
must be taken into account [3,4].
The melting point of pure compound TO which is often known with great accuracy
allows the determination of coefficient C :
A
C = S- Sm - - - Bln(TO)-DTO-oo. (13)
TO
- The molar enthalpy of phase change given by:
(14)
becomes identical to the enthalpy of fusion at the congruent melting point of the
compound and can be used for the determination of coefficients [5]
- The heat capacity of phase change of pure components:
~ CA = R (B + 2 D TA + ....) (15)
Furthermore eutectic and peritectic points are common to two solubility curves.
6.2 Simple systems of higher order
When the order of a system is greater than 2 the coefficients A, B, C, are no more
00'
independent of composition and general relations can be derived, if we assume that all
coefficients A, B, C, D, ... can be expanded in similar series:
* * k ...
with i j
In the former relation the subscript i concerns a solubility surface involving species I
and Vi is the stoichiometric coefficient ofI in the solid compound.
6.3 Reciprocal systems
The derivation of an equation is much more difficult and a general relation has not yet
been derived.
7 CRITICAL EVALUATION OF DATA
The experimental determination of solubility relies on two different methods: analysis

of the saturated solution under isothermal conditions or measurement of the
temperature of phase change for samples of fixed composition. In the first case the
temperature is usually more accurate than the composition, while, on the contrary, the
precision on composition is better with polythermal measurements.
The relative deviations ~xjlXj = r and ~TjlTj = t have been adjusted in order to
accomodate more than 80 % of the available data, without taking into account the
experimental method of solubility determination. An iterative procedure summarized
in the flow chart shown in Figure 3 has been used. A set of coefficients are calculated
by linear regression and the deviations are measured. The aberrant data are set aside
and a new set of coefficients is determined.
The data omitted in former calculations are re-examined in order to check if some of
them comply with the proposed deviations. The calculation is recommenced until the
coefficients remain unchanged after two successive iterations.
yes -1 selection of data I

no
Figure 3 - Flow chart for critical evaluation of data
8 ApPLICATION TO THE TERNARY SYSTEM NaCI-KCI-H 2 0
Four solid phases (Ice, NaCl, KCl, NaCl·H20) are observed, but the equations of
solubility surfaces were developed, in the present paper, only for NaCl taken as an
example, using the data ofComec and Krombach [6] at a temperature below lOocC.
8.1 Binary systems
The limiting binary systems, e.g. NaCI.H20, were compiled and evaluated in the
S.D.P. series [3]. The values of coefficients AI, BI, CI, DI ... were calculated for all
solubility curves.
In Table 2, the values of coefficients obtained for the liquidus curves of NaCl are
presented as an example:
Coefficients Conditions introduced in Range K

calculation
Al = 99.14456 K melting point ofNaCI 273-1073
B I = - 1.53935 peritectic point ofNaCI·2Hp
Cl= 7.24959 lO- j K- 1 l~x/xl<o.OI ifT< 110°C
DI = 2.86411 I ~x/xl < 0.25 ifT > 110°C
Table 2: System NaCI·2H 20

Coefficient of fitting equation (liquidus ofNaCI)
8.2 Solubility surface of NaCI in the ternary system NaCI-KCI-H 2 0
The expression of solubility products S - Sm is presented in Table 1 for all solid

phases observed in the system. The solubility surface ofNaCI can then be written:
(17)
The development of coefficients AI, BI, CI, DI according to relation 16 gives:
Cl2 x 2 + cl3 x 3 + +cI23 x 2x 3 (18)

CI=-=~--~~--~~~
x2 +x3
where aI3, bI3, Cl3, dl3 are the coefficients of the liquidus curve ofNaCI presented in
Table 2. Equation 17 has six adjustable coefficients which can be evaluated directly
from experimental data by linear regression.
The calculation of coefficients may also be performed in two steps:
1- The expressions for AI, BI, CI, DI which were introduced in (17) may be written:
(19)
i=I,2,3
Equation 19 is a fitting equation of an isothermal section of the liquidus surface of

NaCI in the ternary system NaCI-KCI-H20. It involves two adjustable coefficients,
V 12 and V 123 since V 13 is a function of a13, b13, C13, dB already determined in the
binary system NaCl-H20. V12 and Vl3 are calculated by linear regression for each
isothermal section of the liquidus surface.
2- The variation of V 12 and V l3 with temperature allows the determination of

coefficients a12, b12 ... , a123, bl23 by linear regression.
9 EXPLOITATION OF FITTING EQUATIONS
9.1 Solubility at fixed temperature
At a fixed temperature equation 17 is reduced to a relation between Xl and X2 and

gives the liquidus curves ofNaCI of the ternary system at the considered temperature.
A comparison between experimental and calculated solubilities ofNaCI for isothermal
sections at 0, 10, 40, 60 and 100°C is presented in Figure 4. The agreement between
experiments and calculations is very good.
o 0.02 0.04 0.06
Figure 4: Solubility ofNaCI

Isothermal sections 0, 40, 60, 80, 100°C; • experimental, - calculated values
9.2 Polythermal phase diagram
The same treatment was performed for the solubility curves of ice, KCI and
NaCI·2H20 at various temperatures and the polythermal phase diagram was deduced.
For each isothermal section the double saturation points are the intersects of two
solubility curves. In Figure 5 the double saturation curve involvingNaCI and KCI was
determined graphically. The agreement with experimental data is very good.
\
010 4060 \ 100°C
0.12 \ \ \ \ \
\ \ \ \ \
\ \ \ \ \
\ \ \ \ \
\
\ \ \ \ \
\ \ \ \
\ \ \
\
\
0.08
0.06
0.04
0.02
o 0.02 0.04 0.06 0.08
Figure 5 - Ternary system NaCl-KCl-H20

NaCI-KCI double saturation curve in NaCI and KCI;
• experimental and - calculated values
9.3 Solubility for fixed composition
The resolution of fitting equations for fixed values of Xl and X2 will give four values
of temperature, T}, T2, T3, T4 corresponding to the saturation ofNaCl, KCl, ice and
NaCl·2H20. The highest temperature corresponds to the stable equilibrium, the others
are relative to metastable equilibria. For example ifT3 < T4 < Tl < T2 the saturation
point for composition (x}, X2) is located at temperature T2 on the solubility surface of
KCl.
9.4 Sequence of crystallisation
In the same way the variation of solubility with temperature can be followed, and the
quantities of phases in equilibrium can be calculated by application of the lever rule,
for a sample of fixed initial composition.
10 CONCLUSION
A model and a procedure making it possible to critically evaluate numerical data in

salt systems were developed within the framework of the Solubility Data Project of
IUPAC (commission V8). In an initial step this model and procedure were applied to
the binary systems involving water and alkali halides [3].They were subsequently
extended to multicomponent simple salt systems.
The work is presently being developed in two directions:
-Extension to reciprocal salt systems

-Derivation of an exploitation software.
KEYwORDS
salt-systems, solubility, critical evaluation, fitting equation.
REFERENCES
[I] R. Cohen-Adad, Pure & Appl. Chern., 57, (1985),255-62

[2] K. S. Pitzer, J. Phys. Chern., 77, (1973), 268-77
[3] R. Cohen-Adad, J. Lorimer IUPAC, Solubility Data series, vol 47, Alkali Metal
and Ammonium Chloride in water and heavy water, Pergamon press, Oxford
(1991)
[4] M.-T. Cohen-Adad, R. Cohen-Adad, Entropie, nO 160, (1991), 47-55

[5] M.-T. Cohen-Adad, R. Cohen-Adad, D. Chehimi, JEEP XIX, Barcelona, M.A.
Cuesvas-Diarte, J. L. Tamarit, E. Espot, eds., ISBN 84-604-5729-X (1993), pi
[6] E. Cornec, H. Krombach, Ann. Chim. (Paris), 18, (1932), 5
ON THE EXPERT THERMODYNAMIC ANALYSIS OF
POWER ENGINEERING PROBLEMS
Vyacheslav E. ALEMASOV*, Anatoly F. DREGALYN** and

Rouzalia R. NAZYROVA **
* Energy Section ofthe Kazan Science Center ofRAS, Tatarstan, Russia

** Kazan Tupolev Technical University, Tatarstan, Russia
ABSTRACT
Power possibilities have expanded in many directions of science and technology;

energy needs have caused the interpenetration of investigation methods and means.
The postulating of a new fundamental theory, EXPERT THERMODYNAMICS is on
the agenda. This theory includes the investigation of different energy transforming
processes for designing knowledge models, the analysis of different knowledge models
with extrapolation and interpolation and estimation of energy result characteristics.
Logic and linguistic directions for studying thermodynamic processes are among the
bases of EXPERT THERMODYNAMICS.
RESUME
Les possibilites energetiques ont determine l'expansion dans bien de directions de la
science et de la technologie; les besoins en energie ont conditionne l'interpenetration
des methodes et des moyens de recherches. La postulation de la tMorie
THERMODYNAMIQUE EXPERTE est a l'ordre du jour. La tMorie comprend les
recherches des processus de transformation de formes differentes de i'energie pour
construire des modeles de connaissances, l'analyse de modeles differents de
connaissances avec l'extrapolation et l'interpolation et l'estimation des
caracteristiques energetiques. Des demarches logiques et linguistiques dans les etudes
des processus de la thermodynamique font partie des bases de la
THERMODYNAMIQUE EXPERTE.
1 INTRODUCTION
The XIXth and XXth centuries will be known in the history of civilization as times of
«industrial» intensification of obtaining, transforming and consuming energy [1-8].
Industrialization has caused the qualitative and quantitative predominance of

ecological factors that far outweigh the means at our disposal for limiting them. At
present energetics and environment ecology make it necessary to:
• design fundamentally new energy-saving and clean technologies,
• develop fundamental and applied investigations to revise basic terms of classic
theories,
• improve scientific and technical thought.
What is the essence of "old" problem solving in the post-industrial and present
information society? [9]
2 EXPERT THERMODYNAMIC ANALYSIS
2.1 Why?
The postulating of a new fundamental theory EXPERT THERMODYNAMICS

investigating the correlation problems of energy and knowledge models is on the
agenda. A brief historical analysis of the development of society reveals, among
others, the following.
During the Vlth-I1Ird centuries B.C.E.:
• new and original results were obtained based on deductive analysis of the research
of scientists of preceding generations (Alexandria Academy).
From the end of the XVIIIth century to the beginning of the XXth century:
• building the logic of natural science (B.Bolzano, D.Hilbert);
At the end of the XXth century the following conclusions were postulated.
• «Growth of machines over the course of time occurs as a geometrical progression
in the structure of human society ... We are experiencing a radical break up of the
scientific world outlook during our life time» (V.I.Vemadsky);
• At present the problem of a logical concordance of the structure and language of
science appears;
• «In natural science history ... First of all, the empirical correlations come to the
foreground ... and, second, slowly and instinctively, the expansion of axioms and
main principles of a logic base has come to the fore. A logic base is basic to all
scientific hypotheses and empirical generalization, as well as to mathematical or
logical layout, a model which we use in scientific work» [10] (V.I.Vemadsky).
The EXPERT THERMODYNAMICS apprehends:

• the investigation of different energy transforming processes for designing
knowledge models;
• the analysis of different knowledge models with extrapolation, interpolation and
estimation of energy result characteristics.
Power Engineering Data III
The EXPERT THERMODYNAMIC ANALYSIS is one of the main methods of expert

thermodynamics. It is summarized below.
2.2 What?
At present, engines and energy sets are operated by traditional energy resources;
tomorrow, non-traditional resources, composed of thermodynamic processes and
cycles will be used. Universal use of thermodynamic methods has caused some
authors to build a unified transformer theory (Kharkevich A.A., Alexeev G.N.) which
has in turn instigated both a review of basic thermodynamic principles (Veynick A.I.,
Heywood R.V., Rumer Yu.B., Ryvkin M.Sh.) and an extension of its sphere of
usage. A deeper level of knowledge engineering development makes it possible to
carry out the logic-linguistic analysis of classical theories, e.g. classic, technical and
chemical thermodynamics. During the development of thermodynamics, attempts at
logical analysis and validation were undertaken by setting and solving the problem of
axiomatization. Such axiomatization of thermodynamics was done by G.Falk and G.
Young, N.N.Schiller and T.A.Afanasyeva-Erenfest, K.Karateodory [11]. The present
axiomatization of thermodynamics is defined by building a model based on the
knowledge concept. Representation of the classical thermodynamic models of
knowledge including descriptions of heat and mechanical energy interconversion
processes is based on formulating conceptions and relations, logic axioms and laws
[12].
The classes of conceptions are:

• thermodynamic system S,
• thermodynamic state N,
• thermodynamic process P (isobaric Pp, isothermal PT, isochoric Pv, adiabatic
PQ, cyclic Pc, reversible PB),
• thermodynamic characteristics C (heat Q, internal energy U, pressure p,
temperature T, volume V, mechanic expansion W-, mechanic reduction W+,
efficiency 11).
The classes of relations are:

• to be involved in process (fJ),
• to be increased in process (r2),
• to be reduced in process (r3),
• to be constant (q),
• to include (r5),
• to be defined by (r9)
• to differ at infinitely small (r12),
• to occur or in around (r13),
• to follow (fJ4)
For example,
• (S rl P)-system S is involved in the process P,

• (U r4 P)-internal energy U is constant in the process P.
• (P r5 PQ)-process P includes the adiabatic process PQ,
• (P r9 (C2rI4CI»-process P is defined by the transition from state CI to state C2·
The set of axioms is formed by axioms of Relations and Thermodynamics. Examples

of axioms:
1=
(S riP) !\ (P rSPI)~ (S rlPI)
1=
(NIrI3N2) B (CI r12 C2)
1=
(S rIPQ) !\ (PQ rs w+)~ (S rlPI)
I = (U r2P) B (T r2 P)
1=
(P r5 Q) ~ (U r2 P) v (P r5 W-)
1=
(S riP) ~ (P rsQ) v (P r5 W-) v (P r5 W+)
1=
(S rIPy) ~ --, (P r5 W-) !\ --, (P rs W+)
1=
(S rIPQ) ~ --, (PQ rs Q)
In particular, the set of rules includes expressions:
I=A, I=A~ B
I=B
I= A -+ B, 1= B -+ C
I=B-+C
1 = A -+ B v C, -+ 1= .B
I=A-+C
I=A!\B-+C I=A
I=B-+C
2.3 How?
The process of deductive analysis is defined by the logical search for expressions [\3].
For example, the analysis of the two formulas:
1= (S rl Py) ~ (T r2 Py)
1 = (S rl PQ) ~ (T r2 PQ)
is presented by the following, for the first expression:
I= (SrIPV ), I= (SrI Py ) -+ .(Pr5 W-) /\ .(Pr5 W+)

1= .(Pr5 W-) /\ .(Pr5 W+)
Power Engineering Data 113
Expression -, (P r5 W-) /\ -, (P r5 W+) which is equivalent to (P r5 W-) v (P r5 W+)
Then 1= (S qPy) ~ (Py r5 Q) v (Py r5W-) v (Py r5W+)

is included 1= (S q Py) ~ (Py r5 Q)
However 1= (P r5 Q) ~ (U r2 P) v (P r5 W-)
Therefore 1= (S rl Py) ~ (U r2 Py)
From axioms 1= (S rl Py) ~ (T r2 Py) is possible.
The analysis of the second expression is carried out similarly.
1= (P r5PQ)
1= (S rIPQ) ~ (PQ r5 W-) v (PQ r5 W+)
1= (PQ r5 W+) ~ (U r2 PQ)
1= (S rl PQ) ~ (U r2 PQ)
1= (S rl PQ) ~ (T r2 PQ)
2.4 Where?
To carry out investigations on the correlation of energy and knowledge models in

engine building and the heat energetics field, the authors of this work are developing
an EnergyBrain program-information system. The core of the system is the software
program TDsoft [14,15] and its environment. It also includes the set of knowledge
bases both on processes and the working medium, made by forms and sources,
methods and meanS of obtaining energy, its transformation and consumption. The
practical aim of the Energy Brain system is optimization of energy unit parameters,
either On carrying out individual investigations in a complex environment or by using
an autonomous operation expert system.
3 CONCLUSION
Power possibilities have enabled the expansion of science and technology in many
ways. Power needs have caused the interpenetration of investigation methods and
means. At present it is imperative to formalize the knowledge aspect. If in the past,
axiomatization was harshly criticized (M. Planck, A. Putilov), today the development
of expert systems underlies its growing importance. Some of these knowledge
databases must take into account the interdependence of the time factor and
differentiation characteristics. The results currently obtained, and partially presented

in this work allow us to stress the growing use of logic-linguistic methodology to
investigate various thermodynamic processes.
KEYWORDS
expert thermodynamic, process, energy, knowledge model
REFERENCES
[I] Dobrokhotov V.L, Energy saving problems. Thermal Engineering, 4, (1991), p2-
5
[2] Myema E., New and renewable energy source usage possibilities, Science
World, 36, 3, (1992), p5-8
[3] Bashmakov LA, World energetics in 1990-2020., Izvestiya AS. Engineering, 3,
(1992), p. 18-28
[4] Dobrokhotov V.L, Nontraditional energetics: problems and decisions., Thermal
Engineering, 4, (1992), p.2-5
[5] Kozlov V.B., UN program on new and renewable energy sources, results of the
realisation., Thermal Engineering, 4, (1992), p.II-15
[6] Olkhovoky G.G., Gorin V.I., The state and prospects of heat energetics
development., Thermal Engineering, 2, (1992),p. 13-20
[7] The energy equation changes., Engineering, v.231, (1991), 1, p.30-32
[8] Demirchyan K.S., Global and local problems of ecology and development of
the country., lzvestiya AS. Engineering, 3, (1992), p.3-17
[9] Rabtoy AM., Computer revolution philosophy. - Moscow Politizdat, 1991-287
[10] Vemadoky V.I., Nature consideration. Space and time in living and non-living
nature., Moscow Science, (1975)., p 176.
[11] Francfurt V.I., In history of thermodynamic axomatization, ColI. The
development of modem physics., Moscow Science, (1964), p. 257-292
[12] Pospelov D.A., The logic-linguistic models in administration systems.,Moscow
Energyatomizdat, (1981). P 232.
[13] Teyz A, Griboman P., Luy G., and others., The logical approach to artificial
intelligence: from classical logic to logic programming World, (1990), p32
[14] Dregalin AF., Nazyrova R.R., An introduction of Artificial Intelligence elements
into heat energetics., Izvestiya VVZ: Aviatsyonnaya Tekhnika, 4, (1993), p.90-
94
[15] A.F. Dregalin, R.R.Nazyrova, T.R.Sitdikov and others., On the TDsoft program-
information system, Izvestiya VVZ:Aviatsyonnaya Tekhnika, 1, (1994), p.l02-
106
LIQUID-SOLID TRANSITIONS WITHIN MULTIPLE
EMULSIONS. ENTHALPY AND TEMPERATURE DATA
ApPLIED TO MASS TRANSFER STUDIES.
D. CLAUSSE, 1. PEZRON, L. POTIER and S. RAYNAL
Departement de Genie Chimique, Division de Thermodynamique et

Physicochimie de Pro cedes Industriels, Universite de Technologie de
Compiegne, BP 529, 60205 COMPIEGNE Cedex, France.
ABSTRACT
Solidification and melting phenomena occurring in a W/O/w multiple emulsion are

described. These studies are carried out on multiple emulsions containing urea in the
inner aqueous phase and for which mass transfers through the oil liquid membrane
may occur. From differential scanning calorimetry performed on these emulsions, the
enthalpies and temperatures (LJH, T) of liquid/solid transitions were determined..
Information about the ice and urea nucleation phenomena were deduced.
A correlation between liquid/solid transition data (LJH,T) and the composition and
masses of the outer and inner aqueous phases has been made in order to point out
water flux through the oil liquid membrane.
RESUME
L'article decrit les phenomenes de solidification et fusion se produisant dans une
emulsion multiple du type E/H/E. Ces etudes ont ete realisees sur des emulsions
contenant de l'uree dans la phase aqueuse interne et pour lesquelles des transferts de
matiere peuvent se produire a travers la membrane huileuse. A partir d'une analyse
enthalpique differentielle des emulsions, nous avons determine les enthalpies et les
temperatures (LJH, T) des transitions liquide/solide et deduit des informations sur la
nucleation de l'uree solide et de la glace dans ces systemes.
Nous avons effectue une correlation entre les donnees (LJH, T) et les compositions et
masses des phases aqueuses interne et externe, ce qui nous a perm is de mettre en
evidence un flux d'eau atravers la membrane huileuse.
1 INTRODUCTION
Water in oil in water (w/o/w) multiple emulsions are made of oil globules dispersed
within an aqueous medium, these oil globules themselves containing aqueous droplets.
Due to their complex structure [1], it is expected that specific thermal transitions will
occur when these emulsions are submitted to steady cooling and heating. These
possible transitions are essentially solidifications and meltings of both aqueous
phases, one dispersed within the oil globules and the other wherein the oil globules are
dispersed. Another possibility that will not be considered in this article is the
solidification of the oil phase insofar as the oil used does not show such a transition in
the temperature range investigated.
Solidification appears to be the result of the growth of critical nuclei formed inside
undercooled liquid (pure compounds) or supersaturated solutions (solvent + solute
systems). In this article we shall describe how it is possible to get information about
undercooling/supersaturation and nucleation phenomena by using a technique that
detects solidification and melting. For that purpose, we have used differential
scanning calorimetry (DSC) that gives the changes of enthalpy ~H and the
temperatures T of a system during solidification or melting. Furthermore, from the
analysis of the ~H and T data concerning the bulk phase (external aqueous phase) and
the dispersed phase (internal aqueous phase) it is possible to determine their mass
fractions and compositions. Previous works on multiple emulsions seen as liquid
membranes [1-5] have pointed out mass transferred through the oil phase when
referring to W/O/W emulsions. This transfer may occur in both directions, from the
outer to the inner phases or the reverse, depending on the thermodynamic driving
force resulting from a difference in the compositions of the two aqueous phases.
Should this transfer occur, it will cause changes in the mass fractions and
compositions of both aqueous phases, changes that are expected to be detected
through the ~H and T data. The last part of this article is devoted to such an
application of nucleation phenomena for studying water transfer through the oil phase
of a W/O/W emulsion containing urea in the aqueous inner phase.
2 MATERIALS AND METHODS
Figure I is a schematic representation of a multiple emulsion drop. In our studies the

multiple emulsion contains in the internal aqueous phase 5.8% urea, 0.4% MgS04 and
51.4% pure water; in the oil liquid membrane 3.2% of emulsifier 1 and 19.2% paraffin
oil, in the external aqueous phase 0.8% of emulsifier 2 and 19.2% pure water.
The multiple emulsions have been obtained through a two-step process described in
detail elsewhere [5]. From optical microscopy study, the emulsions have been
characterized by the mean diameter of the entrapped water droplets (approximately
Liquid-Solid Transitions within Multiple Emulsions 117
lJ..lm) and the mean diameter of the oil globules (around 10J..lm). In order to obtain
these data it is impossible to avoid first diluting the multiple emulsion and this
procedure presents an actual picture of the emulsion. It is known that in such
emulsions containing relatively huge amounts of water droplets within numerous oil
globules, compactness can introduce local stresses [6].
Oil liquid membrane

External aq ueous phase Internal aqueous
phase ~ phase: MgSO, and
urea solution
Emulsifier 1
oil soluble water soluble
low HLB high HLB
Figure 1: Schematic illustration of a multiple W/O/W emulsion drop
From time to time samples from an undiluted emulsion preserved at 20°C have been
taken and put into a calorimeter cell, the volume of which is: 270mm 3 . Then, the
sample introduced into a flux calorimeter DSe III SETARAM is submitted to a
steady cooling (rate: 2°C min-I) from 20°C down to -60°. For specific purposes
related later on, the sample has been quenched to a subambient temperature (-30°C)
and then steadily cooled. As soon as -60°C is reached, the sample is heated up to
20°e.
3 SOLIDIFICATION AND MELTING OF A MULTIPLE W/OIW

EMULSION. RESULTS AND DISCUSSION
In order to proceed to a discussion of the results obtained as soon as they are given,
we shall first recall the general rules of solidification and melting of binary systems
that have been pointed out from previous studies [7,8]. Let us call A and B the two
components of the system. We shall assume that only pure component solid phases
may be present when they are in equilibrium with liquid phases containing A+B
components and that this system shows an eutectic point. In these conditions when a
system of composition XM (Figure 2) is at equilibrium temperature TM and pressure P
= Po it is made of one liquid phase whose composition is given by XL and one solid
phase whose composItIon is given by Xs= 0 % (A) or 100 % (B). When the
temperature is less than the eutectic one T E , the equilibrium state is total solidification
e
of the system. When point M belongs to the domain referred to as III, the system is
made up of a liquid phase in equilibrium with a solid phase the composition of which
is XA = 100 %.
A
Temperature
II III
/'
/ €e" "-
, l1'/ / , , re /
" r '- L I
" , IV ,/
_~/ _ _ _ _ _ '/0:
,/ /
-T'~----/P
/
/
,, I
/
_ _ _ _ _v
10~% x M XL x£e x£ 10~%
Figure 2: Solidification and melting temperature of a binary A+B system
It is well known [9-13] that the liquid to solid transition does not occur for all the parts
of the liquid at the same time, but on the contrary, it needs the birth of at least one
solid particle, called a nucleus. As its specific area is relatively important, surface
effects are more important that bulk ones, and its equilibrium temperature with the
remaining liquid can be much lower than the one predicted by the equilibrium curves
(f e when XM < XEe, Le when XM > XEe). Another aspect is the kinetic one. Solid
particles whose sizes are less than the nucleus one vanish and those whose sizes are
greater, grow and macroscopic solidification occurs. One consequence of this is that
only a probability of nucleation (birth of a nucleus) and then solidification can be
given. It is then necessary to study a certain number of identical samples to know this
probability. It appears from general studies that a most probable temperature T* of
solidification can be found. This temperature corresponds to a maximum of freezing

events around it and broadly speaking, 50 % of the samples have undergone
solidification. The dotted lines r and ~ of Figure 2 give these most probable
temperatures of component A solidification when XM is less than XEand of component
B solidification when XM is more than XE. At this temperature T* it is possible for
instance, to evaluate the total amount of component A that will solidify. This is given
by:
1- __x---,M~_ (I)
x r e '(T *)
Xr ' (T*) being the composition of the supersaturated solution with regard to
e
component B; solution that is in equilibrium with the solid phase formed of pure
component A. r'e appears to be the metastable extension of the equilibrium curve r e.
From experimental studies and thermodynamic analysis it is possible to get
information about this curve [7,8]. Tu* give the most probable temperature at which
the remaining solution in equilibrium with pure B crystals will completely solidify, as
at this temperature the conditions of solidification of component A given by ~ curve,
are satisfied. This supposes that B crystals have no nucleating effect on the A crystals.
To summarize, when a system of concentration XM is steadily cooled, it is expected

that B crystals will appear at T* (curve r - probability 50 %) and total solidification
(crystals A and the remaining crystals B) at Tu * (intersection of curves ~ and r e' -
probability 50 %). This picture holds when XM is less than Xu,. For XM included
between XE and xu, the system solidifies totally at the same temperature given by
curve r. This is understood when it is seen that when crystals B appear (curve r) the
temperature is lower than Tu and then the conditions for solidification of crystals B
are satisfied instantaneously. From this analysis, it can be deduced relatively easily
what will be the behavior of a system of composition XM >xEwhen it is cooled down.
First crystals A will appear at a temperature around T* given by curve ~ Then total
solidification will most probably occur atTp* if XM > xJ3' or at the same temperature
T* (curve~) ifxE < XM < xJ3'
Hopefully, the melting of any totally solidified system is much simpler than
solidification insofar as there are no nucleation phenomena involved. If T* (curve r)
is less than TE e (eutectic point), melting begins only at this latter temperature. If XM <
XEe, all crystals A dissolve at TEe and a certain number of crystals B, the total melting
of which being when the temperature is the one given by curve r e for x = XM. When
xM> XEe the reverse occurs. If only crystals A or B have appeared during the cooling,
the melting of the corresponding crystals begins as soon as the heating starts. For the
study reported in this article we shall refer to water as component A and to urea as
component B. When considering the composition of the multiple emulsion reported
before, it appears clearly that other components are involved. Due to their low
solubility in water or the very slight amount introduced (MgS04) we shall not
consider them in the analysis.
As we announced at the beginning of this section, before describing the solidification

and melting phenomena taking place within the multiple emulsion, we shall describe
the behavior of a bulk aqueous phase and a dispersed aqueous phase. All the results
obtained from DSC measurements and described in detail elsewhere are seen in
Figure 3. We recognize the equilibrium curves Ie and Le that, at a temperature T
under atmospheric pressure, provide the composition of a solution (urea + water) in
equilibrium with pure ice (curve Ie) or with pure urea (curve Le) [14,15].
150
125
.
100
rc •
75
"
50 •
25
+ + +
-25
-50 1 r
-75 _ "
-100 -'-~_-L-_~-'-_~--I._~_'--~--'
o 20 40 60 80 100
urea mass fraction (%)
Figure 3: Solidification and melting temperature of a urea + water systems in bulk (B)
or dispersed (J..l) in emulsion
The eutectic point Ee is found at XE = 35% and T e = -12°C. The dotted lines IB and
LB give the most probable temperature T* at which in a bulk aqueous phase the ice
will appear when composition XM is less than XEB or the urea will appear when XM is
more than XES' For these bulk systems we have found that complete solidification
occurs at TuB* when x is less than Xu' or at T~B * when X is more than xw. For x
between xu' and x~' total solidification occurs as soon as ice (x < XEB) or urea (x>
XEB) crystallize. Figure 4 is an illustration of the DSC thermograms obtained for three
different compositions showing the behavior just described above.
For aqueous solutions dispersed within an oil phase, solidification does not exactly
follow the general behavior. The dotted line r Il gives the most probable temperatures
of ice solidification for composition x less than 60 % wtlwt. No delay for urea
solidification has been observed in these conditions. When x is more than 60 %, total
solidification appears at a temperature that seems composition independent.
Furthermore, till now, we did not succeed in getting the solidification of urea first for
dispersed solutions the composition of which being more 60 %, as would be expected.
With these results dealing with bulk and dispersed systems that simulate the outer and
inner phases of a multiple emulsion, we can interpret the DSe thermograms obtained
when such an emulsion is cooled and heated steadily. Figure 4 shows the solidification
of the outer (signal I) and inner (signal II) phases of a multiple emulsion, the
composition of the inner phase being urea 10 % wtlwt. The melting signal appears to
be the superposition of three signals related to :
1. Eutectic melting at T Ee = - 11°e

2. Progressive melting of ice in equilibrium with an aqueous solution of urea
3. Ice melting at around ooe from the nearly pure water of the outer phase.
1..-_ _ __ (a)
-50 -40 -30 -20 -10 o 10

Temperature (0C)
Figure 4: Thermograms showing the solidification of the outer (signal I) and the inner
(signal II) and the melting of the outer + inner (signal III) phases ofW/O/W
From these results on solidification and melting of bulk or simply dispersed or doubly
dispersed (multiple emulsion) systems it is possible to get information on ice and urea
nucleation in these systems as shown in the next sections:
4 ICE AND UREA NUCLEATIONS
As recalled previously, solidification is the result of nucleation taking place in an

undercooled compound or in a supersaturated solution. Numerous attempts have been
made in order to deduce nucleation data from solidification studies especially in the
field of ice nucleation within aqueous media because of the necessity of knowing
these data for application purposes in meteorology [11] [16] and cryobiology [17,18]
for instance. The parameter characterizing nucleation is the nucleation rate, J, that
gives the number of nuclei formed per unit of time in a unit of volume. From
thermodynamic analysis applied to a pure compound [11] it follows:
kT _n_
J=cb- Q
h n-2/3
f?£
-9
1t
r
exIt-(~F *+~Fn)/kT] (2)
where:
c: Number of mono molecules per unit of volume

b: Number of molecules per unit of area of a liquid in contact with a
solid
nn: Area of a nucleus
n: Number of molecules in a nucleus
A: Constant for a given compound
AF*: Activation free energy per molecule for viscosity
AFn: Free energy of formation of a nucleus.
Instead of relation 2, the approximate formula
is sometimes used, insofar as the product of the missing terms is close to one. The free
energy of formation AFn of a solid embryo considered as a sphere of radius r, is the
sum of two opposing terms:
(4)
The first one is the energy involved for "condensation" of molecules from the liquid
and the other is related to the energy of formation of a new liquid-solid interface.
Then A and B are two constants related to intermolecular forces that create the solid
cohesion and to the interfacial liquid-solid energy, a, respectively. This energy of
formation shows a maximum between two equilibria states corresponding to the liquid
state (r = 0) and to the macroscopic solid state (r ~ 00)' The maximum is
characteristic of an unstable equilibrium of an embryo of radius rn called the nucleus.
It can be shown that:
rn= 2q (5)
n Llli (T-T J
and
L\Fn = ina
3 r.n2 (6)
where ~H is the solidification enthalpy at the temperature T less than the stable
equilibrium temperature Teat the same pressure. From relations 5 and 6 it can be seen
that the lower the temperature, the smaller rn and~Fn and the greater the contribution
of ~Fn to the nucleation rate, 1. This effect can be screened when a high viscosity
liquid is concerned, as when T is lowered, the viscosity increases and ~F as well. This
phenomenon has not been observed in pure water but it has been observed in aqueous
solutions of electrolytes that fail to crystallize [8,19,20,21].
The formulae given before are valid only for a pure mother phase. When another
component is present it can be expected that its presence will modify the nucleation
rate. More has been done in the field of nucleation in gaseous phases [22,23] than in
the field of nucleation in condensed systems. In this article we shall not go into this
complex phenomenon; we shall just recall some previous estimations. For water +
sodium chloride, it has been found that the higher the amount of sodium chloride, the
bigger the nucleus and the smaller the nucleation rate. For the diffusion process, it can
also be understood that if a nucleus grows in a mixture, it becomes surrounded with a
region impoverished in the precipitating component and this will increase ~F* and
then decrease the nucleation rate as well [11].
If mononucleation is considered and if there is no problem of crystal growth, a sample

will solidify as soon as a nucleus forms within it. The smaller the sample, the better
this assumption is verified. Nevertheless, the appearance of a nucleus is an essentially

random phenomenon, for although it is possible to estimate the nucleation rate, it is
impossible to predict at what points in the sample the nuclei are formed. If the sample
is slit up into a large number of small droplets, the appearance of a nucleus in anyone
of these droplets and then solidification of anyone of these droplets is a phenomenon
for which only a probability can be predicted.
Therefore it appears an absolute necessity to study a sufficient number of identical

samples to obtain reliable data on nucleation phenomena. As has been stated and
verified by numerous scientists whose work dealt with nucleation phenomena, this
dispersion of solidification temperatures does not prevent our recognizing a very
characteristic value that has been called the mean freezing temperature T c or the most
probable temperature T* as we did. T c has been defined as being the temperature at
which 63.2 % of the drops solidified according to an analysis based on probability
considerations [11 ]. We have chosen to define this characteristic value as being the
one corresponding to a maximum of solidification events. T* is determined from
experimental data only and corresponds roughly to the temperature at which 50% of
the drops or samples solidified [24].
Following a statistical study of nucleation of identical droplets [9-11] we shall

introduce the probability p(V, t) that a given drop of volume V should have solidified
during the time interval between the initial instant t = 0 at which cooling commenced
and the instant t. For a steady cooling rate t = dT/dt, p(V, t) may be expressed in
terms of volume V and temperature T. When a large number (No) of identical drops
are considered, the number NT of drops which have been nucleated and therefore
frozen when temperature T is reached is given by :
p(V,I) =~
N (7)
o
The number of drops which freeze while T changes to T + dT is :
(8)
Dividing by No and integrating equation (8) between Te (solid-liquid equilibrium

temperature) and T, the relation obtained is :
In (l - P (V, t) ) = TV JTT e J (T) dT (9)
This equation shows clearly that the bigger the volume, the higher the probability of
nucleation and then solidification of a sample at a given temperature. Speaking in
terms of the most probable temperature T* that we have defined by p(V, t) = 0.5, it
appears that the smaller the volume, the lower T*. Referring to the results obtained on
water + urea systems and shown in Figure 3, it can be seen that the most probable
temperatures given by the dotted lines, r Band LB for bulk systems and r!! and Lil for
microsized systems are actually higher when the volume is greater. This effect can be
quantified by calculating the undercooling or supersaturation ~T given by:
~ T = T r e (or TIe) - T r (or T I) (10)
The values obtained for bulk ~TB or microsized ~T Il systems are gathered in Table 1.
Urea ~TB ~T!!

Concentration (0C) (0C)
0 14.3 41.0
10 14.5 44.7
20 16.1 48.2
30 19.6 51.8
40 17.9 53.6
Table 1
These results show also that the nucleation rate and the probability of solidification is
smaller at a given temperature, when the amount of urea is higher. This result is in
agreement with what has been stated in sections 3 and 4.
In the next section we shall see how it is possible to detect mass transfer within
multiple emulsions by studying solid phase nucleation by differential scanning
calorimetry as has been described in the preceding sections.
5 MASS TRANSFER WITHIN MULTIPLE EMULSIONS
We have seen that the most probable temperature T* of solidification of the dispersed
inner phase is composition dependent. Furthermore other data that give DSC signals
are the changes of the enthalpy, ~H, when solidification occurs. These data are
deduced from the area of solidification signals I and II. If at a temperature T the
enthalpy changes per mass unit, ~h, are known, it is possible to obtain the mass that
has solidified at T and then the masses of the inner and outer phases. Should a mass
transfer occur in the emulsion maintained at 20°C, it will be pointed out by changes in
the T and ~H values of the inner and outer phases. In Figure 5 we have grouped the
results obtained in this way.
4.0 B
3.5
3.0
2.5
2.0
Ill\,
1.5
1.0
0.5
c
O.O.L.....C---'---.L.....l.---'--.l..-I.---'--.l..-I.---'--.l..-I.+-'
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
rrJ/1T\
Figure 5: Curve showing water transfer through the liquid membrane of a W/O/W
emulsion. A, no transfer, C, W/O emulsion; B, creaming. Points between AC, water
transfer from the outer to the inner phase.
More details of this study are available elsewhere [5]. In this figure we have plotted
the points whose coordinates are the ratios mlo/mo and mli/mi, mlo and mli being the
masses of the outer (0) and inner (i) phases deduced from DSC, and mo and m i the
masses of the same phases deduced from the multiple emulsion formulation. When
these ratios equal 1, there are no differences with the initial values and no transfers
occurred. This situation, depicted by point A in Figure 5, has been encountered for
undiluted emulsions despite the urea concentration differences between the inner
phase (10 % wt/wt) and the outer phase (0% wtlwt). This behavior has been observed
by other scientists [2,4] using viscosimetry as a means of investigation. When the
emulsion is diluted in water, a water flux is created from the richest water
concentration phase (outer phase) towards the inner phase. Then the ratio mlilmi
increases and the ratio mlo/mo decreases as can be seen in Figure 5. Two extreme
situations are indicated by point C (the multiple emulsion has changed to a simple
W/O emulsion) and point B corresponding to a situation for which there are no longer
dispersed liquids in the system, oil and water are supposed to be partitioned into two
bulk phases (creaming).
4 CONCLUSION
On studying, by differential scanning calorimetry, the solidifications and meltings

taking place in a steadily cooled and heated W/O/W multiple emulsion, we have
shown how it is possible to get data on ice and urea nucleation rates. The results
obtained are in agreement with the classical nucleation theory and with previous
results obtained on binary systems taken separately in bulk and dispersed as sample
emulsions. For a more thorough investigation, it is necessary to carry out isothermal
measurements in order to obtain the nucleation rate values. In this case, the effect of
temperature is replaced by a time effect with the advantage that the nucleation rate is
supposed to be a constant. This study is undertaken in our laboratory not only to
obtain more information on nucleation phenomena but also to obtain more information
about mass transfer in view of its applications in different fields. For instance in
cryobiology these systems may simulate the situations encountered when
cryopreservation of cells and tissues or devitalization of undesirable tissue are wanted.
In the first case intracellular ice freezing (IIF), similar to the solidification of the inner
phase of the W/O/W emulsion, must be avoided in order to prevent deterioration of
the tissues by ice expansion; in the second case, IIF is wanted [17]. Mass transfer
studies concern the controlled release of entrapped compounds such as vitamin B2 or
vaccine]. These experiments also find applications in cosmetology.
KEYWORDS
multiple emulsions, calorimetry, solidification-melting, enthalpy, mass transfer
REFERENCES
[1] N.N. Li, U.S. Patent 3,410, (1968), 749.

[2] S. Raynal, lL. Grossiord, M. Seiller and D. Clausse, J. Contr. Released,26,
(1993), 129.
[3] S. Matsumoto in: ACS Symposium Series n0272, Am. Chern. Soc., D.O.
Shah, ed., Washington D.C, (1987), 415.
[4] N. Garti and S. Magdassi, J. ColI. Interface Sci., 104, (1985), 587.
[5] L. Potier, thesis, Universite de Technologie de Compiegne, France, (1993).
[6] D.M. Buzza and M.E.Cates, Langmuir, 9, (1993), 2264.
[7] D. Clausse, J. Chern. Phys. Abstract, 76-1, (1976), 333.
[8] D. Clausse, Encyclopedia of Emulsion Technology, P. Becher, ed, Dekker,
New York, (1985), 77.
[9] E.K. Bigg, Proc. Phys. Soc., B66, (1953), 688.
[10] A.E. Carte, Proc. Phys. Soc., B69, (1956), 1028.
[11] L. Dufour and R. Defay, Thermodynamics of Clouds, International
Geophysics Series, Vo1.6, 215, New York and London, (1963).
[12] D. Clausse, L. Babin, F. Broto. M. Aguerd and M. Clausse., J. Phys. Chern.,
(1983),4030.
[13] D. Clausse, J.P. Dumas, P. Meyer and F. Broto, J. Disp. Sci. Tech., 8,
(1987), 1.
[14] F.W. Miller and H.R. Dittmow, J. Amer. Chern. Soc., 56, (1934), 848.
[15] W.A. Noyes, Ind. Eng. Chern., 47, (1925), 2170.
[16] H.R. Pruppacher and J.D. Klett, Microphysics of Clouds and Precipitation, D.
Reidel Publishing Compagny, (1980).
[17] J.O. Karlsson, E.G. Cravalho and M. Toner, Cryo-Ietters, 14, (1993), 323.
[18] F. Franks, S.F. Mathias, P. Galfre, S.D. Webster and D. Brown, Cryobiology,
20, (1983), 298.
[19] M. Fariane, R.K. Kadiyala, C.A. Angell, J. Chern. Phys., 78(9), (1983), 3921.
[20] C.A. Angell, E.J. Sare, Cryo-Ietters, 1, (1980), 257.
[21] D. Clausse, L. Babin, 1. Sifrini, F. Broto and J.P. Dumas: "Water and Steam,
their Properties and Current Industrial Applications", J. Straub and K.
Scheffler, eds, Pergamon Press, (1979), 664.
[22] P. Mirabel, J. Katz, J. Chern. Phys., 60(3), (1974), 1138.
[23] W.J. Shugard, R.H. Heist and H. Reiss, J. Chern. Phys., 61(12), (1974), 5298.
[24] J.P. Dumas, D. Clausse and F. Broto, Thermochimica Acta, 13, (1975), 261.
Chapter 3
UNDERSTANDING COMPLEX SYSTEMS
INVESTIGATION OF THE STRUCTURAL AND ACIDIC

PROPERTIES OF BULK OFFRETITE USING FIRST
PRINCIPLES MOLECULAR DYNAMICS
J. WEBER (a), L. CAMPANA (a), (b), A. SELLON] (a), A.

PASQUARELLO (b), 1. PAPA] (e), and A. GOURSOT (e)
(a) Department of Physical Chemistry, University of Geneva, 30 quai Ernest-

Ansermet, CH-1211 Geneva 4, Switzerland
(b) Institute IRRMA, Swiss Federal Institute of Technology, PHB-Ecublens,
CH-l 015 Lausanne, Switzerland
(c) Ecole Nationale de Chimie, URA 418, 8 rue de l'Ecole Normale, F-34053
Montpellier, France
ABSTRACT
Local density jUnctional theory within the framework of the Car-Parrinello molecular
dynamics method has been used to study the structural parameters and the energetics
of the zeolite offretite, when a Si4 + ion is substituted by (AI3+,H+). The calculations
have been performed for a bulk system made of a periodically repeated unit cell with
54 atoms and a proton. In agreement with previous cluster calculations, it is
concluded that the sites with the lowest (AI,H)/Si substitution energies are also those
with the largest proton affinities. In addition, a previously reported correlation
between site acidity and AI-O-Si bond angles is confirmed.
RESUME
La tMorie de lafonctionnelle locale de la densite, dans sa version connue sous Ie nom
de methode de dynamique moIeculaire Car-Parrinello, a ete utilisee afin d'etudier les
130 Understanding Complex Systems
parametres structuraux et energetiques de la zeolite offretite apres substitution d'un

ion Si4+ par (AI3+, H+). Les calculs ont ete effectues sur un modele du systeme solide
comprenant la maille eJementaire formee de 54 atomes et d'un proton, avec des
conditions aux limites introduisant la periodicite du systeme. En accord avec des
calculs anterieurs effectues sur des agregats, il a ete etabli que les sites presentant les
energies de substitution (AI,H)ISi les plus basses sont egalement ceux de plus grande
affinite protonique. En outre, une correlation obtenue precedemment entre I'acidite
des sites et la valeur des angles AI-O-Si a ete confirmee.
1 INTRODUCTION
Zeolites are inorganic solids with remarkable structural, adsorptive and catalytic
properties, which explains their importance in industrial chemistry [1]. The
aluminosilicate framework of zeolites is made of comer-sharing [Si04]4- and
[AI04]5- tetrahedra, which tend to form rings giving rise to channels or cages in the
material (Figure 1).
CANCRINITE
/CAGE
HEXAGONAL
--- PRISM
T"'2--
Figure 1: Model of the framework topology of the zeolite offretite.
Because of their porous character, which is at the origin of their unique catalytic
properties, zeolites have often been given the name of molecular sponges or sieves.
The modeling of structural and physico-chemical properties of zeolites is a topic of
growing interest as the information provided by theoretical methods is of great value
in rationalizing the behavior of these important materials [2].Offretite is a commonly
Investigation of the Structural and Acidic Properties of Bulk Offretite 131
used acid zeolite, exhibiting the interesting properties to sorb cyclohexane, to convert
isoparaffins or decalin, and to show a better efficiency than ZSM-5 for dewaxing gas
oils. It was therefore of primary interest to investigate the structural and acidic
properties of offretite using theoretical models, and the work reported here is a
continuation of our previous studies [3,4]. However, contrasting with the latter
calculations, which were performed on model clusters using standard quantum
chemical methods, the present study was carried out on offretite modelled as a bulk
crystal exhibiting the same periodicity as that of the aluminum-free structure. For that
purpose we used the Car-Parrinello [5] method implemented with ultrasoft
pseudopotentials [6]. This approach enables us to take into account long range effects,
which can play an important role on the local properties of zeolites.
Our work is therefore aimed at: (i) studying the stability of the two non-equivalent
sites of offretite towards substitution of Si4+ by (AI3+,H+); and (ii) evaluating the
acidity of the different oxygens bound to these sites through calculation of the
corresponding proton affinity.
All the computational details were reported in a previous publication [7]. The
calculations were performed on the unit cell of offretite (Fig.2), namely on a system
consisting of a periodically repeated hexagonal box with 36 oxygen, 18 - n silicon and
n aluminum atoms, where n is either zero or 1.
Figure 2: Unit cell of offretite with site labelling.

We first optimized the structure of the aluminum-free structure (n=O). The results are
presented in Table 1 together with X-ray crystallographic data [8], which refer to a
structure exhibiting an AI/(AI+Si) ratio of about 0.3. The bond lengths reported for the
experimental data are averages over the actual Si-O and AI-O distances weighted by
the aluminum distribution over the lattice sites, because the X-ray analysis could not
differentiate AJ3+ from Si4+.
One third of our calculated distances are significantly shorter than the experimental
ones. As this figure is close to the AI/(AI+Si) ratio, we suggest that these distances
actually correspond to AI-O bonds. This conclusion is supported by the fact that the
related experimental distances appear to be too large for typical Si-O distances in
zeolites which are within the range 1.62-1.65 A.
Parameter Calculated Experimental (b)

(unsubstituted)
TI O I 1.639 1.628
TI 0 2 1.646 1.721
TI 0 3 1.629 1.608
TI 0 4 1.625 1.681 Bond
T204 1.632 1.593 lengths
T20S 1.621 1.627
T206 1.642 1.639
T207 1.632 1.593
°IT I 0 2 113.1 119.5
°2T I 0 3 109.1 108.2
°3T I 0 4 108.3 107.5
°4T I 0 l 110.0 109.1
TI03T'1 144.2 142.1 Bond
T2 06 T'2 151.2 151.6 angles
04T2 Os 108.0 106.8
°4T2 0 7 109.6 109.0
°ST2 0 6 111.3 113.1
°6T2 0 7 109.9 110.4
Table 1 : Calculated and experimental geometry (a) of the T 1 and T2 sites of offretite.
(a) Bond lengths in A, angles in degree.
(b) Ref [8].
Then we investigated two structures of offretite for which Si4+ has been substituted by
AI3+ in a Tl site (AI(Tl» or in a T2 site (AI(T2». The latter form has been found to
Investigation of the Structural and Acidic Properties of Bulk Offretite 133
have an energy lower than AI(Tl) by 3.8 kcal/mole. Changes in calculated structural
parameters resulting from Si4+IAJ3+ substitution are presented in Fig.3.
Figure 3: Calculated differences (substituted minus unsubstituted) in structural

parameters due to Si4+IAJ3+ substitution in Tl (left) and T2 (right) sites.
The results show an increase of the bond lengths of the aluminated T site by 0.08-0.1
A. For each structure the four AI-O bond lengths are nearly equal, whereas one AIOSi
bond angle is larger than the other three by about 15° for Tl and 25° for T2. The
acidic properties of offretite were next studied by attaching a proton to each non-
equivalent oxygen of AI(TJ) and Al(T2), followed by a full atomic relaxation. As
some oxygens are equivalent for symmetry reasons, there are seven different
possibilities labelled TIOiH for the TI aluminated site and T20iH for the T2
aluminated site, respectively. Substitution energies for the reaction corresponding to
the replacement of Si4+ by (AI3+,H+) were calculated as well as proton affinities.
Proton occupancies of the various sites at 298 K were also calculated using a
Boltzmann distribution. The results show that only 03 (TO and 07104 (T2) are
protonated at room temperature. Since the binding energy for 03 is larger than that of
07 by 4 kcal/mole, this means that T2 is more acidic than 03, which is in agreement
with experiment [9]. Finally, examination of the structural parameters of the
protonated systems reveals that the most acidic sites are characterized by largeAIOSi
and small AIOH angles, which confirms the trend observed in a previous theoretical
study [10].
3 CONCLUSION
Present results show that the first principles molecular dynamics method is a reliable
and powerful tool to investigate the structural and acidic properties of materials such
as zeolites. Extension of such studies to the adsorption properties of zeolites with

respect to neutral incoming species will be of particular interest.
KEYWORDS
Car-Parrinello, density functional theory, substituted offretite, site acidity, structural

parameters, quantum dynamics.
ACKNOWLEDGMENT
Financial support by the Swiss National Science Foundation and the OFES, acting as
the Swiss COST office, is gratefully acknowledged. Calculations were performed on
the Cray YMP at EPF-Lausanne, and on the NEC-SX3 at CSCS, Manno
(Switzerland); the authors are grateful to these computer centers for generous grants
of CPU time.
REFERENCES
[1] c.B. Dartt and M.E. Davis, Catalysis Today 19 (1994) 151.
[2] "Modeling of Structure and Reactivity in Zeolites", C.R.A. Catlow, ed.,
Academic Press, London (1992).
[3] A. Goursot, F. Fajula, F. Figueras, C. Daul and J. Weber, Relv. Chim. Acta
73 (1990) 112.
[4] A. Goursot, F. Fajula, C. Daul and J. Weber, J. Phys. Chern. 92 (1988) 4456.
[5] R. Car and M. Parrinello, Phys. Rev. Lett. 55 (1985) 2471.
[6] D. Vanderbilt, Phys. Rev. B 41 (1990) 7892.
[7] L.Campana, A. Selloni, l Weber, A. Pasquarello, I. Papai and A. Goursot,
Chern. Phys. Lett. 226 (1994) 245.
[8] lA. Gard and lM. Tait, Acta Cryst. B28 (1972) 825.
[9] B. Chauvin, M. Boulet, P. Massiani, F. Fajula, F. Figueras and T. Des
Courieres, J. Cat. 126 (1990) 532.
[10] A. Redondo and PJ. Ray, J. Phys. Chern. 97 (1993) 11754.
SURFACE THERMODYNAMICS OF SOLID
MATERIALS BY INVERSE GAS CHROMATOGRAPHY
Mohamed M. CHEHIMI
Institut de Topologie et de Dynamique des Systemes, Universite Paris 7 Denis

Diderot, associe au CNRS (URA34), 1 rue Guy de la Brosse, 75005 Paris
ABSTRACT
Inverse gas chromatography (IGC) is a very useful technique for the characterization
of surface thermodynamics of a wide range of finely divided materials such as
polymers, fibres, mineral fillers and clays. IGC permits determining the dispersive
component of the surface energy (rl) and acid-base constants describing the ability
of the materials to interact via London and Lewis forces. These forces are important
in wetting, adhesion and mixing properties of materials. However, experimental
factors such as the sample injection and the flow rate on the one hand, and data
treatment on the other hand strongly affect the accuracy in assessing quantitative
properties of the materials under test.
RESUME
La chromatographie en phase gazeuse (CPG) inverse est une technique tres utile pour
la caracterisation des proprietes de surface de materiaux finement divises tels que
polymeres, fibres, charges minerales et argiles. La CPG inverse permet de determiner
Ie composante dispersive de l'energie de surface et les constantes acMe-base qui
decrivent les reactions des materiaux a travers les forces de London et de Lewis. Ces
forces sont importantes en mouillage, adherence et melange des materiaux.
Neanmoins, les parametres experimentaux tels que la quantile de solute injectee et Ie
debit d'une part et Ie trailement de donnees d'autre part font que les proprietes de
surface des materiaux ne sont determinees que d'une maniere semi-quantitative.
1 INTRODUCTION
Over the last two decades the use of IGC to characterize the surface energy of finely
divided materials such as polymers, fibers and fillers has considerably increased [1-3].
Such a property is important because it controls many practical applications such as

adhesion, wetting and mixing. In IGC, the term "inverse" means that the stationary
phase rather than the mobile phase is the main object of investigation. Volatile probe
molecules are injected at infinite dilution (zero coverage) in order to allow stationary
phase-probe molecule interactions only and rule out probe-probe interactions (for IGC
at finite concentrations see [1]). For crystalline materials and amorphous (or semi-
crystalline) polymers below their glass transition temperature (Tg), adsorption of the
probes is the main retention mechanism. The fundamental datum in GC is VN, the net
retention volume of the volatile probe, which corresponds to the volume of carrier gas
required to elute a zone of solute vapor:
V
N =J··F·t
cN (I)
where j is the compression correction factor, Fe the corrected flow rate and tN the net
retention time. The higher the VN, the greater is the affinity of the probe for the
material under investigation. VN is the essential link with AG a and AHa' the free
energy and the heat of adsorption, respectively:
-AGa = RTLn(VN) + C (2)

-AHa = d(RLnVN)/d(l/T) (3)
where R is the gas constant, T the working temperature and C a constant which
accounts for the weight and the specific surface area of the stationary phase, and the
standard states of the probes in the mobile and the adsorbed phases [4]. The
determination of AG a or RTLn(VN) values for apolar n-alkanes and molecules capable
of acid-base interactions will lead to London and acid-base properties of the material
under test. However, the choice of experimental factors and methods for data
treatment is crucial in determining reliable materials properties. It is the aim of this
paper to describe these aspects and the capabilities and limitations of IGC in
determining accurate surface thermodynamic properties of materials.
2 EXPERIMENTAL FACTORS
2.1 Injection size
Characterization of the materials surfaces at infinite dilution requires the injection of

extremely small amounts of probe vapors (10-3 to 1 mg). VN should be constant in
the range of variation of the injection size (IS). In this case Henry's law applies and so
does equation (2). However, this does not seem to be always the case, and it is a rather
common observation that VN increases as the IS decreases [1]. Extrapolation to zero
IS might then be necessary. The effect of IS is, for example, depicted in the
Surface Thermodynamics of Solid Materials 137
determination of the isosteric heat of adsorption (qst) of n-nonane on carbon fibers

(CF) [5]. Indeed qst decreases with the surface coverage of the CF from 60 to 45
kJ/mol, a value matching the heat of vaporization (~Hvap) of n-nonane. Figure 1
shows that ~Hvap is reached for a n-nonane monolayer on CF (~2.6 10-6 mol/m 2 ).
65 , - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
60
.,.. •
"0
E
55 •
~ •
VI 50
0""
••••
• • ••
45 • •
40 L -______J -_ _ _ _ _ _ ~ _ _ _ _ _ _ _ _L __ _ _ _ _ _ ~ ______ ~
o 2 3 4 5
surface coverage x 106 { mol.m-2
Figure 1. qst for n-nonane on carbon fiber vs the surface coverage at 50 °C [5]
2.2 Flow rate
The flow rate (FR) is a very important factor and should also be varied until VN is
found constant. A typical FR is in the range of 20-60 mllmin for packed columns.
However, some problems may arise with porous materials or semi-crystalline
polymers. Whilst high FR may lead to a non-equilibrium adsorptionldesorption
process [1], low FR leads to a slow diffusion of the probes into the bulk of amorphous
or semi-crystalline polymers on the one hand [6], and the diffusion of small probe
molecules in the pores of micro porous materials on the other hand [7]. Slow diffusion
into the micropores can be minimized by using high FR because the time available for
the small probe molecules to penetrate the micropores is reduced considerably as well
as the effective surface area for adsorption. Similarly, in the case of amorphous or
semi-crystalline polymers, the use of high FR minimizes bulk diffusion and pennits
determining surface properties above Tg [8].
3 DATA TREATMENT AND MATERIALS PROPERTIES
3.1 London component of the surface free energy
For the n-alkanes series adsorbed on a material surface, LlG a or simply RTLn(VN )
values are linearly correlated with n C' the n-alkane chain length. The slope of the plot
is referred to LlG CH 2, the free energy of adsorption of a methylene group, and permits
determining ysd , the dispersive contribution to the surface energy [9] :
ysd = (LlGCH2/NaCH2)2 /4YCH2 (4)
where N is the Avogadro number, aCH2 the cross-sectional area of an adsorbed CH2
group (6 A2) and YCH2 is the surface free energy of a solid containing only methylene
groups such as polyethylene (YCH 2 = 36.8 - 0.058 T(0C) mJ/m 2). Figure 2 shows plots
of RTLn(VN) vs nc for conducting polyaniline (PANI) and PVC. The slopes lead to
the following ysd values: 87 and 32 mJ/m 2 , respectively.
16,------------------,---------,
14
12
z
> 10
• PANI
C
...J .. pvc
b:: 8
2L-L-~ _ _ _ L L __ _ ~ _ _ _ _ ~_ _ ~_ _~
4 5 6 7 8 9 10
n-alkane chain length

Figure 2. RTLn(VN ) vs the n-alkane chain length for PANI and PVC at 67.5 DC.
Carbon fibers (CF) are widely characterized by IGC because they are used for the
fabrication of e.g. high modulus composites whose performances strongly depend on
the strength of the fibre-matrix interface. However, two problems arise in the
determination of their ysd values. Indeed, as-received CF usually have a ysd value of
30-50 mJ/m 2 at 50°C [5,10] which is rather low. Pretreatment at 160°C produces
"clean" CF surfaces of higher ysd value, 77 mJ/m 2 [5]. It has been reported [5] that
aCH2 for a methylene group adsorbed on graphitized carbon black is in the range of
5.2 - 5.5 A2. Applying (4) to CF with these values leads to an increase ofysd of20 to
30%. In the case of microporous materials, equation (4) is not reliable because it
yields very high values compared to those of the reference non-porous ones [11].
Surface Thermodynamics of Solid Materials 139
3.2 Acid-base contribution to the free energy of adsorption
For polar probes capable of acid-base interactions with the packing material it is
assumed that AG a has two additive contributions:
d AB
AG a = AG a + AG a
where AG ad and AG aAB are the London dispersive and Lewis acid-base components
of AG a, respectively. Various methods can determine AG aAB with a certain degree of
accuracy [12]. For example, one may relate RTLn(VN) to AHvap d, the dispersive
contribution to AHvap or to Tb, the boiling point.
20 20.-------------------~b~
15 15
• • o alkanes
Z 10 Z 10 ~ CHCI3
~ >
C c
......Jc::: 5 ic:::=! 5
• EtAc
• THF
0 o
-5
20 30 50
a) llHvapd I kJ.mol-1 b) Boiling point (OC)
Figure 3: Plots ofRTLn(VN) vs AHvapd (a) and vs Tb (b) for n-alkanes and
polar probes adsorbed on tosylate-doped polypyrrole (PPyTos) powder at 57.6
°C. Both methods show markers located off the linear plots and thus indicate that
PPyTos is an amphoteric solid. 0: n-alkanes, + : CHCI3, • : ethylacetate, and
+:THF.
Figure 3 shows that n-alkanes produce a reference linear plot whereas "polar" probes
(e.g. the Lewis acid, chloroform and the Lewis base THF) interacting specifically with
the solid material have their corresponding markers lying above the reference line.
The vertical distance between the n-alkane plot and the data for the polar probe of
interest is :
where VN,ref is VN of a hypothetical reference n-alkane having the same AHvapd.

Figure 3 shows that depending on the property used to characterize the probes, AG/B
values might significantly differ especially when self-associated probes such as THF
are considered [12].
3.3 Acid-base contribution to the heat of adsorption
The acid-base contribution to the heat of adsorption (AHaAB) enables one to determine
either Gutmann's donor and acceptor numbers or Drago's parameters E and C. Usually
this is done by determining AG/B at several temperatures:
(6)
Although widely applied [2,3], this method may suffer from some limitations inherent
to equation (5) on the one hand and due to an increase in AGaAB with T yielding
positive values AHaAB [13,14], on the other hand. An alternative to this equation has
recently been suggested [IS] :
(7)
where AHad can be estimated by AHvap d, the dispersive contribution to the heat of
vaporization of the probes [IS]. Evaluation of AHaAB for Lewis acids and bases with
known Drago's parameters [16] permit determining those for the solid under test using
the following four parameter equation:
where E and C describe the propensity of an acid (A) or a base (B) to undergo
electrostatic and covalent binding, respectively. Using IGC it was possible to
determine both sets of Drago's constants for chloride-doped polypyrrole (PPyCI) :
These constants showed that PPyCI is a stronger Lewis acid than pyrrole and behaves
as a hard species in the concept of Pearson [17]. However, it was shown that the
determination of Drago's constants is linked to the accuracy of equation (7) in
estimating AHaAB. Another approach for the evaluation of surface acid-base constants
relies on the extended Gutmann's equation suggested by Saint Flour and Papirer [18]:
- AHaAB = KA"DN + KD·AN where DN and AN are Gutmann's donor and acceptor
Surface Thennodynamics of Solid Materials 141
numbers for the probes [19], and KD and KA characterize the basicity and acidity of
the material, respectively. Evaluation of either Drago's or Gutmann's constants for e.g.
polymers and fibres is an important step in understanding the strength of the polymer-
fibre interface in composites [10].
4 CONCLUSION
Inverse gas chromatography (IGC) is a unique tool for the characterization of surface
thermodynamic properties of finely divided materials such as polymers, fibres and
fillers. These properties are very important for understanding and predicting their
adhesion properties among other uses. However, the problems involved in the
experimental conditions and the quantitative manipulation of data to obtain accurate
materials properties data appear to be of a higher order of difficulty in some cases.
KEYWORDS
inverse gas chromatography, surface properties, divided materials, London and Lewis
forces
REFERENCES
[1] J. R. Conder and C. L. Young, Physicochemical Measurement by Gas

Chromatography, (Wiley, Chichester, 1979)
[2] D. R. Lloyd, T. C. Ward and H. P. Schreiber, 'Inverse Gas Chromatography
Characterization of Polymers and Other Materials', ACS Symposium Series nO 391
(American Chemical Society, Washington D.C., 1989)
[3] Proceedings of the American Chemical Society, Division of Polymeric Materials
Science and Engineering, 70 (1994)
[4] E. F. Meyer. J. Chern. Ed., 57 (1980) 120
[5] A. J. Vukov and D. G. Gray in ref. 2, chap. 13
[6] B. Chabert, J. Chauchard, G. Edel and J. P. Soulier, Eur. Polym. Sci., 9 (1973) 993
[7] J. E. Oberholtzer and L. B. Rogers, Anal. Chern., 41 (1969) 1590
[8] P. Mukhopadhyay and H. P. Schreiber, Macromolecules, 26 (1993) 6391
[9] G. M. Dorris and D. G. Gray, J. Colloid. Interface Sci., 77 (1980) 353
[10] J. Schultz, L. Lavielle and C. Martin, J. Adhesion, 23 (1987) 45
[11] H. Balard and E. Papirer, Prog. Org. Coat., 22 (1993) 1
[12] M. M. Chehimi and E. Pigois-Landureau, J. Mater. Chern., 4 (1994) 741
[13] M. M. Chehimi, E. Pigois-Landureau and M. Delamar, J. Chim. Phys., 89 (1992)
1173
[14] M. Nardin, H. Balard and E. Papirer, Carbon, 28 (1990) 43
[15] E. Pigois-Landureau and M. M. Chehimi, J. Appl. Polym. Sci. 49 (1993) 183

[16] R. S. Drago, Structure and Bonding, 15 (1973) 73
[17] R. G. Pearson, J. Amer. Chern. Soc., 85 (1963) 3533
[18] C. Saint-Flour and E. Papirer, J. Colloid Interface Sci., 91 (1983) 69
[19] V. Gutmann, The Donor-Acceptor Approach to Molecular Interactions, Plenum
Press, New York, 1978
DIFFERENTIAL SCANNING CALORIMETRY (DSC)
AND TEMPERATURE DEPENDENCE OF THE
ELECTRICAL CONDUCTIVITY IN THE TERNARY
SYSTEM: WATER + CTAB + PHENOL
K. BUSSEROLLES, G. ROUX-DESGRANGES and A. H. ROUX
Laboratoire de Thermodynamique et Genie Chimique, UPRES A CNRS 6003

Universite Blaise Pascal, 63170 Aubiere, France
ABSTRACT
Specific interactions between cationic surfactant and peculiar solutes lead to the
formation of particular structures in dilute micellar solutions; for example gel-like or
viscoelastic structures can occur depending on the concentration of the solute and the
surfactant, and are very sensitive to the temperature. For the ternary system, water +
CTAB + phenol, DSC and the electrical conductivity measurements have been made as
a junction of temperature. The variation of the conductivity with temperature appeared
to be monotonous. However, for a given CTAB concentration, the relative variation of
conductivity when going from binary to ternary solutions, shows typical changes with
temperature and phenol concentration. These changes, characterizing different
structural domain, can be associated with the modifications of viscosity. Moreover DSC
analysis allows to confirm the existence of strong complexes between CTAB and phenol.
RESUME
Les interactions specifiques entre tensioactifs cationiques et certains solutes conduisent
a la formation de structures particulieres dans des solutions micellaires diluees. Ainsi,
par exemple, des structures viscoelastiques, voire des gels, tres sensibles a la
temperature, peuvent apparaitre dependant de la concentration de solute et en
tensioactif. Avec le systeme ternaire, eau+ CTAB + phenol, des mesures calorimetriques
et de conductivite electrique ont ete faites en fonction de la temperature. La variation de
conductivite avec la temperature semble etre monotone. Cependant pour une
concentration donnee en CTAB, la variation relative de conductivite entre une solution
binaire et une solution ternaire montre des changements typiques en fonction de la
temperature et de la concentration de phenol. Ces changements peuvent etre associes
avec des changements de viscosite caracterisant les differents domaines structuraux.
L 'analyse thermique semble conjirmer l'existence de complexe forts entre Ie CTAB et Ie
phenol
1 INTRODUCTION
Micellar solutions are obtained by addition of a surfactant to water. Depending on the

surfactant concentration, some structural changes occur leading to different shapes
and sizes of the micelles formed. The third component such as an hydrophobic
molecule is located preferentially in the organic heart of the micelles depending on its
hydrophilic-hydrophobic balance. With amphiphilic solutes, the partition between the
aqueous bulk phase and the micelles appears more complex:
• solute acts also on the interface of the micelle and favors micellar swelling
implying shape and size changes leading to microemulsions
• addition of slight amounts of particular solutes in aqueous micellar solutions is

accompanied by drastic changes of physical properties (viscoelasticity, gel
formation) as observed by Hoffmann et al. [1].
A cationic surfactant such as Cetyl Trimethyl Ammonium Bromide (CTAB) in

aqueous solution leads to gel formation in presence of phenol or some aromatic
additives [2]. Phenol is well known as a corrosive and highly toxic agent (RTECS #
S13325000). It is a protoplasmic poison damaging biological cells (so it was used as a
bactericide). In order to diminish its concentration in many specific applications or to
remove it from wastes, phenol should be trapped into gels in order to reduce toxic
effects on the environment.
2 COMPARISON BETWEEN PHENOL AND BENZENE
The transfer properties, from water to micellar solutions, of solutes kept at low and
fixed concentration reveal the structural changes occurring in solutions with the
surfactant concentration, the solute acting as a "molecular probe of its environment".
Heat capacities (ilC3) at 298 K have been determined with a differential flow
calorimeter of the Picker type [3]. Our previous data on micellar CTAB solutions
containing phenol [4] have been compared with those obtained with benzene by
Quirion and Desnoyers [5] using the same techniques. Heat capacities (Figure 1)
reveal complex behavior. Close to the critical micellar concentration (CMC) (9.10- 4
mol.kg- I), as well for benzene as for phenol almost no effect is observable. From
mCTAB=0.03 mol. kg-I, ilC3 between the two solutes diverges showing that phenol
seems sensitive to (or induces) another micellar transition. Clearly, 1t electron
interactions with ionic polar head groups of the micelle are not sufficient to explain
this phenomenon. This observation agrees well with the interpretation based on
enthalpic measurements given by Treiner at al. [6]; they indicate that even if the 1t
electron interactions exist, other predominant interactions are required to explain the
very negative value of the transfer enthalpy. At mCTAB=0.12 mol.kg- I, for both
Differential Scanning Calorimetry (DSC) 145
solutes, a hump appears related to the change of shape and size (spheres or rods to
cylinders) of micelles which is also observed in binary solutions [7] (Fig.1).
400,-----------------------------~
--
.-. 100
~
,!...
eo -200
~
~
~
-500
.,
A
=
Q
...
i
~Q
•
.~ gelated
.~
~OO;_~~-r--~_.--~_,--~--r_-r~
0.00 0.05 0.10 0.15 0.20 0.25
m (mol.kg- I )
CTAB
Figure 1 : Transfer heat capacities at 25°C
The modifications of the viscous appearance of solutions containing phenol is

approximately correlated to the heat capacity variations. Between mCTAB=0.03 and
0.10 mol.kg- l , a viscoelastic comportment appears. For higher concentrations, viscous
solutions (even gels) are noticed. Likewise, a large viscosity change is observed
visually along with the variation of temperature.
3 DSC MEASUREMENTS
In order to correlate the changes of viscous appearance with temperature to any

structural transition, we have performed DSC experiments. Heat capacity dependence
on temperature has been measured using a high sensitivity differential scanning
calorimeter MICRO-DSC (SETARAM, FRANCE). Since the properties of solutions
are very sensitive to the thermal history, a procedure is observed in order to obtain
reproducible data: solutions are introduced in the cell at high temperature (70°C), after
reaching the thermal equilibrium a cooling is performed at constant rate down to the
temperature of experimental beginning (43°C). A first scanning at the fixed low
cooling rate (0.04 Klmin.) is realized on cooling from 43 to - 7°C. The subsequent
scanning obtained for heating conditions is then recorded over the same range of
temperature and at the same absolute scanning rate.
The effect of the phenol concentration has been studied on micellar solutions of
meT AB=O.l 0 and 0.15 mol.kg- i , corresponding to the two kinds of viscous
comportment related to different micellar shape and size. The therrnograms obtained
show complex behavior with many peaks which have a similar evolution for the two
concentrations, peaks appearing or disappearing depending on phenol concentration.
Some typical curves are reported in Figure 2-a. The temperature location of the
maximum of the more important peaks is shown as a function of phenol concentration,
allowing one to distinguish three domains:
• in the first domain, peaks 1 and 2, well-defined on the binary solution, shift and
vanish rapidly with slight amounts of phenol,
• in the second domain, peak 3 appears, its intensity goes through a maximum and
vanishes at an intermediate range of phenol concentration,
• in the last domain, peak 4 grows with increasing phenol content, then broadens
and shifts.
Characteristic temperatures of peaks plotted according to the molar ratio

phenol/CTAB are in good agreement for the two CTAB concentrations studied
(Figure 2-b) : the existence of a complex between CTAB and phenol is well
evidenced. In the first domain, at room temperature around 25°C, solutions are fluid.
In the second domain, the viscoelastic trend increases up to the gel formation which
characterizes the third domain. In the latter domain, solutions initially gelated seem
less and less viscous with higher phenol ratio.
7000.,----------------,
Typical thermograms
Water + CTAB + Phenol
Peak 3 30
m CTAn= O.lmol.l{g-l
~6000
'? III l'hOIl (mol. kg-I)
E --0
~ - - - - - 0.037
20
0.050
0.100 G
;, 5000 ~
>< m CTA8 (mol. kg-I)
:::
.,t;: Peak
0.100 0.150 0.200
o
o
.
1 /\
•
;:; 4000
, ..
,, 2 ()
" Heating
3 0
•
"
3000+--.-,----.--,--.--,-..,---,---/
-10 o 10 20 30 2.5 3.0
teC)
a) b)
Figure 2 : DSC measurements

If DSC measurements allow one to define domains of phenol ratio corresponding to

the viscous appearance at 25°C, surprisingly the temperature location of any peak
does not agree with the temperature where the viscosity appearance seems to change
for a given solution.
4 CONDUCTIVITY AND MEASUREMENTS
The variations of viscosity as well as the formation of a complex between phenol and
CTAB should modify the ionic mobility. Therefore during temperature scanning in the
cooling mode the conductivity has been measured using an automatic RLC bridge
working at 1 kHz (GENERAL RADIO, USA) equipped with black platinum
electrodes. The conductivity perturbation \V due to the presence of phenol is obtained
at a given temperature from the resistance recorded on the ternary system
(W+CTAB+Phenol) and on the corresponding binary (W+CTAB) by the relation:
\V(T) = In[ Xtemary (T) / X binary (T)]
The effect of the phenol concentration has been studied on micellar solutions of
mCTAB=0.15, 0.10 and 0.05 mol.kg- 1.
The plot of \V, the logarithm of relative conductivity between ternary and the
corresponding binary system, as a function of the inverse of temperature (1 IT) shows
similar trends for mCTAB=0.15 and 0.10 mol.kg- 1. On Figure 3-a for the latter CTAB
concentration are represented the temperature scanning conductivity perturbations at
various phenol molalities. Some general observations can be drawn for the two
concentrations:
• for most of the curves obtained during the temperature scanning, \V goes through
a minimum (denoted T*), the amplitude of minimum and the T* value are
dependent on the phenol ratio; the T* value correlates well with the estimated
temperature where the change of viscous appearance is maximum for a given
ternary system
• at a fixed low temperature (30°), with low phenol concentrations, \V decreases as
the phenol quantity is increasing, while with higher phenol concentrations, \V
varies in an opposite way (at an intermediate phenol ratio, close to 1: I, the
minimum is reached).
• the plot of T* versus the phenol ratio (Figure 3-b) shows a broad maximum
between 1: 1 and 2: I for both CTAB compositions.
For the less concentrated CTAB system (0.05 mol.kg- 1), in Figure 3-c, \V(l/T) shows a
quite different behavior and three parts can be distinguished:
• at high temperatures, the relation of\V with liT presents slightly positive slopes
increasing with the phenol quantity
• at intermediate temperatures (from 50 to 20°), the slopes are very negative, the
amplitude of the variation of the property with temperature increases with the
phenol concentration; in this domain viscoelasticity appears, following a
mechanical agitation
• at low temperatures with increasing phenol ratio, \jf initially diminishes, then
reaches a minimum similar to the more concentrated CTAB solutions.
t (Oq
64 56 48 40 32 24 16 8
50
0.2
45
0.1
40
--;::.
" 0.0
e<: G 35
--0 0
-0
en -0.1 1-< 30
~
oS 25 ~ mCTA " = 0.15 mol.kg- 1
-0.2 ~ 111
T • m crAB = 0.1 mol.kg- l
b. 514
20
<> 211 m CTAB = 0.1 mol. kg- 1
•
-0.3
311
15
3.0E-3 3.2E-3 3.4E-3 3.6E-3
Iff (K- l ) nt phOH / DlCTAD
a) b)
65 55 45 35 25 15 5
0.2
m 1m
Phon crAD
()
"'
0.1 •
b.
112
111
~ 514
'4::.
<>
"
211
I'<:
X
----en0 0.0
• 514
..::5
E
-0.1
m CTAB = 0.05 mol.kg-1
2.9E-3 3.2E-3 3.5E-3
lIT (K -1)
c)
Figure 3 : Conductivity measurements

Conductivity variations at low temperatures present a mllllmum with phenol

concentration. Due to its acidic character phenol is partially ionized into phenoxide
ions. As amphiphilic molecules, phenol and mainlyphenoxide ion interact with CTAB
polar head groups at the interface of the micelle. This location had been shown by
Bunton et al. [8] using NMR measurements. A phenol-CTAB (1: 1) complex seems to
present the best efficiency for lowering conductivity. At high temperature,
conductivity increases with phenol concentration because thermal motion tends to
break long micelles into shorter micelles of greater mobility (in addition to the
lowering of viscosity).
5 CONCLUSION
The addition of phenol to CTAB micellar solutions induces a viscoelastic

comportment or gel formation which is related to the formation of a complex (1: 1)
between phenol and CTAB at the micellar interface. The weak acidic character of
phenol plays a more important role than rc-electrons in the interactions with surfactant
to explain the formation of this complex. The partial shielding of repulsive
electrostatic forces between polar head groups at the interface of the micelle by phenol
is a stabilizing factor favoring the lengthening of micelles. This effect is more efficient
when the surfactant concentration is large enough to promote long micelles (rod-like
or cylinder) in a binary W+CTAB. With a phenol ratio corresponding approximately
to complex composition, worm-like micelles are then formed. At high CTAB
concentration for the same phenol ratio, the repulsive interactions between worm-like
micelles are also reduced leading to entangled micelles responsible for the gel
formation. An excess of phenol and/or the thermal motion at elevated temperature,
induce the breaking of micelles and consequently reduce drastically the macroscopic
viscosity. Work is in progress to elucidate why DSC scanning experiments are not
directly sensitive to the structural change concomitant with the gel formation: some
observations of the optical properties (birefringence) of gels seem to indicate a very
low kinetic rate to reach a true thermodynamic equilibrium.
KEYWORDS
cationic surfactant, phenol, DSC, conductivity, complex formation
REFERENCES
[1] H. Hoffman, W. Ulbricht, J Colloid Interface Sci., 129, (1989), 388

[2] Y. Sakaiguchi, H. Hirata, Bull. Chem. Soc. Japan., 61, (1988), 2743
[3] P. Picker, P. A. Leduc, P. R. Philip, 1. E. Desnoyers, J Chem. Thermodyn., 3,
(1971), 631
[4] K. Busserolles, G. Roux-Desgranges, A.H. Roux, Thermochim. Acta, 49, (1995),

259
[5] F. Quirion, 1. E. Desnoyers, J Colloid Interface Sci., 112, (1986), 565
[6] C. Treiner, A. K. Chattopadhyay, R. Bury, J Colloid Interface Sci, 104, (1985),
569
[6] s. Backlund, H. Hoiland, O. 1. Kvammen, E. Ljosland, Acta Chern. Scand, A36,
(1982), 698
[8] C. A. Bunton, C. P. Cowell, J Colloid Interface Sci., 122, (1988), 154
THERMODYNAMIC MODELS FOR MONITORING
DEOXIDATION TREATMENTS AND CONTROLLING
INCLUSIONS IN STEELS
HENRI GAYE, CHRISTIAN GATELLIER and JEAN

LEHMANN
IRSID, 57280 Maizieres-les-Metz, France.
ABSTRACT
A multiphase equilibrium calculation, based on IRSID's statistical thermodynamics

slag model, is used to predict the composition of endogeneous oxide and sulphide
inclusions precipitated as a result of the deoxidation treatment, during metal
solidification, or due to late reoxidations. This evaluation shows that the composition
of inclusions is strongly affected by the content of trace elements (Ca, Mg and Al) in
the steel. On the basis of these models, the monitoring of inclusion control by calcium
treatment (Al-killed steels), or slag treatment (semi-killed steels) will be discussed.
RESUME
Un programme de calcul d'equilibre polyphase, base sur Ie modele de
thermodynamique statistique des laitiers developpe a I'IRSID est utilise pour predire
la composition des inclusions d'oxydes et de suljitres precipitant dans ['acier a la suite
du traitement de desoxydation, pendant la solidification du metal, ou du fait de
reoxydations a la coulee. Cette evaluation indique que la composition inclusionnaire
est imposee par la teneur du metal en elements traces (Ca, Mg et AI). L'optimisation
du contr6le inclusionnaire par traitement calcium (aciers calmes AI) ou traitement
metal-laitier en poche (aciers faiblement desoxydes) est discutee sur la base de ces
modeles.
1 INTRODUCTION
The traditional role of slag in iron- and steel-making processes is to eliminate the
gangue of the charged materials, and to refine the metal, as major contaminants of the
steel can only be removed via the slag phase (S, P, ... ). Another function has more
recently been fully exploited, in the constant drive for higher purity and better and
better controlled steel products: the fine adjustment of steel compOSItIOn by slag
treatment in ladle metallurgy in order to promote an adequate inclusionary state. In
recent years, the optimization of high temperature metal-slag-gas reactions in order to
improve metal purity, and the control of the precipitation of en dog eneo us oxide and
sulphide inclusions in steels have significantly progressed through the use of
thermodynamic models of oxide systems. The type of thermodynamic information
needed concerns slag phase diagrams (definition of liquid domains for adequate
operation of the reactors, crystallization behavior of oxide inclusions) and component
activities (or related quantities, for instance slag-metal equilibrium partition ratios,
sulphide capacity, ... ).
In order to represent industrial processes, thermodynamic models must therefore

describe multicomponent systems, as the metal quality will very often be conditioned
by minor components of the slag. They should also be reasonably time efficient since
the values of slag properties have to be reactualized a large number of times during
the calculation, when used in kinetic reaction models or in multi phase equilibrium
codes.
2 SLAG MODELING ApPROACHES
The main slag systems of interest are summarized in Figure 1, showing the diversity
of components and composition ranges.
CaO - Si02 - AI20a -

Na20 -CaF2 ...
tt~~~*;f~R.r~j~8~_~}~t@!if*
~%l gjii'~Ji:ta.T6~:9.~:i*1~~$@:l; MnO - AI20a - Si0 2 •..
CaO - Si0 2 - AI 20 a - MgO ... CaO - AI20a - Si02 .•.
Al2oa. Si02 •...
Ume aluminates
:@61fs~~Jfu]H!p$~,~p~~t[@}
CaO - Si02 - P20S - FeO ...
CaO AI20a
FeO x
(MnO) L-______~~~--------~ (MnO)
(MgO)
(Na20) (Cr20a)
(CaF2)
Figure 1: Main classes of iron and steelmaking slags

Thermodynamic Models for Monitoring Deoxidation Treatments 153
Until the development of statistical thermodynamics models, one had to rely on rather
crude correlations of slag thermodynamic properties as a function of temperature and
composition. Among the most successful of these methods is Flood-Grjotheim's
model and its various adaptations [1,2] whose domain of application, although very
important industrially, is limited to extremely basic refining slags. Correlations of
thermodynamic properties (for instance, sulphide capacity) in terms of « optical
basicity » were recently proposed [3]. Although they can be useful for limited
composition ranges in some specific systems, their extrapolation over domains in
which they have not been fitted can lead to considerable errors (typically, several
orders of magnitude). Indeed, as illustrated in Figure 2, the slag properties may
change drastically over very limited composition ranges, when going from the domain
of basic slags (CaO- rich slags) to that of acid slags (Si02- rich slags). In the pseudo-
binary system considered, the activity coefficient of Si02 increases sharply in the 0 to
25% Si02 domain and keeps a value of around I at higher silica contents, whereas the
sulphur equilibrium partition coefficient decreases from about 3000 to 1 in the basic
domain and is well below unity in the acid domain. These sharp variations of
thermodynamic properties also explain that regular solution models [4], or polynomial
representations in terms of contents of oxide components should be used cautiously.
log Y5i02 log (5)/[5]

2.0 r----.----.,----~---....., 4.0
0.01-4.---+---=--I----+--!---1 2.0
-2.0 I-----;~--"Id_---_+---+---__I 0.0
-4.0 ~---~---~--.....;;:::::;",_--..-I-2.0
o 25 50 75 100
% 5i02
Figure 2: Variation ofSi02 activity coefficient and S partition coefficient at

equilibrium with liquid steel containing 0.3% Si, in pseudo-binary 60%CaO-
40%Ah03/Si02 at 1600°C
The pioneering paper of Toop and Samis [5], focussing on an equilibrium between
three oxygen configurations (free oxygen 0 2-, singly bonded 0- and doubly bonded
0 0 to Si), and a model based on the polymerization of silicate tetrahedra proposed by
Masson [6] have, in their time, stimulated considerable interest inthe development of
structurally-based models of silicate melts. Yet, no real breakthrough has been
achieved to this day to represent, with these polymerization models, the

thermodynamic properties of multicomponent slag systems.
A novel approach using a concept of oxygen and cation sublattices was introduced in
the early 1970's by Yokokawa and Niwa [7] and Kapoor and Frohberg, [8], with,
however, no applications beyond a few ternary systems. This approach was then
generalized at IRSID to represent the properties (component activities and phase
diagrams) of systems containing large numbers of oxide components [9], and was
later on extended to oxysulphide and fluoride melts [10].
In this model, the liquid slag is represented using an anionic sublattice filled with the
anions, oxygen, sulphur and fluorine and a cationic sub lattice, filled with the different
cations in decreasing order of their charges. The structure is then described in terms
of cells (i-A-j), composed of a central anion (A) surrounded by two cations (i and j).
Starting from this microscopic description, the expression of the degeneracy of the
system is written, using the quasi-chemical approximation proposed by Guggenheim
[11]. Two types of parameters are used to evaluate the energy ofthe system:
- WijA associated with the formation of asymmetric cells from the corresponding
symmetric ones according to the reaction 112 (i-A-i) + 112 (j-A-j) = (i-A-j), and WjA ,
representing the relative stabilities of the A and oxygen symmetric cells, according to
the reaction (i-O-i) + A = (i-A-i) + 0, in which a convenient reference state for
°
elements and A is the 1% solution in liquid iron.
- EijA, representing the interaction between cells (i-A-i) and (i-A-j) and EijAB the
interaction between (i-A-i) and (i-B-i).
Thus, for a system composed of a anions and c cations, ac(c-I)+2(a-l)c parameters are
needed. They are binary parameters and have, for all the systems evaluated so far,
been assumed to be temperature independent. Although all the model parameters are
binary parameters, it is often necessary to assess them on systems containing more
than two components. This can be due to the fact that binary data are lacking or not
accurate enough, in particular because the liquid domain of binary systems of interest
is often too narrow in the relevant domain of temperature. In order to fit the model
parameters on multicomponent data, a computer code has been written, based on a
least squares technique. This code can handle various types of data:
• slag component activities,

• various quantities directly derived from the slag component activities, such as
sulphur capacity or slag/metal equilibrium partition coefficients,
• phase diagrams. Data on phase diagrams can be expressed as chemical potentials
of stoichiometric compounds, but also in terms of the position of the liquidus
line. In this case, the regression is no longer based on chemical potential data but
on composition variables data.
Thennodynamic Models for Monitoring Deoxidation Treatments 155
To the liquid phase model are associated the values of energy of formation of the
various stoichiometric compounds that can be formed at lower temperature, as well as
solution models for various solid solutions (spinels, olivine, ... ). Some of these values
have been adapted in order to obtain a best fit of the phase diagrams, while remaining
within the range of uncertainty of the experimentally determined thermochemical data.
At present, the model has been validated for the system: Si02 - P205 - Cr203 - AI203
- Fe203 - CrO - FeO - MnO - MgO - CaO - S and work is in progress for systems
containing, in addition, CaF2, Na20 and Ti oxides.
3 MULTIPHASE EQUILIBRIUM CALCULATIONS
The principle used for the calculation of the equilibrium inclusions composition is
shown in Figure 3. It rests on an original procedure of multiphase equilibrium
calculation that, from the global analysis, determines the composition of liquid metal
and the compositions and amounts of oxides, sulphides (and also nitrides and
carbides) that have been precipitated at a given temperature. This calculation
procedure, based on the minimization of the free energy of the system, is especially
adapted to the situation to be described (a few ppm of precipitates in the metallic
phase). It calculates the equilibrium in the presence of completely liquid, partially or
completely solid oxides (taking into account solid solutions). It is much faster and
more reliable than the direct insertion of the slag model into classical codes of
multiphase equilibrium calculations such as SOLGASMIX [12].
Program for the

calculation of
multiphase equilibria
Figure 3: Procedure for the calculation of inclusion composition

(in liquid metal or during solidification)
Starting with the global metal analysis (samples taken during ladle or tundish
treatment, or from the final product), this calculation can be done not only at treatment
temperature but also during, subsequent temperature evolution, for example, during
cooling and solidification of the steel. In this last situation, an original method of
combining the microsegregation equations for elements dissolved in liquid metal
(Clyne-Kurz equations), with or without diffusion in solid metal, and the equilibrium
conditions between liquid steel and oxide, sulphide, (and also nitride and carbide)
inclusions has been developed. The calculations also give the liquidus temperature of
oxide inclusions and their crystallization path during cooling,. Thus it is possible to
trace the history of the origin of endogeneo us inclusions. For metal-slag equilibrium, a
similar program calculates the complete composition of liquid metal in equilibrium
with the slag. It uses the value of oxygen potential calculated for the relevant
element/oxide couples (for instance Si and/or Mn in the case of semi-killed steels),
and deduces the transfers that will occur between slag and metal, especially for trace
elements: Ca, Mg and AI.
4 EVALUATION OF INCLUSION COMPOSITIONS
4.1 Calcium-treated Aluminum-killed steels:
A validation of the model for Ca-treated AI-killed steels is supplied by the example
shown in Figure 4 [13]. For these grades, the equilibrium dissolved oxygen content in
liquid steel is very small, so that the large majority of the endogeneous inclusions
consist of deoxidation products that were already present in the ladle. Their
composition has been estimated from the analysis of a large number of samples taken
in various heats during elaboration and on the final product. The inclusion analysis
was compared to analyses obtained by microprobe, or from the extracted residue
obtained by nonaqueous electrolytic dissolution of the metallic matrix. The
comparison of calculated and analyzed amounts of aluminum fixed in the oxides is
shown in Figure 3a, for steel grades with variable sulphur contents (between 0.03%
and 0.08%) and total AI contents ranging from 100 to 300 ppm. The agreement is
very satisfactory, with deviations between the two values that do not exceed 5 ppm.
The same is true for calcium (Figure 3b), an element for which it is possible to
determine quantitatively, by analysis and by calculation, the amounts fixed in the
oxides and in the sulphides. For these steel grades, the calculation model is commonly
used to optimize calcium treatments and for the purpose of product testing.
Alox analyzed (ppm) Catot Ca ox analyzed (ppm)

, 40 ,
,,
40
, ,, ,
9' ,,
8,'rP ~,'
,,
'0
c~
I,-3 ,,
K·
20 20
oyi''' y}V
,,
00.08%$
, .0.03%5
,,
o o
o 20 40 o 20 40
Alox calculated (ppm) Ca ox calculated (ppm)
Figure 4: Comparison of calculated and analyzed inclusion compositions in Ca-

treated AI-killed steels
Thermodynamic Models for Monitoring Deoxidation Treatments 157
4.2 Semi-killed steels
The model has also been used to estimate the composition of the inclusion population
of steels with low-aluminum contents, that is Si-Mn deoxidized steels generally used
for bar and wire products [14]. For these steel grades, the objective is to obtain oxide
inclusions that will remain glassy and plastic during metal shaping operations, and to
avoid the formation of hard phases such as alumina or spinels. The example presented
concerns a continuously cast, high carbon steel, whose composition in main
deoxidizers is 0.7% C, 1% Mn and 0.35% Si. To be able to make a valid diagnosis, it
is necessary to have reliable analytical values for the total oxygen content and for the
traces of oxidizable elements (AI, Ca, Mg, ... ) that will enter the inclusions at one stage
or another of elaboration. For the considered heat, chemical analyses were made by
the Unimetal Recherche laboratory on an as-cast sample that was also used for
micrographic examinations and microprobe analyses (quantitative microprobe
analysis of about fifty inclusions).
Deoxidation Solidification Reoxidation

Computed Analysis Computed Analysis Computed Analysis
Matrix
% Si02 31 32 - 36 40 35 - 39 39 37 - 40
(65) (52-55)
% A1203 25 26 - 33 35 20 - 26 - <4
(18) (5 - 8)
%CaO 33 18 - 30 - - - -
%MnO 6 3-8 25 30 - 37 61 52 - 59
(19) (25-35)
%MgO 5 2-5 - - -
Precipitates Spinel Spinel Alumina Alumina Silica Silica
(Mg- (Mg-
Mn)O Mn)O
AI203 AI203
(-) composition of inclusions formed at the end of solidification

Table 1: Composition of inclusions precipitated at various stages of elaboration
and remaining in the final product. Comparison between calculation and micro-
analyses.
Steel composition: 16 ppm 0- 8 ppm AI- 3 ppm Ca- 0.4 ppm Mg
The detail of the calculation is given in Table I, showing a very good agreement
between calculated and analyzed compositions. The oxide inclusions population can
be classified into three categories:
• unfloated deoxidation products composed essentially of Si02, Ah03 and

CaO and containing small amounts of MgO and MnO. They were liquid when
precipitated and, consequently, have spherical shapes in the as-cast product.
During cooling, a (Mg-Mn)O-AI203 spinel phase crystallized in some of them,
the matrix remaining homogeneous and glassy with a composition only slightly
modified by this crystallization. Once these inclusions have precipitated, the Ca
and Mg contents remaining in solution in the liquid metal are practically zero.
The ones that will form later will consequently have a composition in the Si02-
MnO-Ah03 system. They represent nearly 70% of the residual inclusions (11
ppm of oxygen out of the 16 ppm analysed) and are globally distributed among
two large classes.
• inclusions formed during metal solidification. The ones precipitated at the

beginning of solidification are located in the alumina primary phase field, and
alumina crystals appear in some of them during cooling. During the later stages of
solidification, as a result of segregation, their Si02 content increases, and
inclusions close to silica saturation may be formed.
• inclusions resulting from late reoxidations by the atmosphere, essentially

composed ofSi02 and MnO with only traces of Ah03.
To avoid the formation of harmful alumina and spinel phases, Al contents not in
excess of 5 ppm in liquid steel must be obtained.
5 CONTROL OF INCLUSIONS IN SEMI-KILLED STEELS BY SLAG

TREATMENT
The only practical method for decreasing the liquid metal contents in trace elements
(AI, Ca, Mg) below the levels that would result in the precipitation of deleterious
inclusions consists in equilibrating the metal with a ladle slag of adequate
composition. Figure 5 illustrates the selection of optimal slag compositions in the
CaO-AI203-Si02 system. In order not to exceed an aluminum content of 5 ppm while
keeping a metal that is as little oxidized as possible, it is necessary to aim for a slag
composition corresponding to a Si02/CaO ratio of about 0.9 with Al203 contents that
do not exceed 10%. For actual industrial slags containing, in addition, MgO and MnO,
the calculations, as well as industrial experience show that an increase in the MgO
content of the slag (and generally an increase in slag basicity) greatly increases the
residual aluminum content. An increase in treatment temperature has a relatively
smaller effect on the aluminum content, but results in a higher dissolved oxygen
content and therefore in a higher inclusion content. It is therefore advisable to perform
this ladle stirring at the lowest temperature compatible with adequate casting
conditions. Similar metal-slag transfer calculations can be done for calcium and
magnesium. The possibility that these elements will strongly affect metal quality, for
Thennodynamic Models for Monitoring Deoxidation Treatments 159
these semi-killed steel grades, is particularly acute for treatments perfonned in ladles
with magnesia or dolomite lining. Considering their low solubility in liquid steel and
their high vapor pressure at these temperatures, the amounts of Ca and Mg remaining
in solution are generally lower than the ones corresponding to the metal-slag
equilibrium. The calculation models can, however, be used to evaluate the risks of
reaching too high Ca or Mg contents in the metal. These risks are especially marked,
even when the alumina content of the slag is low enough to avoid the precipitation of
solid Ca-aluminates or spinels, when the slag's basicity is too high (leading to the
precipitation of 2CaO-Si02 inclusions), or when its MgO content is too high (leading
to the precipitation of2MgO-Si02 inclusions).
Ladle slag at 1550· C
5i02
Inclusions at 1470· C
0.35 '1'.5i
1.0%Mn
Figure 5: Influence of slag composition during ladle treatment (1550 0c) on the
composition of inclusions precipating at the beginning of solidification (1470 0c) for a
high carbon steel grade
6 CONCLUSION
In aluminum-killed steels, calcium treated or not, the endogeneous oxide inclusion

population is relatively homogeneous. It is approximately an image oftheinclusionary
state in the tundish.
In semi-killed steels, on the contrary, this population is highly heterogeneous. It is a

juxtaposition of residual deoxidation inclusions (silico-aluminates of Ca and Mg), of
inclusions precipitating during metal solidification or due to reoxidations (Mn silico-
aluminates). If highly oxidizable elements (AI, Ca, Mg) are not maintained at low
enough levels through treatment with a ladle slag of adequate composition, harmful
phases (spinel, alumina, possibly di-calcium or di-magnesium silicates) can appear at
the time of inclusion precipitation or crystallize during cooling of initially liquid
inclusions.
The multiphase-equilibria calculation based on the IRSID slag model offers an

accurate description of the various classes of inclusions and is an efficient tool for
guiding the choice of optimal ladle slag composition. These calculations rely on a very
.accurate knowledge of the global metal analysis, especially the 0, AI, Ca and Mg
contents. In addition, confrontation with microanalysis of inclusions must be done on
the as-cast product, since the multiphase inclusions may be very highly deformed and
their original phases dissociated during rolling.
KEYWORDS
slag model, multiple equilibrium, AI, killed steels, Semi-killed steels
REFERENCES
[1] H. Flood and K Grjotheim: J.I.S.I., 171, (1952),. 64.

[2] H. Gaye, J.e. Grosjean, P.V. Riboud: in Proc. Conf. "Physical chemistry and
steelmaking" Societe Frans:aise de Metallurgie, Versailles, (1978).
[3] D.J. Sosinsky, 1.0. Sommerville: Metal!. Trans. B, 17 B, (1986), 331.
[4] S. Ban-ya : Proc. of the 4th Int. Conf. on Molten Slags and Fluxes, The Iron
and Steel Institute of Japan, (1992), 8.
[5] G.W. Toop, C.S.Samis: Trans. TMS-AIME, 224, (1962), 224.
[6] C.R. Masson: Proc. Roy. Soc., A 287, (1965),201.
[7] T. Yokokawa, K. Niwa : Trans. Japan Inst. Metals, 10, (1969), 3 and 81.
[8] M.L. Kapoor, M.G. Frohberg : in "Chemical metallurgy of iron and steel", The
Iron and Steel Institute, London, (1973), 17.
[9] H. Gaye, J. Welfringer : Proc. of the 2nd Int. Symp. on "Metallurgical slags
and fluxes", The Met. Soc. of AIME, Warrendale, PA, (1984), 357.
[10] 1. Lehmann, H. Gaye : Rev. Int. Hautes Temper. Refract., Fr., 28, (1992-
1993), 81.
[11] E.A. Guggenheim: "Mixtures", Clarendon Press, Oxford, (1952), 270.
[12] W. Yamada, T. Matsumiya, A. Ito : Proc.of the 6th IISC, Nagoya, (1990),.
618.
[13] H. Gaye, e. Gatellier, M. Nadif, P.V. Riboud, J. Saleil, M. Faral : Rev.
Metallurgie-CIT, 84, N°ll, (1987), 759.
[14] e. Gatellier, H. Gaye, 1. Lehmann, 1. Bellot, M. Monce! : Rev. Metallurgie-
CIT, 89, N°5, (1992), 361.
A TECHNIQUE FOR STUDYING THE PARTICLE
IMPACT PHENOMENA IN PLASMA SPRAYING
A. VARDELLE, M. VARDELLE and P. FAUCHAIS
Laboratoire de Materiaux Ceramiques et Traitements de Surface, URA 320-

CNRS - Equipe Plasma, Laser, Materiaux, 123 Avenue Albert Thomas, 87060
Limoges, Cedex, France
ABSTRACT
In a plasma spray process coatings are built up by the impact of many individual
particles on a solid substrate. The physical properties of these coatings depend on
their specific lamellar microstructure which is controlled by the parameters of the
impacting particles and the parameters of the substrate. A better understanding of the
phenomena involved during the flattening and the cooling of the droplets on the
substrate may help to control deposit microstructure. Therefore an experimental
device has been developed to investigate the particle impact and connect the
observations with the spraying conditions.
RESUME
Dans une technique de projection de plasma, Ie depot est construit par l'empilement de
nombreuses particules qui sont projetees, if grande vitesse et dans un etat fondu ou
semi-fondu, sur la piece if recouvrir. Les proprietes de ces revetements dependent de
leur microstructure qui est controtee d'une part, par les parametres des particules au
moment de l'impact et d'autre part, par les parametres du substrat. Pour avoir un
meilleur controle des proprietes des depots et de leur reproductibilite, nous avons
developpe un dispositij experimental permettant d'etudier !'etalement et Ie
refroidissement des gouttes sur Ie substrat et de relier les resultats obtenus aux
conditions de projection.
1 INTRODUCTION
In plasma spraying, finely divided materials are deposited in a molten or semi-molten

form on a prepared substrate. Almost any material, including high melting temperature
ceramics, can be efficiently sprayed on a variety of materials and structures. The use
of this technology has been extended to a wide range of situations, many of which
demand close control over deposit properties [1].
Within the framework of the European COST 501 programme ("Advanced Materials
for power engineering components"; work package 15 : "advanced coating technology
for gas turbines "), research efforts have been focussed on the improvement of thermal
barrier coatings which are plasma sprayed on different turbine components such as
vanes and blades ... [2]. The use of 7% yttria-stabilized zirconia coatings provides up
to now, the best results in higher turbine inlet temperature, longer service life of the
metallic substrates and lower air flow rate for turbine cooling.
The phenomena involved in the spreading and freezing of the impacting droplets and
the interaction between the resulting splats and between the splats and the substrate,
depend both on the particle parameters (velocity, size, molten state) and the substrate
parameters (temperature, nature, roughness). Therefore, a better understanding of the
impact phenomena and their effect on the properties of the coating, may help to
establish predictive relationships between process parameters and deposit
performance [3].
To investigate the particle impact and the splat formation, an experimental device
comprising two high-speed pyrometers has been developed and is described in this
paper.
2 DESCRIPTION OF THE EXPERIMENTAL SET-UP
The surface temperature of a single particle in flight and its thermal history upon
impact and cooling on a substrate are determined from measurements of the thermal
radiation emitted by the particle by means of two custom-built two-wavelength
pyrometers. One pyrometer (P 1) is focused 1.8 mm in front of the substrate and the
other (P2) is focused on the substrate (Figure 1). An optical sensor (CS), focused at
the same point as the first pyrometer, allows one to reduce the measuring volume for
in-flight measurements and to provide coincident triggering. Each pyrometer consists
of an f=80 mm achromatic lens operating at an optical magnification of 1.3 for PI and
2.4 for P2, a 200 ,.un core Corning Glass silica fiber, a monochromator (HIO IR Jobin-
Yvon, 600 grooves/mm) and two photomultipliers (Hamamatsu R928).
The lenses image one end ofthe optical fibers either in the plasma jet (pyrometer PI)
or on the substrate surface (pyrometer P2). For the in-flight measurement the cross-
section of the measuring volume is approximately 0.05 mm 2 while the monitored area
on the substrate is about 0.25 mm 2 . The opposite ends of the optical fibers are linked
to the entrance of the monochromators. The output signals, filtered respectively at
632.8 and 832.8 nm, are transmitted through two 600 11m core Corning Glass silica
optical fibers to the photo-multipliers. For a monochromator resolution of 160 Almm
The Impact Phenomena in Plasma Spraying 163
and an optical fiber of 600 J.1m diameter, the spectral bandwidth is of 96 A. The
coincidence sensor head contains an f=80 mm achromatic lens operating at an optical
magnification of 1.3 which images the end of a 200 J.1m core silica optical fiber in the
plasma jet (in the measuring volume defined by PI). The opposite end of this optical
fiber is linked to a photomultiplier (Hamamatsu R928). The three optical sensors (PI,
P2 and CS) are aligned using a He-Ne laser beam.
x= 1. 8 mm
Detecto r
Ou tput (I)
Velocit y+Size
(X/I) (I)
Ti me
Figure 1: Schematic diagram of the experimental set-up used to monitor particle
impact.
The output signals of the photomultipliers are amplified by linear home-made

amplifiers and then led to a digital oscilloscope (Lecroy 9424). The time response of
the two photomultipliers and the following electronics is approximately 50 ns. The
recording of the signals is triggered by a coincidence signal when a particle is detected
simultaneously by the first pyrometer and the coincidence sensor. The coincidence
line is made up of two timing single channel analyzers (Ortec 551) fed with the output
signals of CS and PI sensors, and a universal coincidence unit (Ortec 418 A). The
output of this unit provides a logical signal which is used as a gating signal to the
oscilloscope.
The surface temperature of the in-flight particle is derived after calibration [4] from
the ratio of the detector outputs of the first pyrometer by assuming that the particle
behaves as a gray body. The temperature evolution of the impacting particle is also
computed from the ratio of the two photodetector outputs of the second pyrometer up
to the mean time required for the signals to decrease by one order of magnitude from
their maximum value; this corresponds to a temperature drop of about 700-900 dc.
After this point the temperature evolution is computed from the 832.8 nm signal on
the basis ofthe evolution of material emittance with temperature (generally known for
the solid material). This technique avoids using the ratio of two nearly equal signal
values and provides a better estimate of temperature changes below a certain level.
The precision of particle temperature measurements depends essentially on the

knowledge of the emissivity of the material and on the accuracy of the calibration. It is
estimated to be of the order of 10% for in-flight measurements. The accuracy is lower
when measuring the particle temperature at the moment of and immediately after the
impact on the substrate surface. This is due to the stray light scattered and reflected by
the substrate depending on the plasma conditions (e.g. arc current, gas flow rate, etc ... )
and on the substrate roughness and degree of oxidation. In most cases the temperature
of the impacting particle is equal within 10% to that measured in flight 1.8 mm above,
but sometimes the difference approaches 20%.
Other data obtained from the measurement system are the velocity and the diameter of
the particle at impact as well as the diameter of the resulting splat. The particle
velocity is deduced from the time of flight of a particle between the two measuring
volumes as determined from the time delay between the 832.8nm numerical signals.
Measurement errors for particle velocity may arise mainly from readings of the
distance between the two measuring volumes and of the time delay between the two
signals. The estimated accuracy of the measurement is better than 10%.
The diameter of the impacting particle and the diameter of the corresponding lamella
are determined, after calibration, from the maxima of the amplitudes of detector
output signals. This calibration consists of recording by means of one of the two
pyrometers, the amplitude of the light signal emitted by the spherical electrode of a
tungsten arc lamp viewed through pinholes of different sizes in a sheet placed in front
of the lamp electrode. Thus, different emission areas are simulated. The accuracy of
the measurement of particle and splat size is linked to the accuracy of the temperature
measurement and the precision of the calibration. It is estimated to be of the order of
15%.
It should be noted that the results obtained with the system are generally scattered.
This scattering is explained partly by the measurement errors (calibration procedure,
reflection of plasma light on the substrate, deviation from gray body behavior of the
radiating surface, presence of temperature gradients at the splat surface, etc ... ) and
partly by the distributions of velocity, size and temperature of the impinging particles.
The large velocity and temperature gradients within the plasma jet and the
distributions of particle size and injection velocity result in a range of trajectories and
thermal histories for injected particles. The splats collected at a given point of the
substrate are thus characterized by distributions of molten state, diameter and velocity.
The data obtained with the pyrometric device, under various experimental conditions,
have been compared with those obtained by other diagnostic methods (laser
velocimetry and high-speed pyrometry for the measurement of particle velocity and
temperature respectively, image analysis for determining particle and splat size
distributions). The results obtained from two different techniques for the measurement
of a given parameter (size, temperature or velocity) were in good agreement: the
difference between the mean values was less than 10% [4].
3 EXAMPLE OF SIGNALS COLLECTED BY THE PYROMETRIC

DEVICE
Figure 2 shows an example of signals recorded when a particle crosses the first
measuring volume and then impinges on the steel substrate. Some differences in
signal shape and intensity are apparent between the first and the second couple of
pulses. The light signals collected from the in-flight particle are almost symmetrical as
the particle crosses the measuring volume at a constant velocity. Their amplitudes are
one order of magnitude lower than the amplitudes of signals collected at particle
impact.
Detector Outputs(V)
0.6r--------------------r----------~
0.5
0.4 Signals collected during Impact
0.3
0.2
0.1
O~----~----~----~~~.J
o 10 20 30 40
Time (j1s)
Figure 2: Example of signals collected in flight and at impact.
The rise of the signals detected during the flattening process is explained by the rapid
increase of the radiating surface as the molten particle spreads on the surface. These
signals exhibit first a steep rise corresponding to the spreading of the molten particle
on the target, and then a longer decrease corresponding to the cooling of the lamella
principally by conduction to the substrate. However, the occurrence of the maximum

intensity corresponds to the termination of the spreading process only if no significant
amount of cooling or solidification has taken place before spreading is completed [5].
The flattening duration is computed from the rise time ofthe signals at impact.
Thus, the computed time corresponds to the real flattening time only if the cooling rate
is not too high. On the other hand, the splat size determined from the maximum
amplitude of signal intensity may be underestimated when the surface temperature
drops during the flattening process.
4 EXAMPLE OF RESULTS FOR THE INVESTIGATION OF SPLAT

FORMATION: FLATTENING DEGREE
The flattening degree z is defined as the ratio of the diameter of the resulting splat to
the diameter of the impinging particle. The dependence of the flattening degree on
particle parameters and substrate temperature for zirconia particles plasma-sprayed on
steel substrates with low roughness (Ra = 0.1 - 0.4 !lm), is shown in Table 1.
Substrate Mean value Flattening degree dependence of particle parameters

of flattening
degree
TO Roughness Particle Change in Multiplicative Particle
parameters flattening coefficeint parameter
degree range
-75°C 0.4 !lm 3.4 Temperature
Velocity i - 2.3
- 4.5
2500-4000K
100-300m/s
-200°C
300°C
0.1 !lm
0.4 !lm
4.7
2.9
Temperature
Velocity
Temperature
i -1.1
- 1.2
-2
2500-4000K
100-300m/s
2500-4000K
oxidized Velocity + -2.1 100-300m/s
Table 1 shows that increasing the impact velocity and/or the temperature of the
droplets leads to a larger final splat and a higher flattening degree. This effect is less
pronounced when the substrate temperature is higher than 200°C. In that case, the
mean flattening degree is 40% greater than that for droplets impinging on a substrate
maintained kept at 75°C but its variation with particle velocity and temperature is
relatively low. When the substrate surface is oxidized, the flattening degree is
decreased. This can be attributed to the modification of the surface roughness and of
the wetting of the flowing liquid on the substrate (which could result in part of the
liquid flowing away). It was also found that the flattening degree increases with
particle size except for the larger impacting droplets which can be underheated or
undermolten.
For completely molten particles, the dependence of their impact parameters on their
flattening can be expressed as a function of Reynolds number. The results of
experiments carried out on droplets impinging on a smooth surface held at 200°C
show a reasonable agreement between the experimental values and those predicted by
the well-known Madejski's correlation [6] :
s= 1.2941 ReO.2
10.--------------------------------------,
a> 8f--
a>
....
0
0')
a>
Cl 61- o 0 ___
0')
t: &~9I,'io O~\--
~W'?Jo((jfJ <J)
t: 41-
a>
......
......
CIS Madejski's Correlation
U. 2
OL-~~--~~~~--~~------~-L------~~
200 600 1000 1400 1800

Reynolds Number
Figure 3: Degree of flattening as a function of Reynolds number.
5 CONCLUSION
A measurement system has been developed for monitoring the impact and cooling of
plasma-sprayed particles on a substrate. This device, consisting of two high-speed
two-color pyrometers, was used to study the flattening of a particle and the freezing of
the resulting splat as a function of particle parameters (size, velocity, temperature) at
impact. The technique has proved to be a useful tool for a better understanding of
particle-substrate interactions.
Similar investigations with different materials may help to validate mathematical

models of particle impingement during plasma spraying and coating growth, and to
relate the coating microstructure and physical properties to the process parameters.
ACKNOWLEDGMENTS
This work is part of a program supported by the Commission of the European

Communities under the Cost 501 action and Brite-Euram contract.
The authors would like to thank Professor N.J. THEMELIS of Columbia University,
NYC for fruitful discussions.
KEYWORDS
plasma spray, particles, spraying, coating, cooling process, microstructure
REFERENCES
[1] J.H. Zaat, Thermal Spraying, Ann. Rev. Mater. Sci., 13, (1983), 9-42.
[2] COST 501, Rounds I, II, III, programmes work package 15 : Advanced
Coating Technology for Gas Turbines, M. Malik (Lufthansa, Hamburg)
coordinator.
[3] Berndt, C.C., et aI., Current Problems in Plasma Spray Processing, Journal of
Thermal Spray Technology, 1, (1992), 341-356.
[4] M. Vardelle, A. Vardelle, P. Fauchais, C. Moreau, Pyrometer system for
monitoring the pmticle impact on a substrate during a plasma spray process,
Measurement Science Technology, 5, (1994), 205-212.
[5] C. Moreau, P. Cielo, M. Lamontagne, Flattening and solidification of thermally
sprayed particles, Journal of Thermal Spray Technology, 1, (1992), 317-323.
[6] 1. Madej ski, Solidification of droplets on a cold surface, Int. J. Heat Mass
Transfer, 2, (1976), 1009-1013
THE ApPLICATION OF THERMODYNAMICS TO THE
DEVELOPMENT OF PROCESSES AND MATERIALS
P.J. SPENCER, G. ERIKSSON, A. VON RICHTHOFEN
Institute for Theoretische Huttenkunde, RWTH-Aachen, D-52056 Aachen, Germany
ABSTRACT
Some excellent thermodynamic calculation ''packages'' are now available. They account
for theoretical studies that reduce the experimental and development phases. The
Scientific Group Thermodata Europe (SGTE) presents here some applications of
thermodynamic data from their databases. Examples deal with the use of the
thermodynamic database COST 507 for developing new light alloys as well as complex
metastable, refractory coatings obtained by physical vapor deposit.
RESUME
L 'utilisation de donnees thermodynamiques validees de bonne qualite avec des logiciels

sophistiques autorisent l'execution de calculs thermodynamiques tres performants tant au
niveau de la conception de nouveaux materiaux et composants qu'a celui de procedes
d'elaboration. Une action de la base de donnees europeenne COST 507 permet d'aborder
facilement Ie developpement de nouveaux alliages zegers. Les donnees stockees
concernent des domaines tres vastes relatifs aux alliages d'aluminium, de titane et de
magnesium. Quelques applications sont evoquees, en particulier celles relatives aux
revetements metastables, refractaires par deposition en phase vapeur.
1 INTRODUCTION
The key role of thermodynamic calculations in defining optimum conditions for carrying
out and understanding materials processes has long been recognized. Nevertheless, it is
only through the significant developments in computer software for complex equilibrium
calculations, in the modeling of solution phases with complex structures, in the
accumulation and critical evaluation of experimental thermodynamic data both for pure
substances and for complex mixtures, that the full potential of thermodynamic calculation
methods can now be more fully realized.
There are important practical reasons for making full use of the thermodynamic
calculation 'packages' now available from a number of sources. Apart from the capability
of simulating processes of interest, whereby a process can be improved by determination
and optimization of the critical parameters, the speed of calculation now available offers a
real possibility to use the calculations for process control in certain cases for example, to
control the composition of the gas atmosphere in carburizing or nitriding processes.
Information gained from thermodynamic calculations for complex systems is also
providing new insight into the basis of compositional and phase changes under different
conditions. This information could not be gained with the simplified modeling and
estimated' data available earlier. Still more attractive are the very significant time and cost
benefits associated with the use of thermodynamic calculations in materials and process
development, for such theoretical studies allow a very great reduction in the amount of
experimental development work needed. By proceeding hand-in-hand, calculation and
experiment make much more rapid and reliable progress than that associated with trial-
and-error methods. In this paper, examples are presented of how thennodynamic data
from the databases of the Scientific Group Thermodata Europe (SGTE) are being
combined with different software programs to provide a sound basis for the development·
of materials and processes of different types.
2 REVIEW OF ApPLICATION AREAS
Thermodynamic theory and calculations are now finding regular application in the
development of a variety of new materials. They are also fundamental to establishing the
optimum parameters required to carry out an existing or proposed new process with
minimum wastage of energy and materials. At the same time the possible release of
potentially hazardous substances to the environment can be investigated, and
counteracting measures or alternative process parameters sought. Examples of such
applications are:
2.1 Materials Development
Thermodynamic calculations are being used to investigate

./ optimum compositions and heat-treatment temperatures to achieve a material with
the desired constitution
The Application of Thermodynamics to Processes and Materials 171
./ methods to remove or reduce impurities
./ heat changes and phase transformations associated with casting processes
./ gas compositions and temperatures to produce materials by chemical vapour

deposition (CVD)
./ multicomponent target compositions and deposition temperatures to produce desired

metastable coating structures by physical vapour deposition (PVD) techniques
./ alloy compositions required to give optimum corrosion resistance in particular

environments
./ etc.
2.2 Process Development
Information being gained from the application of thermodynamic calculations to process

development and control includes
./ conditions for roasting and sintering of ores to produce charge material with a
composition suitable for subsequent process stages
./ temperatures and amounts of condensed phases deposited from waste gases, thereby
enabling suitable cooling and filtering stages to be designed
./ slag compositions for removal of impurity elements from molten metals in refining
processes and for solution of minority elements in waste treatment processes
./ enthalpy release and efficiency of different fuels for use in different furnace
operations
./ purity of the liquid tin bath and gas atmosphere needed to avoid imperfections in the
product during operation of the "float-glass processes
./ etc.
Selected examples of the application of thermodynamics to different types of materials
processing problems are discussed in more detail below.
3 EXAMPLES OF THE USE OF THERMODYNAMIC CALCULATIONS IN

MATERIALS DEVELOPMENT AND PROCESSING
3.1 A thermodynamic database for the development of new light alloys -

COST 507
The European COST 507 Action represents an excellent example of the use of
thermodynamics in the development of new materials. The Project aims to reduce
considerably the major experimental effort required in the development of new light-
alloys by providing a thermodynamic database for alloy design which will permit
relatively inexpensive and rapid calculation of the phase constitution to be expected in a
particular multicomponent alloy under defined operational conditions.
The stored data relate to a broad range of aluminum, titanium and magnesium alloys for
which thermodynamic calculations can be carried out to obtain detailed, technically
important data with respect to, e.g. liquidus and solidus temperatures, crystallization paths
for equilibrium and non-equilibrium conditions, nature and amounts of precipitated
phases, enthalpy effects associated with phase transformations, etc.
The alloy categories in question, together with some of the major areas of application are:
AI-Mg-Mn-Fe-Si-(Cu,Cr,Ti,C) - cans, extrusions, spaceframes, castings

AI-Mg-Si-Cu-(Fe,Ni) - extrusions, automobiles
Al-Zn-Cu-Mg-(Zr,Cr,Si) - transport, aerospace
Al-Li-Cu-Mg-Zr - airframes
Ti-AI-Mo-Zr-Sn-Nb-(O,N,C) - gas turbines
Ti-Al-V-O-N-C - gas turbines
The database is being developed through a combined programme of thermodynamic data

measurement and evaluation. From the 14 signatory countries, some 40 individual
projects are allocated to four coordination groups dealing with different aspects of the
measurement and evaluation work.
Some results from the Project, illustrating the evaluation work involved as well as the
potential applications of the database, are illustrated in Figs. 1-4.
Fig.l illustrates for a hypothetical binary system the different types of experimental
thermodynamic data used in the evaluation work.
(1) Enthalpies of solution, Am H(Tx)

(2) Component activities, 3.j (Tx)
00 (3) Heat content, cp
(4) Enthalpies offormation, ~f H(T)
00 (5) Enthalpies of transformation, ~
0--_ (6) Temperatures of transformation
(7) Phase equilibria, T, x', x", Jl', Jl"
Figure 1: Types of experimental information used in the thermodynamic evaluation of

alloy phase diagrams
The evaluations are carried out using optimization programs, [1,2] from which sets of
coefficients describing the Gibbs energies of the different phases in the system as a
function of temperature and composition are obtained. The coefficients provide a self-
consistent description of both the thermodynamic properties and the phase diagram of the
alloy systems concerned.
Fig 2 compares the chemical potential of Zn in the liquid phase of the Cu-Zn system,
calculated using the evaluated coefficient set for this system [3], with experimentally
determined values.
0
E -1
"-
-,
C -2
N
....0
0
-3
:;:: Calculated (1273 K)
c
G>
0a.. -4 o Solovev et al. [79Sol] (1373 K)
+ Everelt et al. [57Eve] (1200 K)
Y Oownie [6400w] (1200 K)
0
0 -5 A Baker [70Bak] (1423 K)
·E ¢ Leltgebel [31Lel] (1188 to 1518 K)
G> + Gerling and Predel [80Ger] (1174 K)
.s:: X Kleppa and Thalmayar [59 Kia] (900 K)
U -6 Schneider and Schmidt [42Sch] (973 ta 1123 K)
Azakaml and Yazawa [68Aza] (1123 to 1473 K)
E4 Suglno and Haglwara [86Sug] (1373 to 1473 K)
-7
A 0 0.2 0.4 0.6
Mole Fraction Zn
0.8 1.0
Fig.2 Comparison between the calculated chemical potential ofZn

in liquid Cu-Zn alloys and selected experimental results.
Fig.3 a) illustrates how a set of coefficients from the COST 507 database can be used to
calculate the phase constitution in a section through the ternary AI-Si-Zn system [4].
Here again, calculated phase boundaries are compared with, some experimental
measurements.
In Fig.3 b), the changes in enthalpy associated with the phase transformations taking place
on cooling an alloy of the composition indicated in Fig.3 a) are illustrated. The
information contained in Figs. 3 a) and b) has important implications for casting
processes.
A
o.
1000 J
! L+Fcc L-Si
"; 900 1 - :2
-10-
! j .
..5
:
! 600~
:: -20"';
t I
I Expt.: ~ !
1
0 I
Fcet+tco*Si : i!eJ.: -301
__-+____
0
<'III ••
I
400~------ ~
0.0 0.2 0.4 0.6 0.8

Al:0.9407 X Zn
Si:0.0593
~I:O
-~---------------------
51:0.1193 ~ SOO 800 700 300 900 1000 1100
Temaerarure In K
Figure 3
a) Calculated section in the AI-Si-Zn system b) Enthalpy changes on cooling alloy A
3.2 The development of complex, metastable refractory coatings using

physical vapour deposition (PVD) techniques.
Multicomponent coatings produced by deposition of material from the gas phase onto a
"cold" substrate may often display a structure which is metastable under normal
equilibrium conditions, but which nevertheless posesses properties superior to those of its
pure constituents. By carrying out thermodynamic calculations to predict the ranges of
composition in which particular coating structures will be formed in a given system at
different deposition temperatures and compositions, selection can be made of optimum
process conditions to achieve a coating structure with desired properties.
The basis for the calculations is the hypothesis made by Saunders and Miodownik [5]
with regard to the deposition of metallic alloys on low-temperature substrates. They
suggest that, due to the low substrates temperatures used, diffusion cannot take place to
produce separation into a multi phase structure in the deposited materials. As a result, a
single phase coating is formed from the phase with the lowest Gibbs energy at the overall
coating composition and substrates temperature concerned.
Calculations have already successfully been made to predict ranges of composition for
different metastable coating structures in the Ti-Al-N and Ti-B-C systems [6,7]. Recent
experimental studies based on deposition and analysis of coatings in the AlN-AI 20 3
system [8] provide the basis for thermodynamic calculations describing the variation of
stability of different coating structures as a function of composition and temperature.
FigA illustrates the phase equilibria in the section AlN-AI 20 3 of the Al-N-O system as
calculated using the thermodynamic description of the system reported by Hillert and
Jonsson [9].
2600 LS
a: 2436
r--
N
2334
g 2200 2152
Spinel !
2316
h
1800
1627
1400
AIN 0.2 0.4 0.6 0.8 Al z0 3
xAI203
Figure 4: Calculated phase equilibria in the system AlN-AI 203

To the published coefficient set have been added a description of the hexagonal (A IN)
phase across the system, and thennodynamic data for the amorphous phase. These allow
reproduction of the observed experimental infonnation at two temperatures.
Using the complete set of data, metastable ranges of the spinel, hexagonal and amorphous
phases have been calculated.
Fig.5 shows the calculated Gibbs energy offormation curves at 463K for these phases.
70000r---~-----r----~--~----~
....
o
190°C
....E
;]
c:
~
;;
E
.£
'0
>-
.,...0>
c:
<D
U')
..0
..0
<5
o~--~----~----~--------~
o
Mole fraction Al z0 3
AIN
Figure 5: Gibbs energy of fonnation of stable and metastable phases in the Al 20 3 system:
T=463K
The compositions at which the Gibbs energy curves for the amorphous, spinel and
hexagonal phases intersect were established from the changes in structure of the coatings
as observed directly in Transmission Electron Microscopy experiments.
By calculating such curves for a number of temperatures, the loci of the points of
intersection can be detennined and a plot made of the metastable ranges of the different
phases as a function of temperature. Such a plot is presented in Fig.6.
550
hexagonal 0
spinel 4
500
o
~4-50
f-
400
amorphous x
3SO
300 0
Mole fraction AI 20 3
AIN
Figure 6: Metastable phase regions in the system -Al z0 3 - AIN
The results clearly demonstrate how thermodynamic calculations can be used to assist in
the design of new coating materials.
3.3 The theoretical investigation of toxic emissions associated with

waste treatment processes
Waste gases are of considerable environmental concern with respect to the potentially
hazardous species they may contain. The composition of the gases, as well as that of the
condensed phases forming from them, requires reliable, quantitative modeling in order
that hazardous emissions can be predicted and suitable operating conditions, extraction
methods and treatment processes be selected.
Using the program ChemSage [10], waste gas cooling processes have been simulated. A
recent improvement to the "REACTOR" module of the program allows, for the defined
cooling range, the removal from the system of the condensed phases formed at defined
temperatures. In this way, the resulting effects on the sequence and nature of subsequent
precipitation reactions can be automatically simulated and cooling sequences to achieve
controlled precipitation behavior more realistically investigated.
3.3.1. Incineration of fly-ash
In a first series of calculations, the amounts of condensed phases formed from the gas
phase on cooling to different temperatures have been calculated. The "mapping" feature
of ChemSage allows the exact temperatures of appearance and disappearance of the
different phases to be determined, whereby the assumption is made that a gas of the same
initial composition is cooled to each of the temperatures within the specified temperature
range.
o r--.------.------,--.---.------.-----,-----, 0 AlF3/Gas/
a o AsF3/Gas/
A CaF2/Gas/
""----Jl----"'""""::Z:.:...J + Cd/Gas/
X CdCl2/Gas/
fjZ:~2:;~~=~ <> CI/Gas/

'V CuCi/Gas/
'"""'r~!L-----:::;;>"""=----"""*"--l 181 FeC12/Gas/

~ Hg/Gas/
• KCI/Gas/
Ell NaCI/Gas/
lIX PbCl2/Gas/
EB PbS/Gas/
a)
-10
30000 o 3CaO.A12O:J.3Si~
b
o CaCO:J
I
A CaCi2
+ Cao'A12O:J·2Si~
X CaO,MgO.2SiO
~
.c; <> Cao'~(P)
...."" 'V Caro4

..,0 181 F"304
s::
::s
~ F"2O:J
~ • FeS
§ Ell ~O.A12O:J.6Si~
'1:
:9 lIX KCI
'S EB NaCi
$
181 Si~(q)
~ ZnO,A12O:J
0
100 1100
b) Temperature [el
Figure 7 a) Partial pressures of major b) Amounts of condensed phases formed
gas species from the gas
The Application of Thennodynamics to Processes and Materials 179
Figure 7 a) illustrates the calculated partial pressures of the major gas species of the
different elements present in the waste gas produced by incineration at a rate of 100 kg/h
of a typical fly ash.
Metal chlorides are particularly stable in the gas phase for the given fly-ash composition
and incineration conditions. The irregularities in the various curves at temperatures
around 7000C are associated with the formation of different condensed phases from the
gas phase, as can be seen in Fig 7 b) , which illustrates the amounts of condensed phases
formed per hour from the gas phase. Silicates and iron oxides form the major proportion
ofthe phases deposited from the gas, with potassium and sodium chlorides also present in
fairly large amounts (Fig.7 b). Heavy metals are present in smaller quantifies, mainly as
sulphides at temperatures below about 700°C.
Using the described improvement to the "REACTOR" module of ChemSage together

with a slight modification of the fly ash analysis used for the previous calculations, the
cooling of the gas phase has been considered for stepwise cooling to 1100°C, 500°C and
25°C respectively, whereby the condensed phases formed at each stage are removed from
the system and only the resulting gas phase undergoes cooling to the next stage. The
phases formed at each stage, and their amounts, are listed in Table 1.
Substance Amount (kg) at Cooling temperature °C

llOO°C 500°C 25°C
KCl 4.312 0.84
NaCI 2.528 0.15
ZnS 0.766
CaCI 0.186 2.2 10-3
ZnCl 2 5.9 10-3 1.5 10-3
CdCl 2 7.110-7
S 2.158 0.87
K3AICl 6 4.3 10-3
AICl 3 9.6 10-4
HgCl2 7.8 10-4
K3Al 2Cl 9 1.5 10-6
NaAICl 4 1.8 10-7
Table 1: Phases formed on stepwise cooling of the gas phase resulting from incineration
of fly-ash
The sequence of phase formation resulting from the stepwise cooling and removal of
condensed phases at each stage may be compared with the results for cooling a gas of
very similar composition to each temperature, as illustrated in Fig.7 b.
o ~--'--~--'-----r-----.---r----,--- 0 C12 H2 02Cls(12347)

a
o C12H20zCls(12367)
t:, C12H20zCls(12378)
+ C12 H20zCls(12467)
x C12H30zCl5(12347)
o C12H30zCI5(12378)
~~~~~~ 'V C12H30zCl5(12478)

____ _ tiJ C12~C40z(2378)
~ C12~CI40zh234)
$ C12~Cl40z(1237)
6l C12~Cl40z(1368)
!IX C12~CI40z(1378)
Ell C12HOzCl7(123467)
i8I C120zCla
a) -15 L-__LUL-~~~-ll-L-L~1--J____L-~
o 0 C12 H20zCls(12347)
b
o C12H202Cls(12367)
t:, C12H20zCla(12378)
+ C12 H20zCls(12467)
x C12H30zCI5(12347)
o C12H30zCl5(12378)
'V C12H30zCl5(12478)
tiJ C12~C40z(2378)
~ C12~CI40z(1234)
$ c12~CI40z(1237)
6l C12~CI40z(1368)
!IX C12~C40z(1378)
Ell C12HOzCI7(123467)
i8I C120zCl8
Temperature rei
Figure 8
a) Dioxin partial pressures for the input b) Dioxin partial pressures for the input
mol amounts mol amounts
C=4, H=O.l, 0=4, Cl=O.l C=4, H=O.05, 0=4, Cl=O.l
The Application of Thennodynamics to Processes and Materials 181
3.3.2 Incineration of organic waste
The formation of dioxins has frequently been reported in association with processes for
incineration of organic waste. In particular, the Polychlordibenzodioxins, which include
the highly toxic species 237S-tetrachlordibenzodioxin (TCDD), are found together in
various proportions in the condensates formed from the waste gases. Such findings have
recently been confirmed in the carefully controlled laboratory experiments carried out by
Fangmark [11].
To try to simulate dioxin formation during cooling of waste gases, and thereby enable
process parameters to be determined such that conditions leading to formation of toxic
species can be avoided, thermodynamic calculations have been performed. Since
complete sets of thermodynamic values for the different dioxins are not available,
experimental thermodynamic information has been extracted from the literature and used
as basis for deriving and estimating the missing values.
It was found that the amounts of different polychlordibenzodioxins associated with

different gas sampling temperatures, as reported by Flingmark, could be approximately
reproduced by variation of the CIH ratio in the analysis of input material to the furnace.
Results for two CIH ratios are illustrated in Fig.S a) and b). It should be noted that the
results apply to a situation with carbon and hydrocarbon formation suppressed.
It can be seen that just small changes in CIH ratio can cause marked differences in the
relative proportions of dioxin species present at a particular temperature.
This fact, combined with the inhomogeneous charge and gas compositions pertaining in
practice, can be expected to lead quite easily to the variation in amounts of different
dioxin species observed.
4 CONCLUSION
The availability of evaluated thermodynamic data and sophisticated computer software

enables thermodynamic calculations to make a significant contribution to the design of
new materials and new processes.
The examples presented here are representative of a much wider range of materials
processing operations which are now accessible to development and investigation with the
assistance of thermodynamic calculation techniques.
KEYWORDS
thermodynamic data, software calculation, light alloys, refractory coatings, toxic emission
REFERENCES
[I] H. L. Lukas, S.G. Fries, J. Phase Equilibria 13, (1992),532.

[2] B. Jansson, Ph. D. Thesis, Div. Phys. Met., Royal Inst. Technol.
Stockholm, Sweden, (1984).
[3] M. Kowalski, P.J. Spencer, J. Phase Equilibria 14, (1993), 432.
[4] M.H.G. Jacobs, PJ. Spencer, J. of Alloys and Compounds, (1994), in
press.
[5] N. Saunders, A. P. Miodownik, J. Mater. Res. 1, (1986), 38.
[6] P.J. Spencer, H. Holleck, High Temp. Science 27, (1990), 295.
[7] H. Stolten, PJ. Spencer, D. Neuschutz, J. Chim. Phys. 90, (1993), 209.
[8] A. von Richthofen, R. Domnick, PJ. Spencer, D. Neuschtitz, Proceedings
8th Work Meeting, "Angewandte Oberfliicht:llanalytik", AOFA 8,
Kaiserslautern, Sept. (1994).
[9] M. Hillert, S. Jonsson, Z. Metallkunde 83, (1992),714.
[10] G. Eriksson, K. Hack, Met. Trans. B, 21B, (1990), 1013.
[11] I. Fangmark, Ph. D. Thesis, Inst. Environmental Chemistry, University of
Umea, Sweden, (1993).
Chapter 4
COMPUTER - AIDED- DESIGN AND NEW

MATERIALS
MATERIALS DATA FOR THE ERA OF AGILE

MANUFACTURING
Kenneth PREISS
Sir Leon Bagrit Professor, Global Competitiveness, Ben Gurian University of

the Negev, Beer Sheva, Israel and Senior Fellow, The Agility Forum,
Bethlehem PA 18015
ABSTRACT
Manufacturing is undergoing a system-wide change. Many of the difficulties currently

experienced by industries and industrialized countries are due in large part to the
stress of this change. For a hundred years we have been living in a system where
manufacturers made many identical copies of a product, invested much money in
inflexible machines, and the customer's choice was limited to take it or leave it at the
price offered. It was a producer-push controlled system. Computer-controlled flexible
production systems and computer network technology have changed the capability of
marketing and production so that today every customer can be treated as an
individual; production runs can be short, even one individualized product at a time;
time to design has been cut down remarkably; and individual customers can interact
rapidly and efficiently with suppliers at all stages of the value-adding chain.
Requirements for products and the production processes include:

- the supplier of a product offers the end consumer lifetime support, service and
upgrades
- reuse and recycling of a product is a service which the producer must provide
- tightly-coupled interactive work among cooperating suppliers in an international
network is a usual practice
184 Computer-Aided-Design and New Materials
- much more data than before, relating to the product and its effects, is provided as
the responsibility of the producer.
These factors lead to new requirements and to new opportunities for materials data
activities.
RESUME
L 'ingenierie de fabrication subit actuellement des transformations importantes. Les

difficultes rencontrees dans les industries et les pays industrialises sont liees en partie
aces changements. Au cours de centaines d'annees, nous avons connu des processus
de fabrication visant a produire de nombreux exemplaires identiques d'un produit
pour lequel les industriels investissaient beaucoup de capital sur des machines peu
soupies. Le client n 'avait pas d'autre choix que d'accepter ou rejeter ce produit au
prix offert. Ce systeme etait du type "contr6le de pression du producteur". Les
systemes de production flexibles contr6tes par ordinateur et la technologie des
reseaux d'ordinateurs ont change les capacites de marketing et de production de telle
far;on que chaque client peut-etre traite sur une base individuelle. La production peut
etre centree sur une serie courte et peut meme produire un produit individualise a la
fOis car Ie temps de conception des produits a ete considerablement reduit. Les clients
individuels peuvent agir de far;on interactive et efficace avec leurs fournisseurs a
toutes les etapes de production.
Les exigences pour les produits et la production comprennent:

Ie fournisseur d'un produit offre aux consommateurs en bout de chaine un
soutien, des services et une mise ajour durant la vie du produit
des echanges etroits et interactifs avec les fournisseurs cooperant associes dans
un reseau international releve d'une pratique courante
beaucoup plus de donnees qu 'auparavant relatives au produit et a ses effets sont
proposees sous la responsabilite du producteurlfabricant.
Ces facteurs engendrent de nouvelles exigences et conduisent a de nouvelles

opportunites pour les activites en matiere de donnees sur les materiaux.
1 INTRODUCTION
It has become increasingly clear to anyone involved with manufacturing, that

fundamental change is coming over the industrial business environment, everywhere.
Studies have been in process for some years in Europe, Japan and the U.S., to
understand the changes to the competitive environment, and to plan appropriate
actions to deal with them. All the studies point to the conclusion that a deep, system-
Materials Data for the Era of Agile Manufacturing 185
wide change is indeed under way, and all the studies come to similar conclusions as to
the direction of change. The new system has been named the Agile Competitive
System, and represents the new industrial order following the hundred year
dominance of the Mass Production System.
In the new system, that of Agility, the aims of a company are different than in the
product-centered mass production company; the structure is different from the
hierarchic structure of the mass production company; and relations with suppliers and
other companies are different than in the product-focused relationship of the mass
production system. This new system has far-reaching implications on the requirements
for materials data. General information on the new Agile System can be found in the
three references cited at the end of the paper. The paper will describe the new system
very briefly, then will analyze the implications for materials data for the new era.
2 DRIVERS OF CHANGE
The industrial world is moving into an era of greatly expanded global competition.
Companies from around the world are becoming connected by modem computer-
based communication; well-trained engineers and technologists can be found in
almost every country; production machines are accessible to all, since production
capability has become cheaper by an order of magnitude or more over the last few
decades; design aids (usually computer programs) are also accessible to anyone. The
act of making a product, alone, no longer provides competitive advantage.
Reference (2) sums up the factors driving change as follows:

Continuous change
Rapid response
World-wide competition
Environmental enhancement
Evolving quality
3 THE DIMENSIONS OF THE AGILE CORPORATION
The factors which are new and different in industrial businesses today, compared with
the past, form four dimensions within which one can understand the new industrial
era. The most significant factor with which companies struggle is relentless, rapid
change. The rate of change of all factors affecting business is becoming ever faster.
Internally, companies are organizing to deal with the challenges of change by
reducing layers of management, empowering people in teams, and by taking
advantage of the motivation and knowledge o/people and in/ormation.
Relations with suppli_'rs have become tighter. Customers are "rationalizing" the
relations with their supphl.. ..s by cutting down the number of suppliers to as low as 5%
to 20% of the previous quam:+v; in doing so, the engineers and others in the supplier
chain and the customer organiz" +ion work in integrated teams, often using modem
computers, and other electronic ,'ommunications. This leads to the fact that
competitive capability is enhanced by c,-'operating even with competitors. Supply of
product alone is no more a competitive differentiator. People around the world have
gained good education; production machinery and design computer aids are available
and accessible everywhere. Distribution and commerce in the modem world have
become global. Profit requires that high value-adding activities, necessary to support
the standard of living associated with first world conditions, go beyond the supply of
product, to providing a total customer solution which is a fusion of product, service,
information, life-long upgrades, and eventual recycling of the product. Relations
between companies used to be based on supply of product. Relations now are based
upon the supplier coordinating the total work process with that of the customer. In one
concise concept, competition has gone from being product-centered to process-
centered.
4 NEW DEMANDS ON MATERIAL DATA
The fact that survival now requires a company to coordinate its processes with those
of its customers, and to look beyond providing product to providing a total solution,
has a large impact on requirements for product data. Product data now need to possess
the following characteristics which, although desirable in the past, have now become
conditions for competitive survival:
1) Timeliness. The reduced time for product development requires that data be rapidly
available.
2) Well-defined. The data will be used by teams cooperating across several

companies, yet at the time it is supplied, the identities of all the persons or computer
systems who will require the data, will usually not be known. This requires accepted,
well-defined definitions for attributes and metrics.
3) Audit trail. Liability considerations, both from the civil and criminal perspectives,
will require that an audit trail be kept of the data, how it was derived, how and who
modified it, and how it was used.
4) Reliability. Increased requirements from products and the integration of products

into total solutions, achieved by cooperation between companies, lead to the need that
the data be sufficiently reliable that the companies or individuals supplying the data be
reasonably protected against liability. This is especially important for environmental
data as is discussed below.
Materials Data for the Era of Agile Manufacturing 187
5 ENVIRONMENTAL DATA
Customers, governments and society in general are requiring that products be recycled
or reconditioned and reused by the manufacturers after the product has reached the
end of its useful life. This in turn leads to products being designed not only for all the
previous considerations of function, quality, manufacturability and reliability, but also
to be designed for disassembly and recycling. Each supplier in the industrial "food
chain" takes back his assembly, disassembles it, sends the supplied components to his
suppliers, then tests and reconditions or recycles his own product, and so on back up
the food chain, recursively. This new responsibility is likely to lead to a restructuring
of the industrial food chain. The decision as to which business to be in and how to
specialize, previously was based only on the capability to design and manufacture a
product which was then sent to the customer with a warranty or liability limited in
time and conditions of use. That business decision now needs to be based not only on
that capability, but also on the capability to recondition or recycle the product in an
environmentally benign way, certifiable according to the requirements of different
countries and different professional or licensing bodies. This condition in turn leads to
greatly increased need for data on the materials from which products are made, and on
the materials used to process products both new and used. These are considerable
demands which are likely not to be met by the old-style manufacturing company
which had specialized in product design and manufacturing, but not in materials data.
It is likely that this new demand will be attended to by a new structure of companies
involved in materials data.
The structure will include the following functions:
1) Product design
2) Product manufacturing
3) Materials data creation
4) Materials data organization and distribution
5) Materials data brokering, finding the right data at the right time
6) Materials data certification
7) Planning and certification of the product reconditioning process
8) Planning and certification of the product recycling process
It is unlikely that all these functions will be in one large company, since economic
imperatives are now forcing the tendency to downsize and focus on core
competencies. Understanding of materials data and how to use it is not usually a core
competency of industrial companies and so they will likely look for such
specialization from other companies. Another tendency, to which we are all witness or
are a part of, is the move to organize as a virtual corporation. A virtual corporation is a
grouping which appears from the outside to be one organization but which in fact is a
cooperative arrangement between many companies. If the legal liability for work rests
all in one vertically integrated company it is easy to understand where the overall
responsibility falls. In a virtual organization the liability for the result of work rests on
all the participants. This requires new inventive agreements as to how to arrange the
legal liability. This requirement may lead to further fragmentation of the materials
data industry, because a company or consultant in the field will have the incentive to
go very deeply into a limited subject so as to be able to tolerate the liability, rather
than being spread thinly over many subjects and hence being responsible for matters
where the company or the consultant does not feel altogether competent. This clearly
will open the need also for companies or consultants who are experts on who has
which data, and how reliable each is, and opens the need also for an accepted
certification or similar professional process.
6 CONCLUSION
International industrial structure is changing so that suppliers and customers, rather

than interacting via the properties of product, interact via the properties of their work
processes. Simultaneously, products are more and more fragmenting so as to provide
an individualized solution to each customer, even while quality requirements are
becoming more and more stringent. This opens up major new requirements for
materials data, but also opens up major new opportunities for individuals and
companies who deal with these issues.
KEYWORDS
agility, global competition, environmentally conscious manufacturing, virtual

organization
REFERENCES
[1] Goldman S. L., Nagel R. N. and Preiss K. Agile Competitors and Virtual
Organizations: Strategies for Enriching the Customer, van Nostrand Reinhold,
September (1994).
[2] Goldman S. L. and Preiss K., Editors; Nagel R. N. and Dove R., Principal
Investigators; and 15 Industry Executives 21 st Century Manufacturing Enterprise
Strategy: An Industry-Led View, 2 volumes, Iacocca Institute at Lehigh University,
Bethlehem Pa. (1991).
[3] Preiss K., Goldman S. L. and Nagel R. N. Cooperate to Compete: Building Agile
Business Relationships, van Nostrand Reinhold, (1996)
MATERIALS DATA REQUIREMENTS FOR COMPUTER
SIMULATION IN DESIGN AND MANUFACTURE
D. R. HAYHURST
Department of Mechanical Engineering, UMIST, Manchester M60 I QD, UK.
ABSTRACT
The paper considers a top-down systems approach to the wealth creation process
starting at the marketplace, progressing to a design specification, the concept design
phase and, through detailed design and manufacture, to delivery of the component or
system to the client. At all stages of the process the need is consideredfor data and in
particular materials data. Whilst the paper refers to the special features associated
with the quality of materials data required at the concept stage of design,
consideration is also given to the type of data required to underpin product innovation
and technological forecasting. The bulk of the paper considers the materials data
requirements for supercomputer simulation of the behavior of components in service
and of products where the material is created and then used in service. The latter
situation is considered via the optimization of the selection of materials for a high-
temperature weldment in a pressurized steam pipe; and also via the assessment of the
performance of a tension panel, containing a central circular hole, fabricated from a
tough ceramic fiber-ceramic matrix composite. These examples show the diversity of
requirements of materials data in supercomputer simulation at the detailed design
stage. In the examples considered, reference is made to visualization and video
animation to transmit two dimensional screen images of the time variation of field
plots of stress and internal damage variables which can be interpreted satisfactorily
by a range of cross-disciplinary specialists. Conclusions are made on the importance
of linking the structure and accessibility of databases with the need to provide
guidance from physics-based mechanism maps for deformation, damage and fracture.
RESUME
On considere une approche systemique descendante du processus de creation de
richesse, en partant du marche pour presenter au client un design detaille et la
realisation industrielle des produits resultants. Cette demarche passe par la
specification de design et par la phase conceptuelle du design. On considere dans
to utes les etapes du processus Ie besoin de donnees et, en particulier, des donnees sur
les materiaux. Bien que l'on se concentre sur les aspects speciaux associes a la
qualite des donnees sur les materiaux necessaires au stade conceptuel du design, on
considere aussi les types de donnees sur lesquels sont basees l'innovation de produits
et les previsions technologiques. L'essentiel de cet article est oriente vers les
exigences en donnees sur les materiaux necessaires dans les simulations sur
superordinateur du comportement des composants en service, ainsi que sur des
produits imposant la creation de materiaux en vue de leur utilisation courante. Dans
ce dernier cas, on considere l'optimisation de la selection des materiaux pour la
soudure ahaute temperature d'un circuit de vapeur sous pression; de meme on evalue
fa performance d'un tableau de tension contenant un orifice central circulaire,
fabrique a partir d'une matrice composite de fibres solides de ceramique. Ces
exemples sont utilises pour souligner la diversite des exigences des donnees sur les
materiaux dans la simulation sur superordinateur au niveau de la conception detaillee
du design. Dans ces cas, nous nous referons a la visualisation et a l'animation video
pour transmettre des images d'ecran en 2 D des variations tempore lIes de champ des
sites de tension et des variables de dommage interne dont l'interpretation est acquise
de fa90n satisfaisante grace a la contribution de specialistes interdisciplinaires. En
conclusion il est essentiel d'associer etroitement la structure et les fonctions
d'accessibilite des bases de donnees a la necessite de procurer aux specialistes des
cartes des mecanismes d'origine physique pour les deformations, les dommages et les
fractures.
DESIGN SPECIFICATION
Figure 1: Top-Down serial approach to Marketing, Designing, and Manufacture

within the wealth creation process
Materials Data .,. Computer Simulation in Design and Manufacturing 191
1 INTRODUCTION
Design and manufacture of new products are key to sustammg a healthy wealth
creational base, but this is no longer a passport to success. Many other factors are
decisive in the determination of successful wealth creation. Some of these may be
appreciated by reference to Figure 1 in which a top-down systems approach is given
to the design process. The diagram is presented as a discussion aid, and it is
recognized that many countries carry out such functions in a highly parallel or
concurrent mode [20).
Marketing research, very different from the sales function, is the key to the
identification of which market sectors, and of their size, that a particular product
should be aimed at. Market research can then be used to create the design
specification. Traditionally technologists have felt able, and qualified, to "know the
minds" of their clients and customers and to be able to bypass the first two stages in
the process, i.e. marketing research and design specification. Current activity in world,
and in national, markets is such that large databases on market information have to be
established and continually updated. Quick access, ahead of the competition, is an
important aspect of maintaining and of extending one's market share. It is recognized
that data and information management associated with marketing is an increasingly
important part of design management. However, it will not be covered in this paper
explicitly.
Having identified a product and a market sector and from this information written an
unprejudiced design specification, in basic or abstract terms, the engineering design
process can commence. It does so with the formation of concept designs by
encouraging the design team to think laterally; to innovate, using new technological
breakthroughs; to use new materials and new manufacturing techniques to get the
product to market quicker, at the required quality, and at lower cost. This process
requires large databases, not just involving the lead company, but those of other
companies such as design out-sources, component suppliers, manufacturers and
fabricators. This leads to the requirement of shared data between companies, often
competing, with a need to maintain confidentiality and one's competitive edge. The
process of sharing data, whilst exercising bounded control over accessibility, can slow
down the very process which needs speed in order to be successful. In this
environment the correct hierarchical structuring of data and the level of accessibility is
vital to success. Hence, data structures and robust software are an essential part of the
competitive process.
At the concept design stage the principal function is to propose design variants and to
carry out assessments of the extent to which they satisfy the design specification. It is
necessary to carry out design calculations operating with lower levels of information
for which the degree of precision need not necessarily be high. The coarse sorting
type of assessments carried out at the concept phase lead to the rejection of
inadmissible concept variants and to the identification of a reduced sub-set; which, in
tum, requires assessment at higher levels of information for the final concept selection
to take place. This further process is often referred to as embodiment design. It repeats
the concept level assessment in more detail and considers upstream and downstream
factors. Examples of this might be further interaction with the marketplace, i.e.
feedback - feed forward; and interactions with the manufacturing-assembly-packaging
functions, i.e. feed forward - feedback. Many of these functions are materials
selection dependent and require the use of materials databases containing different
data sets each possessing a range of information qualities. The embodiment phase
naturally leads to a chosen design preference with clearly delineated options and fall
back strategies. However, in this paper attention will be focussed on the materials
database requirements. The detailed design phase then follows in which a single
design is examined in great detail. Traditionally the role of this phase has been to
satisfy the designer that the technical function and the risk of unacceptable failure, as
perceived by the user and society, are acceptable. Then comes the manufacture of the
product or system and its infeed to the marketplace.
The manufacturing function is key to product quality and reliability. The subject of
manufacturing systems impacts on the cost and time to market, whilst the
technological aspects of manufacture relate directly to product integrity, quality, cost
and technological function. The role of materials processing in manufacture is the
technological aspect considered here. This was selected since it involves an upstream-
downstream coupling with the design stage of the process, brought about by the
common material thread.
The major technological change in recent years is the availability of lower cost
computer workstations and supercomputers, with access to large, low cost, fast-access
data storage facilities. At the same time, numerical techniques and software for the
solution of combined boundary-initial value problems, often involving the finite
element method, are becoming available in robust forms. Hence it is possible, given
the appropriate materials data and models, to simulate complex physical processes in
design and manufacture. In parallel with these advances computer visualization
techniques and the development of video animation facilities have reached a state of
the art where real time simulation, or virtual reality, is an accessible tool for use in
decision making in design and manufacture.
In this paper these aspects are first covered in more detail, then the materials data
requirements for supercomputer simulation in design and manufacture are examined.
The generation of materials data from laboratory testing is addressed, and its
subsequent conversion into higher levels of data and information are discussed in the
context of two applications. The first relates to the simulation of the in-service
behavior of a high-temperature butt welded steam pipe, and to the optimized materials
selection for manufacture of the weldment in order to maximize the pipe lifetime. The
second relates to the simulation of the behavior of a simple component manufactured

in a human engineered ceramic fiber-ceramic matrix composite. In both of these
several aspects are examined which include:
• the level of precision of data required;
• the provision of software to convert data into the different levels of information
required;
• the need to link data with physical modeling for accurate interpolation and
extrapolation purposes;
• the use of visualization and animation techniques to convey the physical
meaning-significance of computer simulations to specialists within the relevant
disciplines.
Before these detailed aspects are addressed, an overview IS presented of data

requirements in engineering.
2 REQUIREMENTS FOR DATA THROUGHOUT ENGINEERING
2.1 The Wealth creation process
A top-down sequential approach to the wealth creation process [10] is shown in

Figure 1. The serial approach from market research to the delivery of the product in
the marketplace is not always enacted in industry. This, depends on the type of design.
If the design is totally original then market research is essential and the entire process
is enacted. If it is adaptive then only part is original, and for that part the entire
process is utilized as shown in Figure I; for the remaining part, only the latter phases
of detailed design and manufacture etc. are implemented. If the design is variant then
this involves the scaling of a previous design without any major conceptual or
procedural changes and only sub-sets of the entire process of Figure 1 are enacted,
usually involving parametric computer techniques. A cost effective solution is then
achieved by implementing what has been done before using the same workforce,
without any innovation.
The serial approach is increasingly less used as the benefits of simultaneous or parallel
operation become more generally accepted [20]. The degree of paralie lizat ion depends
on: company size; the divisibility of the product into sub-units; the multi-disciplinary
nature of the design; and, whether the design is original, adaptive or variant. The shift
to parallelism highlights the need to plan, execute and control the design using a
software based system. Some of the difficulties and the rewards to be gained are
discussed by Hayhurst, Alsop and Stone [13]. The need for data which defines the
current design status, the level of input from several disciplinary groups, the degrees
of interaction, and project management, all require dynamic databases for use with
appropriate levels of interaction, accessibility and user constraints.
./l-l Materials
"'IL~D""a""ta_..J
<J=. Technical
Innovation
&
Market
Forecasting
Company Data-Base
Manufacturing
<1=. Time-Window
Availability of
Manufacturing resource
Scheduling
Figure 2: Concept design: Information Flow and Materials Requirements
The main industrial drivers are to:

(i) shorten the time from concept initiation to the first prototype;
(ii) shorten the time from concept initiation to product launch;
(iii) increase product quality, reduce cost;
(iv) maximize reliability and minimize the risk offailure.
Since the use of materials is central to the creation of new products, their selection and
utilization are essential to success.
2.2 Materials data requirements for concept design
Shown in Figure 2 is an information flow and material requirements diagram for

concept design. On the left-hand side of the diagram it encompasses the first three
boxes shown in Figure 1. This has been extended to include solid-surface modeling,
rapid prototyping, and the need to consider company manufacturing methods,
constraints and costs, and customer liaison. In the right-hand column of the diagram
are features against which arrows indicate the in-feed point into the process given in
the left-hand column. The need for materials data encompassing basic physical
properties, availability and cost is shown prior to the formal concept design stage.
Ashby [2] has discussed the type and level of precision of the data required at this
stage. At the conceptual stage there is a need to technically innovate, and to utilize
methods of market forecasting. These features are crucial to the identification of new
market opportunities; they require a considerable company-industry database,
progressively updated, and which is a major competitive edge for the company
involved. It is therefore a database for which a high level of confidentiality must be
maintained, and therefore access and level of usage has to be carefully controlled. At
the bottom of the right-hand column in Figure 2 the box shows connections with
company manufacturing methods, etc. It is here that the manufacturing systems
aspects of the company are logged in a large database, and opportunities for using
spare manufacturing capacity within given time windows can be identified.
The availability of manufacturing resource, and the potential to schedule new work
within given timeframes, and hence a maximizing plant utilization can be achieved
through use of this database. Thus the interaction between concept design and the
manufacturing function can develop synergy and be used to seize new opportunities.
This can only be fully realized if that the companies involved continually update their
databases and reconfigure to provide access to the right quality of information to make
the necessary decisions; and if the software can maintain a competitive edge for the
company through appropriate access and style of database usage. We will concentrate
on the subsequent detailed design stage, and its interaction with the manufacturing
process.
Welding, Joining and Adhesives
COLUMN 1 COLUMN 2 COLU1tN 3
Figure 3: Detail Design: Information Flow and Materials Requirements

2.3 Materials data requirements for detailed design
The latter part of the diagram given in Fig. 1 is considered in more detail in Fig. 3. It
starts with embodiment design and progresses through the detailed design - analysis -
simulation stage to manufacturing simulation, and on to fabrication, assembly, and
quality assurance testing. This is shown in column I of the figure. In column 2 are the
types of material data required to underpin the activity shown in column 1. The first
box at the head of column 2 shows a materials database linked to the process of finite
element analysis coupled with pre- and post-processing for the analysis. This can be
regarded as the first detailed design analysis of the behavior of the component or
system when subjected to in-service conditions. Coupled with this is a second box
which relates to information on constitutive equations. These relate the deformation
characteristics of the material with stress, temperature and strain rate conditions. The
nature of these constitutive equations will be discussed in later sections of the paper.
The third box of column 2 shows the requirement for materials data regarding the flow
of materials in manufacture, the associated heat transfer, the evolution of
microstructure and the consequent mechanical properties. It is through the
supercomputer modeling of processes such as forging, extrusion, pressing, casting,
and plastic injection moulding that the design engineer can shape the component and
design the process to achieve defect-free components entering service. The box at the
base of column 2 contains information on materials processes, surface durability and
constitutive equations required to model fabrication processes such as: welding,
joining and adhesives etc. These relate to the assembly of discrete smaller sub-
components and units. The latter operations usually involve processes which bring
together different materials into one operation; they also define a set of multi-
materials problems for which detailed and specialized information is needed for
analysis and subsequent design.
Column 3 of Figure 3 gives some generic terms frequently used to integrate the
activities outlined above into the manufacturing systems discipline. The links between
the formal finite element stress analysis, the modeling of the shaping of materials in
manufacture, and the joining of different materials provide a continuous thread
running through the different stages of the top-down systems approach. The data
requirements of some typical examples which encompass this range of activities is
considered in the later sections of the paper.
2.4 From laboratory testing of materials to supercomputer simulation
Shown in Figure 4 is a diagrammatic representation of the route leading from

laboratory materials testing, through materials metrology and supercomputer
simulation to wealth creation. On the far left of the figure is an extended version of
Figure 1. The coupling to the region of interest, namely detailed design and
manufacture/simulation is shown by the arrows entering on the left-hand side of the

wealth creation column. On the right-hand side of the figure, within the broken lined
rectangle headed Materials Metrology, is shown Laboratory Testing of Materials.
This is the source of materials data necessary for use in supercomputer simulation.
The accuracy of the supercomputer simulation is dependent upon the accuracy of the
test data obtained at this stage. This data is usually collected in digital form and stored
on microcomputer based systems to form the first elements of the materials data.
Brought together, these constitute a database of sufficient size and significance, then
accessed by software which automatically selects the type and form of the
mechanisms-based constitutive and damage equations necessary for input into the
supercomputer simulation. At this point of automated selection it is necessary to input
data defining the physical details of the component or system to be modeled by the
supercomputer. This done, one can define the domain of operating conditions over
which physically based models must accurately interpolate and extrapolate the data.
This completed, and assuming that the quality of the laboratory testing meets
appropriate standards, one can expect the predictions of the supercomputer simulation
to be sufficiently meaningful and accurate to be able to make design decisions.
,-----------,-------,------------------,
,
rl c~~ii:~:i~'1T I , Laboratory
H MARKETING ,
I Testing of Materials
y D:i~~FTg1'~g~
CONCEPT DESIGN
I
I
I
I
+
Laboratory
I Teste:
INNOVATION I I Materials Data Base
I
IEMBODIMENT DESIGN I
,
I
r
~="=-~~ ttl- I
Automated Selection
of
H-'-
SIMULATION
Supercomputer Mechanisms-Based
Simulation
I Constitutive
""
MANUFACTURE
II and
I SIMULATION
I,
I Damage Equations
II
I DELIVERY I II
II
I,
II
I APl'ERSALES I I, I,
II I
II II
I II
Wealth Creation I' Simulation I' Materials Metrology
_ _ _ _ _ _ _ _ _ _ _ ILI _ _ _ _ _ _ _ 1 ,_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
Figure 4: Diagrammatic representation of the route leading from Materials Testing,

through Materials Metrology and Supercomputer Simulation, to the Wealth Creation
Process
COMPUTER SPEED DAMAGE XX

RUNTIME
IBM 3090 6 PROCESSOR 40 MFLOPS 200h
CRAY X-MP 4 PROCESSORS 235 MFLOPS
unvectorized 34 h
vectorized 255 min
multi-tasked 106 min
CRAY Y-MP 350 MFLOPS 71 min
CRAYC90 I GFLOP 25 min
JAPANESE NEC SX-3 5.5 GFLOPS 2.6 min
vectorized
IBM Research Projection I TFLOPS 3.6 s
by 2000
Table 1: Effect of Computer CPU speed on run-times of the Creep Continuum
Damage Mechanics Solver DAMAGE xx.
Clearly this process can only be used following rigorous quality assurance, checking
the accuracy of the simulations, and assessing the level of risk associated with making
decisions based upon the results thereof.
2.5 The impact of supercomputer simUlation on design
Shown in Table 1 are the effects of computer central processor unit (cpu) speed on run
times of a particular software package known as DAMAGE XX which has been used
by the author over a number of years to analyze the design of high-temperature
components [7,14]. In the first column of the Table is listed a range of computers
which either have existed, exist or are projected. In the second column the speed of
the central processor unit is shown in Mega, Giga and Teraflops, i.e. floating point
operations per second. In the final column are the computer run times for the same
DAMAGE XX job. We see how a particular supercomputer simulation will be
accelerated over a period of approximately 10 years. At the top of the third column a
figure of 200 hours is given for a IBM 3090 computer. We see it progressively
reduced to a projected figure given by IBM research [21] of 3.6 seconds. This clearly
demonstrates the strength of the forward technological pull brought about by the
increase in computer speed, and by the availability of fast access storage capability.
Projections do not stop at the figures given in this diagram, and discussions with
experts [21] indicate that this is likely to be an ongoing trend. At this point, it is worth
noting that whilst the cpu speed of workstations is in the same domain as that of
supercomputers, this speed can rarely be harnessed if data intensive simulations are to
be carried out with any rapidity. Therefore cpu speed should only be judged in the
context of the overall style of usage of the computer-based simulation facility. The
weak link in the chain which connects laboratory test data to the results of
supercomputer simulation shown in Figure 4 is therefore the quality of the materials
constitutive equations or models, the accessibility to, and the quality of the associated
materials databases.
2.6 Some cross-disciplinary examples

Several examples will now be considered which are first summarized. The first one
considers the data requirements for in-service computer simulation of a high-
temperature pipe weldment [8]. The data requirements associated with the materials
selection for such a typical weldment, and its manufacture are considered in order to
maximize the lifetime performance [22]. These examples util ize the techniques of
creep Continuum Damage Mechanics (CDM) to predict the behavior of a fabricated
component from simple uni-axial test data collected on smalliaboratorytestpieces. In
the next example a ceramic fiber-ceramic matrix tough composite is considered [15],
because it is a human engineered material and therefore enforces an interaction
between the mechanical properties and processing route. This places great onus upon
an ability to simulate on the computer both the material behavior and that of the
component [6] when the precise details and architectures of the fiber arrangements are
to be varied and controlled. The data requirements for this challenging new class of
problem will be addressed [5] .
Figure 5: Creep Rupture in a butt welded O.5Cr O.5Mo O.25V Ferritic steel pipe with a
2.25Cr lMo: O.5Cr .5Mo O.25V multi-pass weld SUbjected to a constant internal
pressure of 45.5 Mpa at 565°C, the heat affected zone (HAZ) is denoted by AB: (a)
micrograph of diametral section of weld, the base-line of the figure coincides with the
weld center-line, and the left hand and right hand edges of the figure denote the inner
and outer walls of the pipe respectively, (b) computed damage field superimposed on
Finite Element mesh at a life fraction oft/tFl, failed regions have damagero>O.8 as
defined in legend, and (c) micrograph of diametral section of weld showing damage at
failure . (see also colour plate on page 393)
3 DATA REQUIREMENTS FOR COMPUTER SIMULATION OF A HIGH-

TEMPERATURE WELDMENT IN SERVICE
3.1 Definition of vessel to be designed
The vessel weldment will be defined using the part micrograph of the weldment taken
on a diametral section of the pipe shown in Figure Sa [8]. The left-hand side of the
figure marked A denotes the internal bore of the pipe which has a 230 mm diameter.
The right-hand vertical edge of the micrograph denotes the outer diameter of the pipe
which is 350 mm; this yields a pipe wall thickness of 60 mm. The vessel is very long
and the effect of the pipe ends on the weldment may be neglected. The pipe is
subjected to a steam pressure of 45.5 MPa. at a temperature of 5650C.
These conditions are maintained steady for the lifetime of the vessel. In Figure Sa the
region close to the lower edge of the figure denotes the weldment center-line. The
weld was prepared using two ICr 0.5Mo and two 2.25Cr IMo multi-pass welds. The
zone denoted by AB is the heat affected zone (HAZ) and the region of the figure
above AB denotes the parent pipe material which is 0.5Cr O.5Mo 0.25V ferritic steel.
Failure of the pipe is known to take place close to the HAZ and the object of the
simulation is to be able to predict the vessel lifetime; deformation, and strain histories;
and the evolution of damage and the formation of macro crack to cause ultimate failure
of the pipe.
3.2 High-temperature creep constitutive and damage equations
In the creep CDM analysis of the vessel we need to characterize the behavior of the
three material zones, namely the weldmaterial, the HAZ, and the parent pipe material.
To describe the creep behavior of the materials using CDM, the following equations
can be used [9,14] for multi-axial creep strain rate Eij and the damage rate cO :
d Ii·· 3G .-II-I
S .. t m
r
=..:::.JL __ e
- U
(I)
dt 2 (1- OJ !I
dOJ
(2)
dt
where 0e is the effective stress, or is the maximum principal tension stress, m, n, G, M,
X and ¢ are material constants over particular stress ranges, and a is the multi-axial
creep rupture criterion .. The constant ¢ may be obtained from tabulated values of n
and ~, where Ll = 1 - n / (¢ + 1).
0=110 0=100
.0 0=100 12
1/ --
(a) 2 (b) 0-85 (c)
2
4
Ii)" to a=02
0=56
... ... ......... "
+::_J--~
"
I I I
0 20 40 60 80 0 20 40 60 80 100 0 20 40 60
time/(lO:l h)
Figure 6: Comparison of the experimental uni-axial creep test data and the predicted
creep curves for (a) the parent metal, (b) the HAZ and (c) the weld metal, for various
test stress levels in megapascals, +++, experimental, - Predicted
The ability of these constitutive equations to predict the results of uni-axial tests
carried out in the laboratory on the parent metal, the HAZ and the weld metal is shown
in Figures 6a, 6b and 6c respectively. Very close agreement may be observed between
the experimental and predicted results.
Stress
Material Range m n G X M ~ IX cr
Parent cr$a -0.2031 4.8971 2.8531x10- 14 3.0110 1.4522x10- 10 0.2365 0.5955 120
cr>a -0.2031 10.3442 1.3485x10-25 6.9613 8.8846x10- 19 0.2365 05955 MPa
Weld cr$a -0.2031 4.3680 2.9397x10- 12 2_8554 1. 1588x10- 9 0.2679 0.4298 100
cr>a -0.2031 7.2496 5.0714x10- 18 5.7669 1.7419x10- 15 0.2679 0.4298 MPa
~ cr$a -0.2148 3.3685 1.5507x10-11 2.3009 3.2591xlO- 9 0.2799 0.4298 180

cr>a -0.2148 8.9364 4.2994xlO- 24 9.2793 5.9539x10-25 0.2799 0.4298 MPa
Table 2: Material Constants for Parent, Weld and HAZ Materials.
To cover the whole range of stress, two groups of constants can be identified for some
materials: one for low stress, and the other for high stress levels. The break stress a-
represents the transition point between levels. This results in a bilinear approximation
to the true behavior which is sufficiently accurate for most practical purposes. The
constants used in the analysis are given in Table 2 for the parent, weld and HAZ
materials. The units of all variables are those ofMPa, h., and % strain. The damage
variable given in equation (2) takes the value of 0) = 0 for the virgin material at t = 0,
and the value 0) = 0.999 at failure. The vessels strains are assumed to be composed of
an elastic component and the creep component given by equation (1). The
supercomputer analysis has been carried out using the finite element method and
creep Continuum Damage Mechanics through the solver DAMAGE XX [14].
10- 1
DYNAMIC FRACTURE
I
DUCTILE TRANSGRANULAR
-
FRACTURE
- / ' --
RUPTURE
INTERGRANULAR
CREEP FRACTURE
o 0.2 0.4 0.6 0.8 1.0
Homologous Temperature ( T / T m )
Figure 7: Schematic representation of a fracture mechanisms map. The upper and
lower shaded regions denote domains of operation for typical high-temperature
engineering components and indicate the operating fracture mechanisms.
3.3 Necessity for physics-based constitutive equations
The long duration of laboratory creep tests render them necessarily expensive. One is
therefore usually limited in the number of tests that can be used to characterize the
material behavior. In high-temperature design one very rarely has test data which
extends over the long periods encountered in service typically 1 to 2 x 105 h. There is
therefore great onus placed upon the ability of the constitutive equations to extrapolate
from short term, typically 7 x 103, to the longer in-service times. To justify the use of
this process the models must reflect the underlying physics of the processes involved.
Guidance in this work has been sought from the mechanisms maps due to Ashby [1,2]
and to Cocks and Ashby [3], a schematic version of which is shown in Figure 7.
Plotted in the figure is the normalized tensile stress on the ordinate and the
homologous temperature on the abscissa. The homologous temperature for the vessel
concerned would be in the approximate region of T/T m = O.S. Here we see that the
mechanism of fracture is dependent upon the stress level; for high stresses the failure
mechanism is transgranular creep fracture, and for lower temperatures it is
intergranular creep fracture. The approach adopted here is to recognize that the stress
level which determines the boundary between the new mechanisms is Cr. Tests have
therefore been collected for ( j > 0- and for ( j < 0-. For each of the zones sufficient
tests have been carried out to characterize the constitutive equations (I) and (2). Care
has been taken to ensure that creep strain rates and damage rates provide continuity at
the break stress Cr. One can thus guarantee that the mechanisms of deformation and
damage evolution in all three metallic regions of the welded component can be
accurately modeled. It is worth pointing out that, in general, classes of material exist
in which several mechanisms can operate concurrently and between which synergisms
can develop. For these materials more state variable equations (cf. equation (2» are
needed together with a knowledge of how the state equations and the strain rate
equation (c.f. equation (1» interact. Additional databases are required for this
additional level of complexity. The CDM approach provides traceability back from
the welded vessel to be analyzed by the supercomputer, through the constitutive
equations, to the tests carried out in the laboratory on uni-axial testpieces.
3.4 Creep continuum damage mechanics supercomputer simulation
The finite element mesh used to carry out the supercomputer simulation using
DAMAGE XX is shown in Figure Sb. The twin row of elements connecting A to B
encompasses the HAZ region. The regions above and below that represent the parent
material and the weld material respectively. The computed damage field is
superimposed on the finite element mesh at the life fraction tltf = 1, the failed regions
are shown for the damage variable (0 > 0.8.
Failure of the vessel can be seen to have taken place close to the outer bore of the pipe
in the fusion boundary between the HAZ region and the weldmetal zone. This may be
compared with a micrograph of the failed vessel shown in Figure Sc, where very close
agreement can be seen with the damage zone of Figure Sb. The predicted lifetime of
the vessel is 43,882 h which compares with the lifetime of the pressure vessel test of
46,000 h. This reflects a very satisfactory supercomputer analysis for predicting vessel
behavior. It validates a CDM analysis approach used in subsequent sections of the
paper to analyze more complex situations. The case study shows that if laboratory
creep test data is collected within the appropriate stress regimes which reflect the
controlling physical mechanisms, the approach can be used for supercomputer
simulations, able to predict longer term behavior of multi-material components.
4 DATA REQUIREMENTS ASSOCIATED WITH MATERIALS

SELECTION FOR HIGH-TEMPERATURE WELDMENT
MANUFACTURE FOR MAXIMUM LIFETIME PERFORMANCE
This section addresses the possibility of using the same analysis method, together with
an enhanced database providing information on the range of mechanical properties for
the HAZ and the weld materials which can be achieved by current welding
technology. The database will simulate the performance of a range ofweldments, each
having different combinations of weld and HAZ materials. We assume that the parent
pipe material remains constant.
This involves the creation of an ability to use the database to predict the constants in
equations (1) and (2) for a wide spectrum of HAZ and weld materials, with a
knowledge of the constitutive equations for the parent pipe material. We study the
creation of such a database from the scant knowledge available from welding
technologists and then its use, via supercomputer simulation [11,12,24], to select a
material combination of HAZ and weldment materials which maximize the lifetime of
the vessel.
4.1 Need for simplified description of material behavior
Discussions with welding technologists [18] have indicated that the level of
information available on HAZ and weld material data is low. It frequently expresses
the material behavior in terms relative to that of the parent pipe material. For example,
the minimum creep rates of the HAZ material would be factored to that of the parent
pipe material, and similar relationships would be available for strain levels and rupture
lifetimes. What is absent is extensive digital strain-time data for the creep curves, as
well as a general knowledge of the shape of the creep curves for both HAZ and weld
materials. However some data indicates that the behavior in this case is not dissimilar
from that of the parent material. Given this paucity of materials data, an approach is
adopted here which factors, the properties of the HAZ and weld materials relative to
the parent pipe material.
4.2 Transformation of simplified materials description to that

provided by the detailed constitutive equations
The approach outlined here is based upon the material data factored relative to that of
the parent material, and upon the detailed constitutive equations for the parent
material. Having couched the material description in this form, a non-linear
mathematical transformation will be sought to convert the data into the same form as
that used to describe the parent material. Some definitions are needed to help describe
the approach.
t Esec
time t
Figure 8: Schematic representation of uni-axial creep curve giving definitions of

primary, cpri, secondary, csw tertiary, Clef' and failure cf' creep strains.
Shown in Figure 8 is a schematic representation of a creep curve defining parameters:

the rupture strain E:R, the primary strain E:pri' the secondary strain E:sec, and the tertiary
strain E:ter (= C R - csec - C pri). Using this terminology it is now possible to define
the following normalized parameters:
The normalized primary creep strain

_ I cpri l _
K = l J where K is average value between 0"1 & 0"2·
cR (0"j,0"2)
_ I cR l
The normalized rupture strain:
r=l-J
c~ (0- J, 0"2 )
where superscript b indicates values for parent pipe material.

The normalized rupture strain at the break stress level:
where superscript /\ indicates values at break stress.
The normalized secondary creep strain: e

-
= lI {
csec
b
/
\Csec /
cR
b
cR
l
)J
(ab a2)
- It l
the normalized rupture lifetime: .; = l :J
tR (al. a2)
the normalized rupture lifetime at the break stress: .;= tRla=o-

t~1 a=(}>
Material Property Ratios Material Constants in

Expressed in terms of base Constitutive Equations
material properties
Figure 9: Schematic representation of non-linear mapping from material property

ratios, expressed in terms of base material properties, to the material constants used in
the constitutive equations
Wang and Hayhurst [22,23] and Perrin and Hayhurst [19] have shown that it is
possible to define a non-linear mathematical transformation between the normalized
parameters defined above and the material constants defined in equations (1) and (2),
which is shown schematically in Figure 9. The non-linear mapping is embodied in a
Normalized Normaliscd creep curves
Materials Parameters Parent -

0.8 Weld-
~=~" 0.050000
0.6
6=Eh 1.1224
7 2.3887 0.4
[ 0.5000 0.2
7" 1.2051
[" 0.1447 0.2 0.4 0.6 0.8 1.0
.y t/tn
1.4472
i 0.3613 Relationship between rupture stress and lifetime
1000 ........~..,.....,~.................'"'""-,-,~or-""..........
A 0.8333 Parent -
Weld-
(1'
Constitutive Parameters (MPa) 100
(Low Stress)
m -0.5053
n 4.4116
G 1.8919 x 10-11
X 2.8990 Relationship between minimum strain rat. and stress
10°r-~~~~~~--~~~~~
M 9.0257 x 10-9 Parent -
10-1 Weld-
ll. 0.2214
10-2
fr = 100MPa
. 10-3
Em;" 10-4
10-5
Constitutive Parameters 10-6
(High Stress) 10-7~~~~~~~~~~~~
10 100 1000
(1' (MPa)
m -0.5053
n 5.0627 Relationships between strains and stress
100 ~--...--.-..,.....,............-~.,...........,..,.......... 100
G 9.4365 X 10-13 eR f. ee
Parent--
X 3.5803 Weld--
M 3.9160 x 10-10 10 10
f,ee
ll. 0.2214 En (%) =E...;..tn
(%)
1 1
'Constitutive parameters
0.1 0.1
have units of MPa, hour, 10 100 1000
and % strain. (1' (MPa.)
Figure 10: Graphical and Tabular presentations of materials data in terms of

mechanical property ratios and of constants in the constitutive equations
software package; the normalized parameters given above are its input, and the
outputs are the materials constants of equations (1) and (2) for stresses above and
below the break stress level u. This output is presented in Figure 10. The three tables,
in the top left-hand comer show the normalized parameters for the weld material; and
the two tables below that provide the constitutive parameters for stresses above and
below the break stress, called low and high stress respectively. On the right-hand side
of the figure four graphs are presented. In the top right-hand comer is the normalized
creep curve for both the parent and weld material; this enables one to judge the
correctness of the shape of the creep curve for the weld material. Below that are two
figures for the creep rupture and minimum creep rates presented on log-log axes. The
figure at the bottom right-hand side ofthe page presents log rupture strain data against
log stress; on the same figure is the Monkman Grant constant [17]. These figures were
constructed so that materials scientists and engineers can graphically assess the
relative merits of the weld material properties as compared with those of the parent
materials. Failure to obtain the desired material properties after the first materials
transformation simply requires repeated iteration with new starting values of the
normalized parameters until one converges upon the desired property ratios. The
output from the two tables at the bottom left-hand side ufthe figure provides the input
to the supercomputer simulation.
4.3 Materials selection for weldment manufacture to yield optimum

lifetime performance
The first question in this section is: what are the values of the normalized parameters
to be selected for the HAZ and weld materials? Discussions with welding
technologists [18] quickly identified a lack of precision in their ability to specify the
property ratios, however they were able to bound the values with some confidence.
This led to three values for each of the parameters K, e, y, and ,;; they are
expressed here in terms of the normalized primary creep strain K; which takes the
particular values Ke for the lower bound, Ku for the upper bound and Km for the
mean value. The same subscript nomenclature is used for all the normalized material
parameters. We now had to systematically group these parameters in order to be able
to objectively assess the behavior of pipe weldments composed of particular materials
combinations. The strategy for this is discussed in the next section.
4.3.1 Strain accumulation and stress redistribution without damage
Since it is well known that in the absence of the evolution of creep damage, stress
redistribution takes place from the initial elastic response to that associated with
steady state creep. With damage and lifetime effects excluded from this process, the
behavior could be reflected by examination of the property combination K e. Table 3
shows a matrix of K e which provides nine combinations about a central value of
Km 0 m· By carrying out supercomputer simulations using these nine material

combinations for the HAZ and weld materials it is possible to map the entire domain
of weldment behavior corresponding to the range of material behaviors which can be
achieved by current welding technology.
Kf!0 f! Kf!0 m Kf!8u
Km 8 f! Km 8 m Km 0 u
Ku 8 f! Ku 8 m Ku 8 u
Table 3: Matrix of the product K 0 of the normalized primary creep strain, K, and
the normalized secondary creep strain parameter, 0. The subscripts £, m and u
denote lower, mean, and upper bound values. The product K 0 reflects the ability of
the material to accumulate creep strain in the absence of damage.
4.3.2 Strain accumulation and stress redistribution due to damage
The factors which influence the strain accumulation and the associated stress
redistribution in structures, due to damage, are reflected by a combination of the
normalized rupture strain r and the normalized rupture lifetime'; . The combination
of these properties r.;
which has been selected was carried out by the same
procedure discussed for Table 3. The material combinations are defined in Table 4
r
where nine values have been selected about a mean value m';m . Variations between
the lower bound value and the upper bound value will map the domain of material
properties achievable by present welding technology. The mean values shown in
Tables 3 and 4 coincide with those for the vessel discussed in Section 3.
rf!~e rf!~m rf!~u
rm~f! rm~m rm~u
rU~f! ru~m ru~u

Table 4: Matrix of the product r.; of the normalized creep strain at rupture, r, and
the normalized time to rupture, .; . The subscripts I, m and u denote lower, mean, and
upper bound values. The product r.;
reflects the ability of the material to accumulate
creep strain in the presence of creep damage.
4.4 Selection of optimum weld and heat affected zone materials

properties and their use to simulate weldment behavior
Given the data presented in Tables 3 and 4 we select one materials property group
each from Table 3 and from Table 4 for both the HAZ and weld materials. These can
then be used together with the detailed constitutive parameters for the parent pipe
material, in the non-linear materials property transformation, cf. Figure 9, to produce
the constitutive parameters for the HAZ and weld materials as required by equations
(1) and (2). This data is then input into the finite element simulation of the same
geometry of welded vessel as that analyzed in Section 3.0, together with the same
temperature and pressure boundary conditions. The performance of the weldment with
the proposed material combinations may be judged against that for the vessel with
mean property values. This process can be repeated for all possible combinations of
the materials listed in Tables 3 and 4, and the optimum combination of materials
properties identified. The best materials combinations for both HAZ and weld
materials are then summarized in Table 5. In both cases we see that the best
combination of primary and secondary properties are those given by the upper bound
and mean values respectively, and the best combination of normalized rupture strain
and normalized rupture lifetime properties are those given by the mean and upper
bounds respectively. It is thus important to accumulate large amounts of primary
strain early in the lifetime of the vessel before damage has had an opportunity to
accumulate. This makes the level of damage growth rate more uniform. The selection
of the normalized rupture strain and the normalized rupture lifetime properties is such
that a mean value of the rupture strain is selected to permit adequate stress
redistribution during tertiary creep, and hence minimizes the stress to which the
material is subjected. In addition, the lifetime of the welded vessel is maximized by
selection of the upper bound value of the normalized creep rupture lifetime.
WELD Material:
HAZ Material:
Table 5: Combinations of best materials properties involving: the primary, K, and the
secondary, e, normalized creep strains; the normalized creep strain at rupture, r;
and the normalized time to rupture, ;. Property groupings are given for both the
weld and heat affected zone HAZ materials.
A material combination has thus been identified which increases the lifetime of the
vessel from that of 43,882 h for the case of the mean value normalized materials
property data to a value of 61,330h for the optimum data set; this corresponds to an
increase of almost 30%. These figures compare extremely well with the lifetime of
69,853 h for an unwelded pipe composed solely of the parent material.
: 3 .1 8xI0" • 4.09xl0·'
• 2.9lxI0" • 3.85xl0·'
• 2.65xI0·3 • 3.4IxI0·'
2.38xI0·' • 3.07xl0·'
2.12dO·' 2.73x10·'
1.85dO·' 2.39xI0·'
• 1.59dO· 3 2.04xl0·'
• 1.32x10·' • 1.70xl0·'
• 1.06xI0·' • 1.26xlO·'
• 7.94x10·' • 1.02xlO·'
• 5.29.10" • 6.82xI0'"
2.65dO·' • 3.4lxlO·'
• 4 .42>10" • 9 .2 3xl0·'
• 4.05xI0·' • 8.46xl0·'
• 3.6 8xI0·' • 7.6 9xlO·'
• 3.3 IxlO·' • 6.9 2xI0·'
• 2.94xl0·' 6.15xI0·'
2.58xlO· 1 5.38xI0· '
2.21.10') 4.62xI0· '
• 1.84xl0·' • 3.85xI0· '
• 1.47xl0·'
• 3.08x\O"'
• 1.10xI0·' • 2.3IxI0·'
• 7.36xlO·' • 1.54xlO·'
• 5 8. 0xl0·' • 7.69xI0·'
Figure 11 : Field distributions of the damage variable w over a diametral section of the
weldment determined using the optimized materials data sets for the weld and HAZ
materials: (a) tltrO .0005, (b) tltrO.109, (c) t/trO .863 and (d) tltrl.O
4.5 Visualization and animation of damage evolution
Figure 11 shows field distribution plots of the damage variable co over a diametral
section of the pressure vessel, determined using the optimized materials data sets for
the weld and HAZ materials at four different normalized lifetimes tltf. Figure II(a)
shows the damage distribution early in the lifetime of the vessel: accelerated damage
growth at the inner bore of the pipe and within the weld material region . The level of
damage reduces as one progressively moves radially outwards towards the outer bore
of the pipe. After approximately 11 % of the lifetime the damage distributions shown
in Figure II(b) indicate that the distribution of damage is relatively unifonn

throughout the weld material region. However, we observe that damage is found to be
maximum within the HAZ region at the inner bore of the pipe. Figure II (c) presents
data at 86% of the lifetime and indicates that the damage levels for the majority of all
three material zones are approximately at the same level, with higher levels of damage
concentrated in the HAZ, on the inner bore of the pipe, and also on the outer bore of
the pipe in the zone known as the Type IV region, located between the HAZ and the
parent pipe material. The damage distribution at failure is shown in Figure II(d)
where failure is almost simultaneously taking place in three regions: the HAZ on the
inner bore of the pipe, the Type IV zone close to the outer bore of the pipe and on the
outer bore of the parent material above the Type IV region. We see that by optimizing
the material properties we achieve a much more unifonn distribution of damage across
all material zones. The detailed way in which this evolution takes place has been
shown by a continuous video animation. This permits one to cross-correlate damage
evolution with the evolution of creep strain; and with the maximum principal stress
and the effective stress, which play an important part in the evolution of creep damage
through equation (2). By constructing screen images so that they replicate what the
materials scientist views in the microscope, cf. Figure 5c, the scientist gains an added
dimension in understanding the weldment. Supercomputer simulation thus provides a
tool which bridges the cross-disciplinary interests of the physical metallurgical
weldment scientist, on the one hand, and the engineer stress analyst, on the other.
5 SUMMARY OF MATERIALS INFORMATION AND DATA

STRUCTURES REQUIRED FOR MANUFACTURING WELDMENTS
WITH OPTIMUM LIFETIME PERFORMANCE
Two main requirements exist here. The first is to establish a database with individual
records of raw strain data at a series of times defined throughout the lifetime of a uni-
axial test testpiece. The frequency of the records will depend upon the level of
precision necessary to describe the creep curve. This infonnation will be stored for a
range of stress levels, and if necessary a range of temperatures. The data will be the
lowest level of data accessible by software. It will then be used to derive the material
constants in equations (I) and (2) using techniques discussed by Dunne et al [4] and
by Kowalewski et al [16]. To identify the operating domains of the appropriate
physical mechanisms further information needed which is incorporated in the
mechanisms diagrams of the type in Figure 7. Given this structure of database for the
parent, the weld, and the HAZ materials one can then carry out a supercomputer
simulation using CDM which will give accurate predictions of strain and damage
accumulation, and failure of the vessel.
The second type of data relates to the analysis with a coarse level of precision in the
specification of the weld and HAZ materials. Here the requirements are different.
However, one still needs high quality data for the parent material, as specified above,
but in addition one has to tolerate the coarser information for the weld and HAZ
materials associated with the property ratios. This type of data is more subjective and
involves the knowledge accumulated over many years by specialists in weldment
technology. The specialist may originate from the fields of physical metallurgy,
engineering and stress artalysis. This information must be acquired and stored in a
suitably accessible form. One then needs software to enact the materials property
transformation described in Section 3.0 due to Wang and Hayhurst [23]. Given these
very different sets, and structures, of material data it is possible to carry out a wide
range of supercomputer analyses involving speculative selections of weld and HAZ
materials properties. The weldment simulations reveal that three basic ingredients are
necessary: (i) raw laboratory data, (ii) subjective human data embodying expert
knowledge, and (iii) software capable of accessing the data in (i) and (ii) to convert
these into usable higher order precision data.
6 INFORMATION AND DATA REQUIREMENTS FOR THE ANALYSIS

OF COMPONENTS MANUFACTURED FROM ADVANCED FIBER
REINFORCED CERAMIC MATRIX COMPOSITES
The ceramic composite was selected for its human engineered characteristics; this
brings about a totally different set of materials data requirements for use in design.
The breadth of the requirements is greater, and the need to provide guidance from
mechanistic-based modeling is stronger, than in the cases examined earlier for
conventional isotropic materials.
Figure 12: Schematic representation of un i-directional Tough Fiber Reinforced

Ceramic Matrix Composite
6.1 Modeling the physical processes of deformation and damage

formation
6.1.1 Uni-axial Behavior
A unit cell of the tough fiber reinforced ceramic matrix composite is shown
schematically in Figure 12. The remote applied stress 1:00 is normalized in terms of
the fiber failure stress aJf The damage and strain evolution laws for this material are
developed. As the composite is loaded in tension, matrix cracking first takes place as
shown in Figure 13a. Further loading results in fiber failure which is modeled as
follows. Assume that the probability of a fiber not failing at stress (j is given by the
Weibull distribution [15]:
G(a)= 1-[ exp ta l a t].
fr
Define the ratio r of failed fibers to total number n:

r I n = G(O') = (j) ,
where OJ is the damage state variable.
Then:
O'o l O'JJ =(l-{j)t[-ln(l-m)f M (3)
where 0'0 is the normalized fiber stress, a = 0'0 I (1 - (j) ), and A reflects the non-
linear effects of damage.
a)
MATRIX
CRACKS
"'' ' ' ' ' /
2R pull-out distance
Figure 13: Schematic representation of: (a) matrix cracking and debonding, and (b)
fiber pull-out in a uni-directional Tough Fiber Reinforced Ceramic Matrix Composite
In addition to the load carrying function of the fibers prior to fiber failure, a second
mechanism results in additional loading bearing capability [15], that of the pull-out of
failed fibers from the matrix, shown in Figure 13 (b). Fiber ~ilure takes place inboard
of the matrix crack and the fiber pulls out over the distance h . A fiber fails at a value
of 0"0 / O"ff given by the modified Weibull equation at a damage value apo.
Subsequently the fiber is assumed to sustain a normalized stress related to m by:
where apdOjfis the maximum individual fiber pull-out stress, also denoted byS, and
D is a constant which determines the 0" - (0 decay characteristic.
The contribution to nominal fiber stress from all fibers failing between OJpo = 0 and
OJpo = m is:
cTO(W)=S(I-Wf -(1-W») (4)

uif (I-D)
Then the total nominal fiber stress is given by the addition of equations (3) and (4):
and the total nominal composite stress is:
where the fiber volume fraction a = Vf / V.
The corresponding composite stress-strain relationship may be determined using the

elastic properties of the fiber from:
d(s", / sif ) = dA", = 1 + (u", / uff)B il{l/ MX-In 1- w \(I-MYM

d(u"'/Uff) d'L", Cll(I-wt Cll(1-wjB+I)Lt (), (6)
-A (-In (I-w ))IIMJI- w )(A-I) +s (I - D r~ l - D(I- w )(D-I»)J.

where &jfis the fiber failure strain determined from o/IE.
0.8
-
en
en
...
U
en
'tl
.~ 0.4
C;;
E
o
c
o 3 6
normalized strain
Figure 14: Theoretical predictions of un i-axial behavior of un i-directional tough fiber

reinforced ceramic matrix composite, parallel to the fibers, shown by full lines; and
the contribution to stress carrying capability provided by the pull-out mechanism,
shown by broken lines. Curves present different values of pull-out stress S(=crpo/crff)
with M=lO, D=0.9, B=2 and A=1.05
Integration of equations (5) and (6) yields a normalized stress-strain curve for the
composite in Figure 14. The solid lines denote five stress-strain curves for different
values of the normalized fiber pull-out stress S. The broken lined curves denote the
magnitude of the component due to fiber pull-out alone for the same values of S.
The shelf on the figure at the normalized stress of 0.4 corresponds to the loss of matrix
stiffness due to cracking. Figure 14 shows how the mechanism of fiber failure and
fiber pull-out introduces ductility to what would be otherwise a brittle material, by
tailoring the interface to achieve the pull-out characteristic [15]. Equation (6) clearly
shows the importance of the parameters Sand D, together with the Weibull Modulus
M, in determining the stress-strain response of the material. These are quantities for
which materials data is required to tailor the material to have the required mechanical
properties. In order to study the behavior of an engineering component fabricated
from this material, and to investigate the implications in terms of supercomputer
modeling, it is necessary now to generalize the uni-axial stress-strain model to two
dimensions.
6.1.2 Bi-axial behavior
The bi-axial properties of the unit cell shown in Figure 12 are determined by the
integrity of the matrix, its elastic properties, and how these are affected by the various
phases of cracking. A model has been constructed based upon the linear elastic
response of the matrix which is changed in a piece-wise linear way according to the
formation of matrix cracks perpendicular to the applied tension stress, transverse to
:J.r:
E.,.A12
(a) ~
.,; ~ - 2.S ---'
1 '\)
~ - .s~ /, E",). ••
""
v ty, - 0 f1
.----
~ /tf:.+
'" 1:" - 0
/1' q= ).,,/)..,
AI I
4' I
!: /~ I
W .... ~r..1 I
a .,;'"
/~ I
l:J 1 ~ 71.0
Vl I
I
'"OJ.~N
~
I
~ .!. 0.6
I
I
I
§ '" I I
Z
0
f I
1
I I
~ ~ 0.6
I I
I I
'".,; I I I
I I I
I
I I I
I
I I
I
I
0.0. 0.06 0.09 0. 10 0. 12
Normalized Strain >." .
(b) ~
.,;
E",)." ~
~
~ - 0.4 ~ - 0.6
~ - 0.8 q = 5."/).,,
o'"
~ . oo 0 .02 0. 0. 0. 06 0.09 O. to 0 .1 2
Normalized Sirain >."
Figure 15: Theoretical predictions ofbi-axial behavior of a uni-directional tough fiber

reinforced ceramic matrix composite when loaded in tension perpendicular to the
fibers and in shear parallel and perpendicular to the fibers for different values of the
parameter 11 (a) ~22-A22 and (b) ~lTA22 with M=10 S=0.20 A=1.02, B=1.10 and
D=0.46
the fibers and in shear on planes perpendicular to the fibers. In this way Haddad [S]
has produced a bi-axial strain relation expressed in terms of the stress tensor crij' the
damage value ill and two additional damage variables 'I'SDP and 'I'TDP given by
(7)
where ill is the damage due to fiber failure, 'I'SDP is the damage due to shear in
planes perpendicular to fibers, and 'I'TDP is the damage due to tension transverse to
the fiber axes.
It is the damage variables 'I'SDP and 'I'TDP which determine the extent of the
modification of the elastic properties of the matrix due to the various cracking modes.
Examples of the results of predictions made using equation (7) are shown in Figure IS
for the shear stress 2:12 parallel and perpendicular to the fibers combined with the
stress 2:22 transverse to the fibers. The boundary conditions are given in Figure IS in
terms of YJ = A22/AI2, where Aij is the normalized strain rate. Figure IS(a) shows
the change of the transverse stress with the transverse strain ,1,22' and Figure IS(b)
shows the change of normalized shear stresses 2:12 with the normalized transverse
strain ,1,22' The two graphs show the interaction between failure due to transverse
cracking and to cracking due to shear. Equation (7) therefore produces the very
tttt
~;,., --~~
II - 'II/
0
- IIIIII ./
111 1
Figure 16: Schematic representation of uni-axial tension panel containing a central
circular hole. The un i-directional fibers are aligned with the tensile loading axis
characteristic stress-strain responses observed in experiments carried out on this

material. To assess the importance of the terms in this bi-axial model with regard to
the prediction of the behavior of model engineering components, equation (7) has
been used to predict the behavior of a tension panel containing a central circular hole.
6.2 Supercomputer simulation of a simple component
The component to be simulated is shown schematically in Figure 16. The uni-

directional fiber panel is subjected to uniform tensile loading parallel to the axis of the
fibers, and the panel contains a central circular hole. A CDM finite element analysis
has been carried out of the plate and the distribution of the shear damage parameter
\}' SDP is shown in Figure 17 close to failure. The computations show that the
dominating damage variable is the shear damage parameter \}' SDP .
For this particular problem the transverse damage parameter \}' TDP is not activated
because of the low levels of the transfer stress.Of particular note is the fact that the
fiber damage failure parameter 0) reaches its critical value of unity in the close
proximity of the edge of the hole where the strain is most severely concentrated, but
that this mode of failure by no means controls the overall behavior of the plate.
Figure 17: Theoretical predictions of the shear damage parameter 'I'SDP field in a
region close to the edge of the hole (bottom left hand corner of figure). The base line
of the figure coincides with the horizontal axis of symmetry of the plate. The yellow
region denotes shear damage failure 'I'SDP =1, the dark blue region denotes virgin
material and intermediate colors denote linearly interpolated values
Hence this analysis shows that for supercomputer simulation of model components
fabricated in this material and subjected to multi-axial states of stress, complex
constitutive equations are required which embody state variables related to the
physical mechanisms which control the damage process. In particular both uni-axial
and bi-axial test results are required to characterize the material behavior and to
detennine these material properties. Thus for such human engineered materials a high
level of complexity of the equations is required to describe the physical response of
the material. In order to detenuine the important parameters and the associated data
requirements, guidance must be sought from models which reflect the physical
mechanisms of deformation, damage and failure.
6.3 Future synergies between design and manufacture of

components with human engineered materials
It is evident from the modeling studies reported in this paper concerning tough
ceramic fiber - ceramic matrix composites that the damage evolution and failure
modes are complex and strongly dependent upon the fiber orientation relative to the
predominant stress and strain field conditions within the engineering component. In
order to avoid triggering unwanted damage and failure modes it is therefore necessary
to design the placement of fibers within components which are to transmit particular
force systems along particular trajectories. We must postulate certain fiber layouts,
and then carry out supercomputer simulations to assess their efficacy. If a first
analysis shows that unwanted damage and failure modes are being activated then the
fiber architectures require suitable amendment to avoid the known failure modes.
The extent to which fiber architectures can be adjusted will be subjected to

manufacturing requirements and constraints. It will be therefore necessary at the same
time to carry out simulations of the component manufacturing processes; and these in
tum will place constraints upon what can be achieved in tenus of load carrying
capability, of the directions of load transmission, and of the damage and failure modes
which can be activated. Hence, we expect a strong synergy between the design and the
manufacturing process which can only be unraveled by a series of successive
supercomputer analyses of both the design and the manufacturing phases. Thus the
optimal component performance will be achieved for given material systems.
7 SUMMARY OF MATERIALS INFORMATION AND DATA

STRUCTURES REQUIRED FOR MATERIALS DESIGN FOR
MANUFACTURE OF ENGINEERING COMPONENTS WITH
OPTIMIZED IN-SERVICE PERFORMANCE
In detailed design using supercomputer simulation the type and level of precision of
the data required is a function of knowledge of the mechanisms of deformation and
fracture. For example in the case of the well characterized weld, HAZ and parent
material encountered in the welded pipe, the detailed creep data coupled with the
deformation and fracture mechanisms maps provide a highly reliable route to
supercomputer analysis. The level of knowledge is decreased with the requirement to
know the constitutive equations for materials in weldments not hitherto produced and
tested; then one requires techniques to translate expert opinion into precision
descriptions which make use of mechanisms-based constitutive equations. Software is
needed to make the required transformation of data. In both of these cases software
then takes the raw data and computes the constants in the constitutive equations.
Hence, for such near isotropic materials the raw, and expert data need to be acquired
in a form suitable for input into software packages which will convert them into the
constitutive equation form suitable for input into supercomputer simulation. However,
strong guidance, and the imposition of relevant constraints, must be inputted from the
physics associated with the deformation and fracture mechanisms. Human engineered
materials are new and involve levels of knowledge and degrees of precision which are
low by comparison with the established isotropic materials. In these situations
guidance is sought ab initio from the physics of the processes of deformation, damage
and fracture. Thinking and modeling must be guided by the basic physics. Short-cuts
often provided by expert knowledge and experience cannot be tapped in this case.
The principal difference with these materials is the dependence of the mechanical
properties on the manufacturing function, and the ability to configure fiber
architectures expedient in maximizing desirable features and properties and
minimizing undesirable ones. These complex optima can only be achieved through
supercomputer simulation, which in tum can only be carried out if the physics-based
deformation, damage and fracture models are available, together with the relevant
input data. In short, whatever the materials system, accurate physics-based models are
required, together with data and software needed to calibrate them.
8 CONCLUSION
In order to be able to carry out supercomputer simulations at the detailed stage of

design, which may also involve interaction with the manufacturing function, it is
essential that materials databases are available. The content of the databases must be
sufficiently wide, complete and accurate to guarantee accurate predictions through
computer modeling and meaningful predictions in terms of simulated in-service
performance, and of materials in manufacture. Without the guarantees of availability
of accurate data, supercomputer simulations are pointless.
The data within the databases must cover a sufficiently wide range of physical
circumstances to make the above objectives realizable. Completeness of a materials
database for a given range of functions is therefore essential. Bearing in mind the long
lead times required to collect data and to establish the database in an appropriate form,
long term forward planning is necessary. In order that the data can be used in an
interpolative and in an extrapolative capacity, it is necessary that the database can be
augmented by information on mechanisms maps which relate to the processes of
deformation, damage and failure.
In this way the raw data will be coupled to constitutive equations which model
macroscopically the physics of the microscopic processes. The establishment of this
coupling is crucial to success in supercomputer modeling. The database architectures
must recognize that new applications will demand use of raw data so incomplete that it
has to be augmented by other inputs. The examples shown here involve the
augmentation of data from expert opinion and experience. To translate basic materials
data into constitutive equations, it is necessary to access the data for input into
software which will carry out various transformation and fitling processes which
involve the use of optimization techniques, and non-linear materials property
transformations.
The data has therefore to be accessible and portable. In the case of human engineered
materials, all the above conclusions are even more pertinent because of greater
ignorance and incompleteness of data. For these new materials the strength of the
synergisms between the design and the manufacturing functions is stronger and more
closely linked.
The achievement of optimum design configurations involves the solution of

optimization problems which are complex and interactive, and require supercomputer
simulation to obtain near optimum solutions. Due to the paucity of data for the newer
materials greater reliance has to be placed upon the physics of the deformation,
damage and fracture processes.
KEYWORDS
design process, simulation, manufacture, optimized selection, deformation, damage,

ceramic matrix composite
REFERENCES
[1] Ashby, M. F., A first report on deformation-mechanisms maps. Acta Metall., 20,
(1972),887-892.
[2] Ashby, M. F., Materials Selection in conceptual design, In Materials and
Engineering Design: The Next Decade, Ed. B. F. Dyson and D. R. Hayhurst, The
Institute of Metals, London, (1989), 13-25.
[3] Cocks, A. C. F. and Ashby, M. F., On creep fracture by void growth, Progress in
Materials Science, 27, (1982), 189-244.
[4] Dunne, F. P. E., Othman, A. M., Hall, F. R. and Hayhurst, D. R., Representation of
uni-axial creep curves using Continuum Damage Mechanics, Int. J. Mech. Sci., 32,
(1990),945-957.
[5] Haddad, S. H., Studies in Ceramic Composite Materials and Structures using
Continuum Damage Mechanics, PhD Dissertation, The University of Sheffield,
UK, (1991).
[6] Haddad, S. H., Hayhurst, D. R., and Leckie, F. A., Design of uni-axially loaded
components fabricated from tough fiber-reinforced ceramic matrix composites,
Proc. Roy. Soc. Lond. A, 434, (1991), 383-397.
[7] Hall, F. R. and Hayhurst, D. R., Modeling of Grain Size Effects in Creep Crack
Growth Using a Non-local Continuum Damage Approach, Proc. Roy. Soc. Lond.
A, 433, (1991), 405-421.
[8] Hall, F. R. and Hayhurst, D. R., Continuum Damage Mechanics Modeling of High
Temperature Deformation and Failure in a Pipe Weldment, Proc. Roy. Soc. Lond.
A, 433, (1991), 383-403.
[9] Hayhurst, D. R., Creep Rupture under Multi-Axial States of Stress, J. Mech. Phys.
Solids, 20, (1972), 381-390.
[10] Hayhurst, D. R., Computer Aided Engineering: integrating themes, In Materials
and Engineering Design: The Next Decade, Ed. B. F. Dyson and D. R. Hayhurst,
The Institute of Metals, London, (1989), 113-117.
[11] Hayhurst, D. R., The use of Computational Creep Continuum Damage Mechanics
to Optimize Materials Selection for High-temperature Weldments, Modeling and
Simulation in Materials Science and Engineering, 2, (1994), 421-438.
[12] Hayhurst, D. R., The use of Continuum Damage Mechanics in Creep Analysis for
Design, Jnl. of Strain Analysis, 29, 3, (1994), 233-241.
[13] Hayhurst, D. R., Alsop, M., and Stone P.G., The Wealth Creation Process:
Experiential Learning through Competitive Industry-led Group Design Projects
and Underpinning Lectures, Jnl. of Eng. Design, 5, (1994), 4, 315-337.
[14] Hayhurst, D. R., Dimmer, P. R. and Morrison, C. J., Development of Continuum
Damage in the Creep Rupture of Notched Bars, Phil. Trans. R. Soc. Lond., A, 311,
(1984), 103-129.
[15] Hayhurst, D. R., Leckie, F. A. and Evans, A. G., Component design-based model
for deformation and rupture of tough fiber-reinforced ceramic matrix composites,
Proc. Roy. Soc. Lond. A, 424, (1991), 369-381.
[16] Kowalewski, Z. L., Hayhurst, D. R. and Dyson, B. F., Mechanisms-Based Creep
Constitutive Equations for an Aluminium Alloy, J. Strain Analysis, 29, 2,
(1994),1-8.
[17] Monkman, F. C. and Grant, N. J., An Empirical Relationship between Rupture Life
and Minimum Creep Rate in Creep-rupture Tests, Proc. ASTM, 56, (1956), 593-
605.
[18] Nuclear Electric, Private Communication with R. A. Ainsworth and M. C.

Coleman, Berkeley Nuclear Labs, Gloucestershire, (1991).
[19] Perrin, I. J. and Hayhurst, D.R., A Method for the Transformation of Creep
Constitutive Equations, Int. J. Pres. Ves. & Piping, 68, (1996), 299-309
[20] Preiss, K., Integration of Materials Data into Concurrent Engineering, Proceedings
CODATA Workshop on Materials Data for Computer Aided Engineering,
February 1993, Frankfurt, Germany.
SERC, Strategic Users, IBM/SERC Supercomputing Joint Study, Science and
Engineering Research Council (SERC), Rutherford and Appleton Laboratory,
Proceedings, April, (1991).
[21] Wang, Z. P. and Hayhurst, D. R., The use of supercomputer modeling of high-
temperature failure in pipe weldments to optimize weld and heat affected zone
materials property selection, Proc. Roy. Soc. Lond. A., 446, (1994),127-148.
[22] Wang, Z. P. and Hayhurst, D. R., Materials Data for High-Temperature Design of
Ferritic Steel Pressure Vessel Weldments, Int. J. Pressure Vessels and Piping, 55,
(1993),451-479.
[23] Wang, Z. P., Hayhurst, D. R., Bilby, B. A. and Howard, I. C., Vectorisation and
parallel processing studies using a Cray X-MP in non-linear computational solid
mechanics. Engineering Computations, 10, (1993), 387-395.
MICROCOMPUTER AIDED TOMOGRAPHY OF
COMPOSITE MATERIALS
Dog/iu WU*, Claude BATHIAS* and Frederic POTTER**
*CNAM, 2, rue Conte, 75141 Paris Cedex 03

**Ecole Nationale des Telecommunications, rue Barrault, 75013 Paris
ABSTRACT
For more than three years our laboratory has been working on applications of a
medical scanner for observation of high performance composite materials used in
aircraft. Computer aided X-ray medical tomography appears very suitable for studying
damage and micostructure of composite materials on a mesoscale. However, the
medical software is not well adapted for scientific purposes. In this respect, we are
developing a new software compatible with PC computers and able to rebuild images of
composite materials at mesoscale dimensions.
This program, called Ultiscan Visu 0.93, is used for displaying, analyzing, three-
dimensional rebuilding of images of tomography. The special procedure for
tomographic images uses optimal pseudo-color and gray levels to show most of the
details. Several examples about composite materials defects are given in this paper.
RESUME
Depuis plus de trois annees notre laboratoire travaille sur I 'utilisation du scanner
medical a l'observation des materiaux composites de haute performance utilises en
aeronautique. La tomogaphie medicale a rayon X assistee par ordinateur semble tres
utile a I'etude des dommages et des microstructures des materiaux composites a
moyenne echelle. Cependant, Ie logiciel medical n 'est pas bien adapte aux objectifs
scientifiques. Dans cette optique, nous avons developpe un nouveau logiciel pour
ordinateur compatible PC et capable de reconstruire I 'image des materiaux composites
amoyenne echelle.
Ce programme, appele Ultiscan Visu 0.93, est utilise pour l'affichage, I 'analyse, la
reconstruction d'images 3D. La procedure specifique pour les images tomographiques
utilise des pseudo-couleurs et des niveaux de gris pour mettre en evidence les details.
Plusieurs exemples relatifs ades defauts dans des materiaux composites sont presentes
dans ce papier.
1 INTRODUCTION
For more then ten years our laboratory has been working on the application of medical
tomography for the observation of high performance composite materials used in
aircraft. Computer-aided X-ray tomography looks very suitable for study of damage
and microstructure of composite materials at a mesoscale. An important problem is
that the medical software is not well adapted for scientific purposes. In this respect,
we are developing a new software compatible with PC computers and capable of
rebuilding images of composite materials at a mesoscale in three dimensions.
The image data coming from the floppy disk which is to be reconstructed by medical
tomography, should be backed up and converted to a PC format; from this will be
extracted a 256x256x12bit or 512x512xl6 bit image matrices, and all parameters of
the slices will be written on the head of a new file. An 80486 based PC computer with
VESM SVGA board can well show the tomographic image; with 16MByte extended
memory, it is possible to simulate the tomography console and carry out some special
functions for scientific purposes.
2 MEDICAL TOMOGRAPHY
A medical tomographic image is described by the Houndsfield density HD, which

depends upon the linear attenuation coefficient f.1
where f.1w is the water attenuation coefficient; K is a constant that depends on the
particular tomography machine [I]. A narrow beam of monoenergic photons with
energy E and incident photon intensity 10 on passing through a homogeneous absorber
of thickness x, will have an emerging photon intensity I given by :
I == 10 exp[ -f.1(p,Z,E)xj
where p is the physical density and Z is the atomic composition of the material; f.1 is
related to three modes of photon interaction: (i) coherent scattering f.1R (Thomson or
Rayleigh scattering); (ii) photoelectric effect f.1T and (iii) Compton effect f.1C
Micro-Computer Aided Tomography of Composite Materials 227
The mass attenuation coefficient)lm is defined as )l divided by the material physical

density p. )lIp is proportional to the total photon interaction cross-section per electron,
cr, as:
where N A is Avogadro's number and A is the atomic mass of the material. cr is also
the sum of the contributions from those individual photon interaction mechanisms, as:
Normally in medical scanning, from 100 KV to 140 kV of X-ray energy have been
chosen to treat low-Z materials, for example, carbon composite materials, rubber,
polyethylene. The major contribution of the attenuation coefficient comes from the
Compton scattering (more than 60% ) and the coherent scattering ( less than 24% ).
[2,3] The differential scattering cross-section of photon interaction can be given by the
Classical Electrodynamics theory:
with v = 1+r(1- cose)
where ro and me are the classical electron radius and mass, C is the photon velocity
[4]. It is convenient to get the X-ray attenuation coefficient from the tomographic
image pixel value, and hence to get more detailed information about the material from
the attenuation coefficient. Table 1 show the linear attenuation coefficients of some
materials.
Material )l (cm-I) Material )l (cm-I)

Polyethylene 0.172 Elastomer 18160/52 0.224
Water 0.191 Derlin 0.262
Nylon 0.210 Ebonite 0.288
Polyester 0.217 Elastomer 119199/48 0.340
Araldite 0.219 Teflon 0.376
Table 1: Linear attenuation coefficient of some materials

3 3-D RECONSTRUCTION
We have used the software on a UNIX work station, but it is easy to transplant it to a
PC computer which use a DOS operating system. The most important problem is that
normally there is just IMByte of memory that can be used by DOS directly. But
under 80386 or 80486 Protected modes with an XMS memory driver program
(Microsoft HIMEM.SYS), it is possible to get a maximum 32MByte of extended
memory supported by the PC. Also we can get virtual memory on the hard disk which
allows us to run programs that require more than the actual physical memory of the
system. Although that will be little more complex for the software, it offers a great
possibility for running our programs on the PC.
The software called ULTISCAN VISU has two parts; one is used to do all the image
calculation including 3-D reconstruction, image processing simulated tomography
console, file conversion and other special functions. Another part is the PC graphic
interface, which does the image graphic operation and displays the image.
First, the program has to convert the CT data into its own format, and then produce a
stack of contiguous or overlapping CT slices (cross-section). Although it is much
easier to perform 3D structural analysis by treating the parts as a stack of 2-D slices,
more problems can result if the part geometry varies significantly from slice to slice,
as is the case with scanning the specimen, one of the causes is the slice width of the
actual scanning.
UL TISCAN VISU has a special software package to convert CT data into extremely
accurate 3-D models of an actual part, and to convert the stack of two-dimensional CT
slices into a complete 3-D model. More accurate 3-D models need more CT slices, but
there is a limited dependence upon the resolution of the tomography machine.
3-D model data include two parts of information: the complete accurate stack of CT
slices in three-dimensions and the surface information of this stack of slices. It takes
thirteen minutes to calculate and rebuild this 3-D model from 11 slices of a
256x256xl2bit image matrix on a PC computer.
In the 3-D model, the pixel value can be expressed as HD = f(x,y,z); the 3-D
projection of any orientation can be given by translating from point 0(0,0,0) to
A(XA,YA,ZA ) and rotating around the vector V(VI,V2,V3) from the original
coordinate ( X ) to the destination coordinate (X'), Figure I.
X'=XRT
whereX=[xyz 1],X'=[x'y'z' 1]
x
z -..1/
...../
Figure 1: Original coordinate and destination coordinate and the relation of e, cI> and
vector V in spheroidal coordinates.
r22
r32
r23
r13
r33
O~lJ
r42 r43
Rr can be given by the rotation matrix R, translation matrix T and its inverse matrix T-
i.
o
1
RT = T-i R* T where
o
YA
R * can be gotten from the product of five 3x3 matrix, in which Rv performs an a.
angle rotation based on vector V.
Rotation matrix Ry, ~ and the inverse matrix Ry-I ~-I are given by the vector V(V 1
,v2 ,V3) in spheroidal coordinates (Figure 1).
(rosa
Ry = 0
0
-s:aJ1
sin a. 0 cosa.
and
[rosa
~J
sin a.
Rz = -s:a. cosa.
0
To rebuild a 3-D projection in some new orientation, the pixel value of the 3-D model
lID' is given by f(x, y, z) and the threshold function Ts (VHDS' V lIDE) in the new
orientation coordinates.
lID'= f(x', y', z') Ts (VlIDS ' VHDE)
The function Ts (VlIDS, VlIDE) allows one to get the 3-D image rebuilt by any segment
of pixel values (Houndsfield Density ).
4 GRAPHIC INTERFACE
It is impossible to identify a total pixel value of the CT image at one time on a monitor
screen by personal vision, because personal vision only can resolve, 24 gray levels or
less than 256 color levels in one picture. But each CT image pixel has a maximum of
212-216 levels in its raw data. There are two solutions for displaying CT images
(Houndsfield Density bitmaps), one is to express the pixel values of the raw data to
view the total features of the image; another one is to use a selective display segment;
this is more significant because actual specimens always have some limited range of
the attenuation coefficient of X-rays, and the interest is not in the total segment across
all CT dynamic ranges (CT detection system dynamic range is 1-106 from air to
metal) [5]. Also, it is more important to use pseudo-color to show most of the details
of the image.
5 TECHNOLOGY
The program is used for display of analysed three-dimensional rebuilt tomographic

images, it runs under MS-DOS 5.0 (or above), working with an ORCillD F1280°
SVGA adaptor; 80386 or 80486 CPU with more than 16MByte extended memory,
more than 100 MByte Hard Disk and a multisync color monitor (1024x768x8bit
resolution).
6 ApPLICATION
Using ND8000 medical tomography we have studied metal matrix composites

processed by squeeze casting. The first step has been to test the alumina preforms
which are disks of 85mm diameter and l5mm thickness. In some disks, spherical
defects were introduced during the processing. Figure 2 presents the results of
tomographic examination. The average Houndsfield density ofthe ceramic preform is
about -200. However, there is a large difference of X-ray attenuation between the
center of the specimen and the edge where the density is maximum -12l. In fact, the
density is lower in the center of the specimen because the volume fraction of alumina
is smaller than near the edge. Thus, it is possible with tomographic observation to
check the processing of the preform as well as the distribution of alumina platelets,
which is very difficult using regular experimental methods. Of course, it is easy to
detect defects in ceramic preforms as is shown in Figure 2. The example shows how it
is possible to study materials using three-dimensional reconstruction.
KEYWORDS
laminated composite, damage mechanics, rupture mechanics, design tools,

tomography
REFERENCES
[1] E.A.Sivers and M.D. Silver, "Performance of X-Ray Computed Tomographic

Imaging System", Materials Evaluation, 48, June (1990), 706-712.
[2] H.Hubbel, "Photom Cross-Section Attenuation Coefficients and Energy
Absorption Coefficients from 10 Kv to 100 Gev", NSRDS-NBS 29 (U.S.GPO,
Washington, DC, 1969).

[3] Edwin C. McCullough, "Photon Attenuation in Computer Tomography",
Medical Physics,Vol.2, W6, (1975).
[4] John David Jackson, "Classical Electrodynamics" (second edition), John Wiley,
New York, (1975).
[5] Robert A. Armistead, "CT: Quantitative 3-D Inspection", Advanced Materials
& Processes Inc, Metal Progress, Vol. 133 ISSUE 3, March (1988).
MODELING OF THE VISCOELASTIC BEHAVIOR OF
NON-HOMOGENEOUS MATERIALS
Nicole ALBEROLA and Patrice MELE
Laboratoire Materiaux Polymeres et Composites, Universite de Savoie, 73376

Le Bourget du Lac, France
ABSTRACT
The viscoelastic behavior of particulate composites constituted of a polymer matrix

reinforced by various volume fractions of spherical particles is predicted through an
original modeling, taking into account the formation of clusters and the maximum
volumetric packing fraction of inclusions.
RESUME
Le comportement visco-elastique de composites constitues d'une matrice de polymere
renforcee de particules spheriques de volume partiel variable, est represente a l'aide
d'un nouveau modele prenant en compte la formation d'agregats ainsi que Ie volume
maximal de compacite des inclusions.
1 INTRODUCTION
The prediction of the complex moduli of polymers filled by rigid inclusions is usually
based on (i) variational methods [1] or (ii) self consistent schemes [2-3], extended to
describe the viscoelastic behavior through the correspondence principle [4].
For low volume fractions of fillers, such modeling gives good agreement between
theoretical real (M') and imaginary (Mil) parts of the complex moduli and the loss
tangent (tan S = Mil / M') and experimental values. But, for volume fractions of
particles greater than 20 vol.%, some discrepancies appear between theoretical and
experimental data [5]. Figure 1 shows the experimental and theoretical variations of
the damping factor (tan S) versus temperature, at 5 Hz, for a polystyrene matrix
reinforced by 15 and 50 vol.% of glass beads. Values of the damping factors are
predicted by Christensen and Lo's model [2]. The predictions do not give evidence for
the strong decrease in the damping factor, shown experimentally by the polymer
reinforced by 50 vol.% of glass beads.
4~ __________________________________________ ~
20 40 60 80 100 120 140 160 180
Temperature (OC)
Figure 1: Experimental and theoretical (-) viscoelastic spectra at 5 Hz of a

polystyrene matrix reinforced by 15 vol.% ( ) and 50 vol.% (e) of glass beads.
Thus, the well-known three-phase model, developed by Christensen and Lo is not

well-suited to describe the viscoelastic behavior of particulate composites for high
volume fractions of rigid particles.
The discrepancy between theoretical and experimental data could be due to any of the
three following origins:
(i) the formation of a rigid interphase, which is not taken into account by this
modeling. But, the polymer used in this study is apolar and then no additionnal
interactions between phases can occur.
(ii) usually in modeling, the Poisson's ratio of polymers is assumed to be constant

and real over the analyzed temperature range. Then, Agbossou et al. [6] attempted to
predict the decrease in the damping ability of such composites by taking into account
the complex character of Poisson's ratio for the polymer in Christensen and Lo's
Modeling of the Viscoelastic Behavior of Non-Homogeneous Materials 235
model. In Figure 2, we have superimposed on the. experimental data, the theoretical

variations of the damping factor predicted by a three-phase model taking into account
the complex character of Poisson's ratio determined for a polymer reinforced by 50
vol.% of glass beads.
4~------------------------------------,
O+-~~~~~~~~~~~-.~--r-~
20 40 60 80 100 120 140 160 180
Temperature (0C)
Figure 2: Experimental (.) and theoretical (-) viscoelastic spectra at 5 Hz of a

polystyrene matrix filled by 50 vol.% of glass beads.
An important discrepancy appears between the simulated and experimental results. In

fact, the reinforcement effect of the polymer induced by rigid particles, i.e. the
mechanical coupling, remains underestimated.
(iii) According to Lewis and Nielsen [7], the strong reinforcement effect observed
for high volume fractions of fillers is due to the formation of clusters of particles. So,
these authors proposed an empirical modification of the classical Kerner equation.
Their phenomenological law gives a good agreement between predicted and
experimental viscoelastic behaviors of polymers reinforced by soft particles, as for
example polymer/polymer composites. But, it also underestimates the mechanical
coupling between the different phases for polymers reinforced by high volume
fractions of rigid particles.
In this paper, an original modeling of the viscoelastic behavior of particulate

composites is proposed, taking into account the formation of aggregates of rigid or
soft fillers, and thus local phase inversions, which occur for a critical volume fraction
of particles.
Such a theoretical prediction is based on (i) the percolation theory and (ii) requires the
definition of a "representative morphological motif', characteristic of the topological
aspect of the clustering.
2 PERCOLATION CONCEPT AND FORMATION OF CLUSTERS

OF PARTICLES
A percolation theory has been developed to provide a new framework to better

understand the properties of non-homogeneous materials [81. The essence of this
theory is to determine how a given set of sites, regularly or randomly positioned in
space, is interconnected according to a defined bonding criterion [9].
At the percolation threshold, i. e. for a critical fraction, a topological singularity occurs

corresponding to a connection between sites on a large scale.
i. For low volume fractions of fillers, lower than the clustering threshold (a),
the spherical particles are randomly distributed within the polymer matrix which
is defined as percolated. Then, all the matrix is connected at the network scale
and acts as the continuous phase. The viscoelastic behavior of such composites
can be predicted by the Christensen and Lo model.
ii. For the maximum volumetric packing fraction of inclusions (fmax = 0.75),
the polymer is entrapped within the interstices of the filler network. All the
matrix is then not percolated (mmin = 1- <l>fmax = 0.25) and a macroscopic phase
inversion occurs. The mechanical behavior of such composites can be described
by the same model, i. e. that of Christensen and Lo, in which the particles now
act as the continuous phase.
iii. For volume fractions of fillers, ranging from the clustering threshold (a) to
the maximum volumetric fraction (finax) of the fillers, the probability of cluster
formation of particles increases, leading to local phase inversions (Fig. 3). The
cluster threshold (a) has been chosen to be 0.2, because experimentally for
volume fractions of particles greater than 0.2, these composites show a strong
decrease in the damping factor. Accordingly, a fraction of polymer is entrapped
within the clusters, while the fraction of polymer surrounding the clusters is
defined as percolated.
Non·percolated Matrix
Partides
Figure 3: Schematic representation offiller clusters embedded in the percolated

matrix
To model the viscoelastic behavior of such composites, it is of interest to evaluate the

"effective" volume fraction of matrix which really contributes to the damping of
composites, Le. the volume fraction of percolated matrix ($mp)' According to the well-
known percolation equation [9] and taking into account for the two following
boundary conditions, i.e. (i) $mp = 0 for $m = $mmin and (ii) $mp = $m for $m = I - $a'
the volume fraction of percolated matrix versus the total volume fraction of polymer
can be expressed as follows:
The rigorous prediction of the mechanical behavior of such particulate composites,

showing local phases inversions, requires definition of a "representative
morphological motif'.
3 DEFINITION OF A REPRESENTATIVE MORPHOLOGICAL MOTIF
To account for the topological aspects of the percolation phenomenon, an original

"representative morphological motif' is defined (Fig. 4). Such a geometric model can
give evidence for the two kinds of viscoelastic medium, i.e. percolated matrix and one
not percolated.
c:::=JPhase 1: Non·percolated Matrix
c:::=JPhase 2 : Aggregated Particles
~Phase 3 :Percolated Matrix
• • • Phase 4: Equivalent Homogeneous Medium
Figure 4: Definition of the "representative morphological motif'
Embedded in the percolated matrix, the particles are considered as a spherical annulus
within which the percolated matrix is entrapped. By assuming perfect bonding not
only between neighboring phases but also between particles forming the spherical
cluster, a "morphological motif' constituted of three-concentric spheres can be
defined.
The modeling of the viscoelastic behavior is performed by using the elastic (n+l)-
phase model developed by Herve and Zaoui [10], applied to a four-phase system and
extended through the correspondence principle to the viscoelastic domain.
4 NUMERICAL RESULTS
In order to illustrate the validity of the developed model, it is valuable to compare

experimental to theoretical damping factors (tan 8) for a polystyrene matrix reinforced
by 15 and 50 vol.% of glass beads (Fig. 5).
The fillers exhibit an elastic behavior over the analyzed temperature range (E f = 70
GPa and Yf = 0.2), while the polystyrene matrix shows a viscoelastic behavior,
experimentally determined. Moreover, in order to take into account the vitreous
rubbery transition undergone by the polymer through the glass transition (100°C, for
polystyrene), it is assumed that Poisson's ratio increases from 0.33 to 0.499 following
an S-shape variation in such a temperature range.
4~-------------------------------------'
o~~~~~~~~~.-~~-.~-.~
20 40 60 80 100 120 140 160 180 200
Temperature (0C)
Figure 5: Experimental and theoretical (-) viscoelastic spectra at 5 Hz of a

polystyrene matrix (.) reinforced by 15 ( ) and 50 (.6) vol.% of glass beads.
It can be observed that there is a good agreement between the theoretical and
experimental tan 8 spectra. Thus, the proposed modeling, based on the percolation
concept, is well-suited to give evidence for the strong decrease in the maximum of
damping factor exhibited by the polymer reinforced by 50 vol.% of glass beads. The
reinforcement effect observed for such a sample is then mainly due to the formation of
aggregates of fillers and then to local phase inversions within the sample. It is also of
interest to compare theoretical data derived from our approach with other theoretical
predictions. Figure 6 shows theoretical variations of E' versus the volume fraction of
elastic spherical particles within a viscoelastic matrix (a).
Also, shown for comparison are the upper (b) and lower (c) bounds derived by Hashin
and Shtrickman and the results from the Christensen and Lo three-phase model (d)
and from the equation of Lewis and Nielsen (e). For volume fractions of fillers lower
than 0.20, it can be seen that our data are in good agreement with other predictions, in
particular with the improved lower bound derived by Hashin and Shtrickman. For the
maximum volumetric packing fraction of spheres, the predicted value of E' reaches the
upper bound predicted by Hashin and Shtrickman. It reveals the macroscopic phase
inversion phenomenon occuring for such a content of fillers.For intermediate volume
fractions, the predicted values of E' resulting from the reported modeling are close to
those derived from the equation of Lewis and Nielsen.
80.--------------------------------------,
60
40
w
20
O+-~._~._~._~._~~~~_.~_.~_.~_4
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
 f (vol.%)
Figure 6: Dependence of the theoretical E' on the filler fraction predicted by:
(a) the present work,
(b-c) the upper and the lower bounds of Hashin and Shtrickman,
(d) the Christensen and Lo model
(e) the Lewis and Nielsen equation.
The validity of our modeling is well underlined when considering the evolution of the
maximum of the damping factor versus the volume fraction of fillers (Fig. 7). In fact,
this figure shows that only our approach is in agreement with the experimental
decrease of the loss tangent of such composites and thus could predict the
reinforcement effect observed in particulate composites.
4.---------------------------------------,
00
3
c
~
'0
E
::l 2
E
·xctI
E
1
O+---~--r_--~~--~--~--~-4~~~~
0.0 0.2 0.4 0.6 0.8 1.0
<l>f
Figure 7: Dependence of the theoretical maximum oftan 0 on the filler fraction
predicted by :
(a) the present work
(b) the Christensen and Lo model
(c) the Lewis and Nielsen equation
(d) the Kerner equation.
5 CONCLUSION
The reported modeling, based on the percolation theory, is well-suited to predict the
viscoelastic behavior of particulate composites over wide ranges of volume fraction of
particles and temperature (or frequency).
ACKNOWLEDGMENTS
The authors wish to acknowledge Elf-Atochem Company (Cerdato-Serquigny) for the

purchase of the materials used.
KEYWORDS
particulate composite, viscoelastic behavior, mechanical modeling, percolation

REFERENCES
[1] Z. Hashin and S. Shtrickman, 1. Mech. Phys. Solids, 11, (1963),127-140.

[2] R.M. Christensen and K.H. Lo, 1. Mech. Phys. Solids, 27, (1979), 315-330.
[3] E. H. Kerner, Proc. Phys. Soc. London, 69B,(1956), 808-813.
[4] Z. Hashin, Introduction to Percolation Theory, Int. 1. Solids Structures, 6,
(1970),539-552.
[5] A. Bergeret, Thesis, (Universite de Lyon 1, France), (1970), 235
[6] A. Agbossou, A. Bergeret, K. Benzarti and N. Alberola, 1. Mat. Sci., 28,
(1993), 1963
[7] T.B. Lewis and L.E. Nielsen, 1. App!. Polym. Sci., 14, (1970), 1449-1471.
[8] D. Stauffer, Taylor & Francis: London and Philadelphia, (1985)
[9] P.G. de Gennes, Scaling concepts in polymer physics, Ed. Cornell UP, (1979)
[10] E. Herve and A. Zaoui, Int. 1. Eng. Sci., 31, (1993), 1-10
MODELING STUDIES OF THE UNIAXIAL CREEP OF
A BRITTLE MATRIX COMPOSITE
J. L. VALLES, M. STEEN and F. LAMOUROUX
Institute for Advanced Materials, Joint Research Centre, European

Commission, 1755 ZG Petten, The Netherlands
ABSTRACT
High temperature structural applications under aggressive environments demand a

constant effort to develop new materials, like ceramics with reduced brittleness
obtained by reinforcing ceramic fibers (CMCs). First, a general experimental
interpretation and a microcomposite model with schematic representative blocks, are
presented Then an internal variable creep model suitable for CMCs and an
additional modeling of the damage development during tertiary creep, are described
and compared to experimental results.
Finally, fiber breaking takes over, leading to catastrophic rupture at high enough
stresses. The modeling results presented provide the stress dependence of the
minimum creep rate as well as the general appearance of tertiary creep, in good
agreement with experiment.
RESUME
Les applications structurelies a haute temperature en environnement agressif,

requierent un effort constant de developpement de nouveaux materiaux, tels des
ceramiques de fragilite reduite obtenue par des fibres de ceramiques de renforcement
(CMCs). Tout d'abord, une interpretation generale des experiences et un modele
micro-composite comportant une schematisation en blocs, sont presentes. Puis une
modelisation du jluage avec variable interne applicable aux CMCs suivie d'une autre
modelisation de l'endommagement present dans la troisieme phase du jluage, sont
decrites et comparees aux resultats d'experiences. Finalement, la rupture des fibres
entraine la rupture catastrophique a un niveau de contraintes suffisamment eleve. Les
modelisations presentees fournissent une relation entre la contrainte et la vitesse
minimum de jluage aussi bien que l'allure de la troisieme phase de jluage, en bon
accord avec l'experience.
1 INTRODUCTION
High temperature structural applications under aggressive environments demand a

constant effort to develop new improved materials. The brittleness of structural
ceramics can be overcome by incorporating continuous ceramic fibers, as a way to
allow for new mechanisms which dissipate the energy otherwise used for fracture.
The mechanical properties of these ceramic matrix composites (CMCs) are expected
to depend strongly on the fiber-matrix interface, which determines the load transfer
condition between fibers and matrix. Therefore, an accurate prediction of the
mechanical properties under service conditions can only be provided by a
microstructurally-informed modeling approach, calibrated with results of mechanical
tests.
2 EXPERIMENTAL MODELING
Uniaxial tensile and creep experiments have been performed on a composite

consisting of alumina fibers in a silicon carbide matrix [1,2]. Since, for this material in
the stress range studied, saturation of matrix cracking is already reached right after
creep loading, the most suitable microcomposite model is assumed to consist of a fiber
inside a matrix mantle which exhibits microcracks perpendicular to the fiber axis.
Essentially, it is thus a series of blocks like the one shown schematically in Fig. 1,
each composed of an inner region where fiber and matrix are perfectly bonded and an
outer debonded one.
As a first step, the stress profiles on the fiber and matrix along the axial direction, as
well as the radial and shear stresses at the interface, have been calculated using a
modified shear lag model which accounts for the existence of two different regimes
along the unbonded interface: total detachment near the matrix crack and relative slip
involving friction close to the bonded region [3,4]. Assuming the continuity of shear
stress at the boundary points between the interfacial regions of relative slip and
unaffected contact, one can solve the equilibrium equations and obtain the stress
distributions. Typical profiles are shown in Fig. 2.
In order to evaluate the model parameters using only experimentally measurable

quantities, one needs to consider the application of the shear lag approach at two
different levels [5]. The first level deals with a model composite consisting of a
collection of longitudinal fiber tows embedded in the intertow matrix. By imposing
linear elastic behavior up to the first matrix cracking stress, the volume fractions and
elastic moduli of both the tows and the intertow matrix can be calculated. Further, by
imposing the condition that full debonding is reached at a stress equal to that of
saturation of matrix cracking, the axial thermal expansion coefficient for a tow is
found, as well as the friction coefficient and the radial interfacial strength at the
Modeling Studies of the Uniaxial Creep of Brittle Matrix Composite 245
interface between the tow and the intertow matrix. At the second level, an individual
longitudinal tow consisting of fibers and the intratow matrix is considered instead.
Using a bundle strength model [6] and values of fiber properties [7] similar quantities
as at the first level can be determined, but this time for the case of individual fibers
and the surrounding intratow matrix. Once these material parameters are available,
the stress profiles calculated as described above can be used in the modeling of
composite processes for which interfacial phenomena are of relevance, such as fiber
pull-out, or to calculate in-situ quantities which are difficult to access experimentally
[5].
(J ...
crack spacing
Figure 1: Representation of a block in the microcomposite model
The most relevant deformation process in CMCs at high temperatures is the creep
process, in which the strain increases under a constant applied load. The strain-versus-
time curves present, for the composite studied, the usual three stages. In the primary
stage, a stress redistribution takes place, leading to a decrease in the strain rate.
The secondary stage, usually a region characterized by a constant creep rate, seems to
be reduced here to an inflection point. The composite then presents an extended
tertiary stage, which appears to be initially associated with a progressive fiber-matrix
debonding. Finally, fiber breaking takes over, leading to catastrophic rupture at
sufficiently high stresses.
300~--------------------------------------~
axial matrix stress
200
100
______ ____________________________
interfacial shear stress (x1 0)
0.0 0.2 0.4 0.6 0.8 1.0

normalised half length [-I
Figure 2: Stress profiles obtained with the modified shear-lag model.
2.1 The internal variable creep model
In order to model the first two stages, an internal variable formalism developed for
metallic matrix composites has been extended to include fiber creep and the axial
stress profiles obtained from the shear lag analysis. The integration of the coupled
differential equations for the strain rate and the rate of change of the internal variables,
produces model creep curves.
{
e= a1 .e *m S n r + a 2 .e *m .( 1 - S) n m
S= H.e - R.S n r
Here, E; and E ~ are the creep rates corresponding to the full applied stress cr for
*
fiber and matrix respectively, S=V[ crr/cr, H=V r E/cr, R= Hl::fNrnr, and al and a2 are
constant with the applied stress.
Fitting the stress exponents of fiber and matrix by comparison between model and
experimental creep curves, as in the case shown in Fig. 3, yields values in agreement
with the literature.
Modeling Studies of the Uniaxial Creep of Brittle Matrix Composite 247
5~-----------------------------------------'
experiment
model
o~------.-------.-------~------r-----~
o 2000 4000 6000 8000 10000
timers]
Figure 3: Comparison between experimental creep curves and those resulting from
the internal variable creep model.
2.2 Modeling of the damage phase
The damage mechanisms activated during tertiary creep can be characterized by

analyzing the results of experimental tests. The initial tertiary stage shows a strain rate
which grows linearly in time, a behavior which can be associated with a process of
progressive fiber-matrix debonding. Because of the large difference in the creep rates
Xj(t) = d j = Xj(O)+~t
Aj Aj
of fiber and matrix, in first approximation the strain rate of block i is assumed to be
equivalent to the strain rate of its debonded part [8].
Ej(t)=ErXj(t)
The debonded fraction in block i, Xi is assumed to be linearly growing in time, i.e. the
rate at which the fiber mechanically debonds is taken as constant, and the initial
debonded fractions are obtained from the initial experimental value of the composite
elastic modulus. In this way, in first approximation the creep strain can be obtained as
the sum of the creep elongation of the debonded part in all the microcomposite blocks,
divided by the total initial length.
After calibration at a reference stress by using literature values for the constituents,
the model has been applied to a prediction of the behavior at other stresses.· Both the
stress dependence of the mInimum creep rate and the general appearance of the
tertiary creep curves show good agreement with experiment (Fig. 4). The evolution in
the stress exponent can be related to the stress dependence of the damage state of the
composite just before the initiation of the tertiary stage. As a consequence, it can be
concluded that no effective creep stress exponent may be determined for this
damageable composite.
100 MPa
120 MPa
~
c: 4
1 2 3
time[h]
0
0 10 20 30 40
time[h]
Figure 4: Modeling of tertiary creep based on interfacial debonding.
Since the rupture of the alumina fiber under tensile loading is induced by the growth
of flaws present in its intergranular phase, an analysis based on Weibull statistics can
provide information about the fiber rupture times. Specifically, by replacing the fiber
length ratio by a ratio of the initial fractions of debonded fiber, for any given
probability of fiber failure the rupture times are found to scale as
where m is the fiber Weibull modulus [7] and b can be found by comparing two
experimental rupture times. The model results can be seen to agree well with
experimental rupture times in Fig 5.
Modeling Studies of the Uniaxial Creep of Britlle Matrix Composite 249
13.0
12.0 • experiment
11.0
~
!!'
"
Q. 10.0
£
2 •
§ 9.0
::::.
c::
...I
8.0
• •
7.0
18.2 18.4 18.6 18.8 19.0 19.2
Ln [stress (Pa))
Figure 5: Stress dependence of the time to rupture under creep loading.
Finally, the rupture of a fiber will provoke a stress redistribution among those fibers
still remaining intact, which may lead at high stresses to a catastrophic failure of the
composite or at low stresses to a simple load increase, causing a more progressive
failure process.
By applying an analysis based on the statistics of a bundle of fibers, the threshold
stress for catastrophic rupture can be found to correspond in this case to a stress of
140 MPa applied to the composite.
3 CONCLUSION
Our study shows that a microstructurally-informed modeling approach, intimately

based on both microscopic information and on the results of accurate mechanical tests
can be an invaluable tool in the design of improved advanced materials.
ACKNOWLEDGMENTS
This work has been performed within the Specific Research and Development
Programme of the European Commission.
KEYWORDS
micro-composite model, internal variable creep model, damage creep, ceramic matrix
composite, CMCs
REFERENCES
[I] F. Lamouroux, M. Steen and J. L. Valles, Uniaxial tensile and creep

behavior of an alumina fiber-reinforced ceramic matrix composite: I -
Experimental study, in Journal of the European Ceramic Society, 14,
(1994),529-537.
[2] J. N. Adami, Comportement en fluage uniaxial sous vide d'un composite
2D A1203/SiC, Thesis of "Ecole Polytechnique Federale de Zurich",
Switzerland (1992).
[3] M. Steen and J. L. Valles, Uniaxial creep of ceramic matrix composites:
experiments and modeling, in Mechanisms and Mechanics of Composite
Fracture, ed. by R. B. Bhagat, S. G. Fishman and R. J. Arsenault, ASM,
Pittsburgh, (1993).
[4] M. Steen and J. L. Valles, Modeling of Uniaxial Creep in Ceramic
Matrix Composites, in Proceedings of the 9th International Conference
on Composite Materials, Vol. 2, ed. by A. Miravete, Woodhead (1993).
[5] M. Steen and J. L. Valles, Interfacial bond conditions and stress
distribution in a brittle matrix composite, Accepted by Compo Sci.
Technol. (1997)
[6] H. E. Daniels, The statistical theory of the strength of bundles of threads.
I, Proc. Royal Soc. London, Vol. A183, (1945), 405-435.
[7] Ch. Lesniewski, C. Aubin and A. R. Bunsell, Property-structure
characterization of a continuous fine alumina-silica fiber, Composites
Science and Technology, Vol. 37, (1990), 63-78.
[8] F. Lamouroux, J. L. Valles and M. Steen, Uniaxial tensile and creep
behavior of an alumina fiber-reinforced ceramic matrix composite: 2-
Modeling of tertiary creep, in Journal of the European Ceramic Society,
14, (1994),538-548.
THE INTELLIGENT SELECTION OF MATERIALS
FROM A DESIGN SPECIFICATION
A.C. WINSTANLEY*, S.P. LOUGHLIN** and F.J. SMITH**
* Department of Computer Science, National University of Ireland, Maynooth,

County Kildare, Ireland
** Department of Computer Science, The Queen's University of Belfast,
BELFAST BT7 INN, Northern Ireland
ABSTRACT
Normally an engineer needing a material for the design of some item, like a bolt or
panel, specifies the properties of the required material to a database of material
properties and the system then searches and retrieves relevant materials. We have
developed a more intelligent materials selection system, called QPS, which goes one
step forther and selects the materials from the characteristics of the item being
designed, i.e. it computes the specification of the material from the characteristics of
the item and then automatically retrieves the optimum material (or materials) as part
of an optimum design.
It does this by being an integrated system which includes both the data system and
design system together; so it includes not only data on the properties of materials but
also knowledge on the geometry and on the formulas needed to compute the necessary
limiting characteristics of the item. It searches for the appropriate formulas in the
knowledge base and applies them automatically in the correct order (using AI
techniques). An early prototype is already in operation.
RESUME
Un ingenieur ayant besoin d'un materiau pour concevoir une piece, tel un boulon ou
un panneau, indique normalement les proprietes requises dans une banque de
donnees de proprietes des materiaux et Ie systeme cherche et fournit Ie materiau
adequat. Un systeme de selection de materiaux plus intelligent est decrit, travail/ant
en integration des deux systemes de donnees et de conception ensemble. Un premier
prototype est deja en action.
1 INTRODUCTION
Computer systems, both hardware and software, have improved so much in power and
flexibility over recent years that it is now time to begin studying the application of
more intelligence to the process of material selection in design. Over the last 20
years, the most that was possible with the less powerful computer systems and
relatively primitive software tools available, was the efficient storage and rapid
retrieval of numerical data on the properties of materials [1,2]. By specifying
constraints on these properties it was also possible to select materials with particular
properties. These selected materials could then be used in the design of an item which
required materials which had these particular properties. The above process, which is
the common one used in the design of almost all items today, from a metal bolt to a
plastic box, involves three separate processes by the design engineer. In the first, the
engineer determines the characteristics of the item to be designed such as the strength
of a bolt of a certain size needed in the design. The engineer secondly selects a small
number of materials which, from experience, he knows might be suitable for the item
he requires and then, using a database, he finds the required numerical values of the
properties of the materials. Lastly, using these values, the engineer computes the
characteristics of the item using formulae or computer code (such as a finite element
analysis package) for each of the materials and checks that the item has the required
characteristics if made from the material. A material is then selected which meets the
requirements. It is common for the engineer to use 3 separate computer systems for
this design process. Firstly, the primary characteristics of the item, such as the
strength of a bolt with a particular dimension, is determined by a CAD system.
Secondly, other properties of the possible materials such as Young's modulus are
found from a database and thirdly the characteristics of the item are computed from
the properties, such as the calculation of the strength of a bolt from the dimensions,
from Young's modulus for each material and from the appropriate formulae. In large
companies these three processes are often carried out in different departments by
different engineers: the design engineers for step 1, the materials engineer for step 2
and, in mechanical engineering, the stress engineers for step 3.
2 AI ApPROACH
The above process is wasteful of human time, is prone to errors due to the
communication of data between the sub-systems and restricts or militates against the
introduction of novel materials. We therefore propose a different approach which
uses artificial intelligence techniques effectively to reverse the order of the last steps
and integrate the systems together with a knowledge base system [3] to produce an
optimum design, including an optimum material. In this new approach at the first step,
CAD, the system determines the limits on the characteristics of the item to be
designed in the form of a set of inequalities or ranges of variables, both geometric and
The Intelligent Selection of Materials from a Design Specifications 253
physical, of the item being designed. A very simple case might be a cylindrical bolt
within a certain range of diameters, d, and a certain length, 1, which would have an
axial strength able to withstand a range of loads F without the bolt extending more
than a certain small range, ""I. This would be specified by the system in the form:
Geometry: cylindrical rod

1 =20 mm
2mm<d<6mm
F = 3000N
""1 < 0.3 mm
The system would begin by noting that the item to be designated is a cylindrical rod.
From the knowledge base it would find that a cylindrical rod has two fundamental
characteristics:
1 : length; d : diameter
It would also note that I is known but that d is unknown, only limited to a range. It
would therefore initially seek to find d more accurately. It would do this by looking
for formulae involving d. One of these is
d =2r
where r is the radius; so by a process of back-chaining, it would seek to find rand

locate the equations:
A= 1t r2 ; ""I = IFlYA
where A is the area, F is the load and Y is Young's modulus.
In this last equation it would find that it knows the following:
""1 <0.3 mm; 1 = 20 mm; F = 3000N; 3.10- 6 m2 < A < 28.10-6 m2
from which it can compute: Y > 70 GPa
It then finds from its knowledge base those materials which have a suitable Young's
modulus and for each material computes the appropriate diameter. This would give a
range of materials from steel with the smallest diameter to aluminum with the
maximum diameter allowed. Price and availability in stock would then determine the
optimum material and its corresponding diameter.
3 CONCLUSION
This type of design process is quite simple for a human; but it needs three ingredients
not found in this type of system previously. First of all it involves a knowledge base
consisting not only of scientific data, but also of scientific formulae [3]. Without the
development of Object-Oriented technology [3,4] this kind of knowledge base would
have been very difficult to implement. The second is the use of AI techniques to select
the data and formulae in the correct sequence to solve the problem. This problem has
been solved in a system called QPS described in another paper submitted to this
conference [5]. The third is the use of inequalities as well as simple equality
equations. Dealing with inequalities automatically has not been studied in this context
before and presents some difficulty. Only very simple cases, such as the one in the
above example have yet been solved. However, for the design of real items a much
larger number of inequalities will be needed to be processed. Another problem is the
automatic processing of "hard constraints" which can also be expressed as
inequalities. For example the constraint that the equation involving Young's modulus
is only valid if the strain is within the elastic limit of the material can be expressed as
an inequality. Adding such constraints will be difficult but solvable, and has been the
subject of study recently [6].
KEYWORDS
AI, material selection, material design
REFERENCES
[1] J R Rumble and F J Smith, Database Systems in Science and Engineering,

Adam Hilger,Bristoi. U.K. (1990).
[2] M F Ashby, Material Selection in Mechanical Design, Pergamon Press,
Oxford, U.K., (1992).
[3] M V Krishnamurthy and F J Smith, Integration of Scientific Data and
Formulas in an Object-Oriented Knowledge Based System, Knowledge Based
Systems Jour, Vol 7, 135-141, (1994).
[4] A Demaid, J Zucker and S Ogden, Object-Oriented Materials Engineering
Information Modeling and Management, Proc. 2nd Int Conf Technology of
Oh-Oh Languages and Systems, Prentice Hall, pp 119-133, 1992.
[5] A Winstanley and F J Smith, Integration of scientific data into an AI system,
"Industrial Information and Design Issues", Eds. J.-E. Dubois, N. Gershon,
Springer Verlag, Berlin Heidelberg (1996).
[6] S.P. Loughlin, J.C. Collis and FJ. Smith, 6th International Conference on Data
and Knowledge Systems for Manufacturing and Engineering, Phoenix,
Arizona, 23-43, (1996)
PHASE DIAGRAM CALCULATIONS AND THE
OPTIMIZATION OF HIGH SPEED STEEL
COMPOSITIONS FOR ECONOMIC POWDER
METALLURGY PROCESSING ROUTES
1. ANSARA * and M. DURAND-CHARRE*

C.S. WRIGHT** and A. S.. WRONSKI**
J. MASCARENHAS*** and M. OLIVEIRA ***
E. LEMOISSON" and Y. BIENVENu+
*LTPCMlENSEEG, Saint Martin d'Heres, France

**University of Bradford, Bradford, UK.
***INETI, DM, Lisbon, Portugal
+ Ecole des Mines de Paris, CDM, Evry, France
ABSTRACT
Processing through powder metallurgy becomes the only feasible way for the most
highly alloyed of high speed steels (HSS), with carbon contents between 0.7 wt % and
2.5 wt % containing substantial amounts of carbide formers Wand/or Mo, V, Cr.
The basis of the project of the European collaborative study to arrive at the definition
of new grades of HSS that meet the sintering temperature through "computer assisted
design of sinterable tool steels", is presented..
RESUME
L'elaboration en metallurgie des poudres devient la seule voie possible pour les plus
allies des aciers ultra rapides (HSS), avec des teneurs en carbone de 0.7% a 2.5% et
contenant des quantites significatives de precurseurs de carbures tels que W et/ou Mo,
V, Cr.
La base du projet de l'etude Europeenne de collaboration pour trouver la definition

de nouvelles nuances de HSS qui atteignent la temperature effective de frittage grace
ala " Determination d'aciers aoutils frittables assistee par ordinateur", est presentee.
1 INTRODUCTION
High speed steels [HSS] are complex alloys with carbon contents between 0.7 and 2.5
w% containing substantial amounts of carbide formers. W, Mo, V and Cr, They can
be heat treated to high hardness levels [up to 1000 Hv] and exhibit reasonable
toughness [up to 25MPam l12 ] . They are used in cutting, die and wear applications.
For the most highly alloyed HSS, the only feasible processing route is by Powder
Metallurgy: HIPing [Hot Isostatic Pressure] of prealloyed, gas atomized powders, or
cold compaction and vacuum sintering of water atomized powders [1]. In the former
process, densification occurs in the solid state, whereas in the latter process Super-
solidus Liquid Phase Sintering [SLPS] is employed to attain densities in excess of
99.5% [2]. Successful atomized HSS powders require the use of high sintering
temperatures (1240-1330 DC), combined with very accurate temperature control since
for each alloy there is a narrow temperature band within which optimal
microstructures and mechanical properties can be attained - "the sintering window" -
illustrated in Figure 1 [3-5b]. Sintering windows range from less than 5 °C to about 10
°C for tungsten grades such as T1 [3,5b]. It is known empirically that the width of the
sintering window is highly sensitive to small changes in powder composition, since
different powders of the same nominal composition exhibit slightly different sintering
windows, or small variations in alloy chemistry may render a sinterable material
unsinterable, e.g. T1 [4]. These factors, when combined with the accuracy of
temperature control in industrial vacuum furnaces (generally no better than ± 3°C),
can produce significant batch-to-batch variability in terms of microstructures and
mechanical properties. It would be of commercial interest if HSS compositions could
be developed which possess wider sintering windows, ideally at or below 1150 °C to
enable continuous processing in mesh belt furnaces instead of the significantly more
expensive batch processing in vacuum furnaces [5b].
1_ sintering plateau -I
Porous I
Microstructures -
sintering
window -
I Coarse microstructures
Poor mechanical properties
100% _
>-
I t t
.~ optim~m distortion
U)
cQ) slntenng eutectic formation
temperature
Cl
70% f--
solidus temperature
+
Temperature
Figure 1: Schematic representation of the sintering curves for a HSS powder
Phase Diagram Calculations ... for Economic Powder Metallurgy Processing 257
2 THEORETICAL CONSIDERATION OF SLPS
According to German [6], a SLPS system should possess a number of desirable

features (Figure 2). The first is a high concentration of alloying elements xA since
this in general gives a greater separation of liquidus TL and solidus Ts temperatures.
A large separation is desirable because it aids process control since the liquid volume
fraction dependence is inversely proportional to it. To minimise sensitivity to small
compositional variations in the alloy, a moderately large (xc-xs) is also desirable
Temperature control would be less critical if the volume fraction of liquid does not
change rapidly with temperature. Thus steep solidus and liquidus surfaces are
desirable.
Desired
high x..
large XL - Xs
large TL - Ts
steep dT / dx
~ TLr---~~----~~
co
Q;
~ T r-------~~--+_--------~~
I-
composition
Figure 2: Schematic phase diagram showing features required for successful liquid
phase sintering
3 EXPERIMENTAL OBSERVATIONS - SINTERING CHARACTERISTICS

- PHASE DIAGRAM CORRELATIONS
Previous work has shown that the sintering windows of HSS powders are located
within the austenite + carbide [M6C and/or M6C+MC in V-containing alloys] + liquid
[L] region. Comparing Figures 2 and 3, it would be expected that since the austenite +
carbide + L field undergoes a considerable expansion with increasing carbon content,
then this would be accompanied by an improved sinterability. Experimental data
supported this view since increasing the carbon content of Tl reduced sintering
temperatures (Figure 4) whilst microstructural evaluation showed that at 1.4w%C, the
sintering window was 40°C compared to 10 °C at 0.8w%C, - the standard
composition. Optimum sintering temperatures were reduced from 1320 °C (0.8w%C)
to 1250 °C (I Aw%), Microstructures are shown in figures 5 and 6,
D.TA.
D1olome"y (begnning)
Oilatometry (end)
1500
~
Q) 1300
~
ftj
:;;
g-
OJ
1100
I-
900
0 ,0 0 .2 0.4 O.S 0.8 1 .0 1.2 1.4 1 .6 1.$ 2 .0

w%c
Figure 3: Phase diagram ofthe C-Cr-Fe-V system (4% Cr, 1% V) [7]

(L: Liquid, ex: ferrite, y: austenite, 8:cementite, 11: M6C, A: intermetallics)
9.0 .-----,-------r----r----,
8.5
E 8 .0
~
'"
~
.~ 7.6
o
• T1 - O.B C
7 .0
- Tl-l.4C
6.6 L - - - - . . . I - - - - - - - - L - - ---'-------;,;;;350
1160 1200 1260 1300
Sintering TemperatlXe · C
Figure 4: Sintering curves for Tl HSS powders containing 0.8 and l.4w% C.
Figure 5: (a) and (b) Microstructures ofTl-0.8w%C at 1315 and 1325 DC,
respectively -the limits of the sintering window. x750.
Phase Diagram Calculations ... for Economic Powder Metallurgy Processing 259
Figure 6: (a) and (b) Microstructures ofT!-I.4w%C at 1230 and 1250 DC,
respectively -the limits of the sintering window. x750.
4 USE OF CALCULATED PHASE DIAGRAMS TO DESIGN SINTERABLE

HSS
Apart from diagrams appropriate for a small number of systems [T!, M2 and M31II] ,
experimental phase diagrams are unavailable for HSS. However, calculation of phase
diagrams is now precise enough to allow for the reliable prediction of the variation in
solidus temperature with alloying content in quaternary and quinary systems. This
close agreement between theory and experiment is illustrated in Figure 7. In this
project, phase diagrams for the following selected compositions (in w%) were
calculated:
1500-<----
p
Q) 1300
~
e
Q)
~ 1\00
Q)
I-
900
0.0 0 .2 0.' 0.6 0 .8 1 .0 1 .2 1.. 1.6 1.8 2 .0

w%c
Figure 7: Calculated phase diagram of the C-Cr-Fe-W system (4% Cr, 1% V)
compared with experimental DT A data [7]
(L: Liquid, a: ferrite, y: austenite, 8:cementite, rr M6C, A: Laves phase, p:M7C3)
Fe + 6-18 W + 0-2.5 C, Fe + 6-18 W + 4 Cr + 0-2.5 C

Fe + 6-14 Mo + 0-2.5 C, Fe + 6-14 Mo + 4 Cr + 0-2.5 C
Fe + 12-18 Mo + 5-10 V + 4 Cr + 0-2.5 C
Fe + 6-18 W + 5-10 V + 4 Cr + 0-2.5 C
Fe + 14 Mo + 4-12 Co + 4 Cr + 0-2.5 C
1700+-'---L-I-L--'-....L-'---L-I-L--'-....L-1-L-I....J..--'---'--'---t-
present work (DTA) {4% Cr. 14%Mol
o liqudus
6. solidus
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
w%c
Figure 8: Calculated phase diagram of the C-Cr-Fe-Mo system (4% Cr, 1% V)

compared with experimental DTA data [7]
(L: Liquid, a: ferrite, y: austenite, 8:cementite, 11: M6C, A: Laves phase, rc:M23C6)
Some of these calculated systems, particularly those with V, were considered

unsuitable for further study since the austenite + carbide + L phase field was either
narrow or absent from them. Other systems though possessed austenite + carbide + L
fields which exhibited the features necessary for good sinterability; of these, the most
promising systems were those with high Mo contents, for example Fe-C-14Mo-4Cr
(Figure 8).
8.6 r----.,.----,-----,--------,
8.0
"E7.6
-a,
r·
.~
o
• P58 - 1.4 C
6.5
6.0 L -_ _ _L -_ _ _-'----_ _ _--'-_ _ _---'

1100 1160 1200 1260 1300
Sintering Temperature °c
Figure 9: Sintering curves for Fe-14% Mo- 4% Cr-1.4% C

(in weight) HSS powder.
Phase Diagram Calculations .. . for Economic Powder Metallurgy Processing 261
Figure 10: Microstructure of experimental Fe + 1.4 Mo + 4 Cr + 1.4 C alloy (in

weight %) at (a) 1190 and (b) 1220 °C, the limits of the sintering window. x750.
Sintering characteristics for an experimental Fe-1.4C-14Mo-4Cr alloy are shown in

Figure 9. The alloy was sintered to full density over a wide temperature range. The
optimum temperature was 1200 °C and the sintering window assessed at about 30°C.
This alloy possessed mechanical and cutting properties comparable to standard M2

and Tl HSS [8]. Microstructures are shown in Figure 10. The thermodynamic
parameters used in the calculations of the phase diagrams relative to the high speed
steels are taken from the Scientific Group Thermodata Europe (S.G.T,E.) [9]. The
calculations were performed with the Thermo-Calc software [10] kindly provided by
K.T.H, Stockholm (Sweden).
ACKNOWLEDGMENTS
The work reported in this contribution is supported by BRITE-EURAM, grant BREU

0165-C.
KEYWORDS
super-solidus liquid phase sintering (SLPS), high speed steels (HSS), powder
metallurgy processing, phase diagram
REFERENCES
[1] Y. Bienvenu, A. Wronski, M. Jeandin, C.S. Wright, F. Lemoisson, and M.

Vardavoulias, Rev. Metallurgie-CIT, Sci, Genie Materiaux, 91, (1994), 693-
705.
[2] C.S. Wright, and B. Ogel, Powder Metall., 36, (1993), 213-219.
[3] P. Beiss. R. Wahling and D Duda, "Modem Developments in Powder
Metallurgy", 17, (1985), 331-358
[4] C.S. Wright, M. Lewicka, W.J.c. Price, and L. Fontaine, Powder Metallurgy,
32,2(19891109-113
[5a] C.S. Wright, "Sintering 91", Proc. Vancouver 23-26 July 1991, Trans. Tech.,
Publ., (1992), 463-470.
[5b] C.S. Wright, "Powder Metallurgy '94", Proc. PM94, June, Paris, Ed. Ste.
Franyaise de Metallurgie et Materiaux, Vol. 2, (1994), 937-944.
[6] R.M. German, Intern. J. Powder Metall., 26, (1990), 23-43.
[7] K. Murakami. and A. Hatta, Sci. Rep. Tohoku Univ., Honda Anniversary
Edition, 882-895
[8] A. Wronski, C.S. Wright, W.J.C. Price, M. Oliveira, Y. Bienvenu, and F.
Lemoisson, "Powder Metallurgy 94", Proc. PM94, June, Paris, Ed. Ste,
Franyaise de Metallurgie et Materiaux, Vol. 2, (1994), 1035-1038.
[9] I. Ansara, B. Sundman, Computer Handling and Dissemination of Data, Ed.
P.S. Glaeser, Proc. Xth CODATA Conf., Ottawa July 1986. Elsevier Sci.
Pub. (1986).
[10] B. Sundman, B. Jansson, and J.-O. Andersson, Calphad, 2, 9, (1985),153-190.
THERMODYNAMIC ApPROACH TO THE DESIGN OF
NEW CERMETS PROCESSED BY LIQUID PHASE
SINTERING
CH. ALL/BERT and H. PASTOR*
Laboratoire de Thermodynamique et Physico-Chimie Metallurgiques, (associe

C.NR.S.) E.NS.E.E.G., BP. 75,38402 Saint Martin d'Heres, France.
*CERMEP, 54 Av. Rhin et Danube BP.65X, 38041 Grenoble Cedex 9 - France.
ABSTRACT
High performance materials can be obtained by mlXlng two phases with

complementary properties and adequate microstructure. The design and the
processing of such materials can be defined using phase equilibrium and stability
data. For example, the design of hard and tough cermets based on TiE2 is described:
- selection of metallic binder (Fe or Fe2Ti) for the TiE2 grains and evaluation of the
liquid phase sintering conditions with the phase diagrams,
- optimization of the sinteringprocess by addition elements chosen for their compound
chemical stability to cancel impurity effects without alteration of the material
constitution.
RESUME
Des materiaux a hautes caracteristiques peuvent resulter du melange de phases
presentant des proprietes complementaires et une microstructure adaptee. La
conception de tels materiaux par une approche thermodynamique est possible.
L'exemple est donne pour des cermets durs et tenaces abase de TiE2:
- selection d'un liant metallique (Fe ou Fe2Ti) pour les grains de TiE2 et prediction
des conditions de frittage du melange TiE2 - Fe(Fe2Ti) a l'aide de diagrammes
d'equilibre,
- optimisation du procede par addition d'elements, choisis a partir de donnees de
stabilite chimique pour neutraliser les impuretes, sans alterer les phases du materiau.
1 INTRODUCTION
For most materials, the various properties required in service can be acquired only by
coupling the specific characteristics of at least two constitutive phases. Cermets, used
as cutting tools, are a typical example of hard but tough materials. Their hardness is
provided by their major component (carbide, boride, diamond ... ). Their toughness is
generated by the small amount of soft binder (often fcc metal) joining the hard grains.
The mechanical characteristics of such composites obviously depend on the properties
and volume fractions of the components, but also on the interfacial wetting and on the
microstructure. The crack propagation, and consequently the strength limit, are
controlled by the interfacial adherence and the absence of brittle secondary phases on
the interface. Optimized properties are obtained in materials consisting of a regular
distribution of fine hard grains embedded in a continuous binder network. Such a
microstructure has to be generated by liquid phase sintering (LPS). LPS is one of the
powder metallurgy routes producing the consolidation of powders. All the previous
requirements are fulfilled by the cemented carbides based on WC-Co. Proposed at the
beginning of the 1920s, these materials were first developed using an empirical
approach. A more scientific work was then carried out, and is still continued, to
acquire the basic knowledge for the understanding and improvement of cemented
carbides processing and properties. Presently the information collected during the 20th
century on the genesis of composite properties and on the LPS behavior leads to
Stell I : Material De.ign
--
• Metal Properties Data
Composite Properties • Solid State Equilibria
(2 phase field)
.L
Possible ComEonents
Stell II : LPS Processing
"Intrinsic" Sinterability,
LPS Conditions -- • Liquid-Solid Equilibria
(solubitility)
J.
If Sinterability:
Material composition,
LPS temperature.
--
Effective Sinterability, • Phase stabilities
Impurity Effect Control (Wettability)
• Liquid-Solid Equilibria
.L
I Processing Schema
Figure 1: Steps in a predictive approach to material processing

Thermodynamic Approach to the Design of New Cermets 265
definition of general guidelines for the design of composites processed by LPS. From
these guidelines, a rapid approach to the processing of new materials with precise
properties is possible using simple thermodynamic tools such as phase diagrams and
phase stability, as schematized in Fig. 1.
As an example, the various steps of this approach are detailed for the design of new
cermets based on TiB2.
2 FIRST STEP: MATERIAL DESIGN FROM SOLID STATE PHASE

EQUILIBRIA
While the chief properties of cutting tools are hardness and toughness, sufficient
mechanical strength and corrosion resistance at temperatures locally reached in
machining (800-1100 DC) are also necessary.
Inasmuch as the hard phase TiB2 is selected a priori, a binder has to be found from the
metal properties database and the solid state phase diagrams of the systems Ti-B-
Metal. A suitable binder should be ductile, should not dissolve significant TiB2S
should permit maintenance of a high hard phase fraction and should not form
intermediate phases with TiB2. From the data published on 13 systems, AI,Cr, Fe and
Mn provide convenient phase equilibria, but only Fe fulfils the other main conditions.
Fe. --======"'""
Fig. 2 shows the isothermal section of the Fe-Ti-B system [1]. The domain TiB2-Fe
solid solution strictly corresponds to the requirements. According to the recent studies
that evidence the ductility enhancement of many intermetallics by small B additions,
the domain TiB2-FeTi could also be considered.
3 SECOND STEP: SINTERABILITY AND LPS CONDITIONS

PREDICTION FROM LIQUID - SOLID EQUILIBRIA AND PHASE
STABILITIES
3.1 General considerations
3.1.1 Ideal systems
LPS applies to the systems involving a large fraction of solid particles S in a minor
liquid binder BL. The densification results from the more compact packing of the S
particles driven by the capillary forces at the liquid meniscus: it occurs only if the
SIBL wetting is good and if the fraction of initial solid, dissolved in BL is sufficient
[2]. Because some dissolution always produces a correct wettability, the S solubility
in BL is the criterion that decides the sinterability and the composition range of the S-
B mixture to be sintered. Effectively, the higher the solubility, the easier the
densification and the larger the S amount possibly densified by LPS. Moreover, two
other characteristics are required for the S-BL domain:
- a composition range consistent with the two-phase domain S-B researched in the
solid state.
- an existence range in temperature T large enough for practical processing,
3.1.2 Actual materials
The above mentioned features hold for an ideal system. But the processing of actual
components includes the contribution of the impurities 0, C, N always adsorbed on
the powder surfaces. The stability of the phases formed between these impurities and
the constitutive elements and their physical state rule the practical processing. Any
phase formed in the gaseous state can be eliminated by flowing in a suitable vector
gas. If one of the material components is present in this phase, its content must be
controlled using additions. The processing of the cemented carbides WC-Co provides
a good example of the composition monitoring by a graphite balance of the C losses
due to the CO, C02 elimination [3]. More difficult to solve is the problem of the
condensed phases. In this case, either addition elements or specific T conditions must
be used to trap the impurities in compounds with locations and microstructure not too
detrimental for the LPS and the material.
Thermodynamic Approach to the Design of New Cermets 267
3.2 Application to the TiB2 Cermets
3.2.1 Ideal system Fe-Ti-8
According to the previous considerations, the composition range available for the
binder must be well defined. To present the literature data [1], the partial isothermal
section at 1050 °C is plotted (Fig.3).1t underlines two important features [4,5]: the Fe-
base binder has to contain 1-5 at % Ti to form the equilibrium with TiB2. Concerning
the Fe2Ti binder, experimentation shows a strong effect of the small 0 content of the
starting materials (see (3.2.2) that renders unreliable the results on the Ti-rich alloys.
On the Fe-rich side, the boundary of the 2-phase field corresponds to TiB2-Fe2.sTi.
x(Til----
Figure 3: Partial isothermal section at 1050°C. The limits of the 3-phase domain TiB2
+Fe +Fe2Ti are defined by Fe 5.4 at % Ti and Fe 28.5 at % Ti
The partial isothermal section at 1450 °C is experimentally determined to evaluate the

TiB2 solubility in the liquid binders (Fig. 4). From DTA on compositions close to Fe-
TiB2 and Fe2.4Ti-TiB2, the vertical cuts are schematized (Fig. 5).
Fe .2 X(Ti)--
Figure 4: Part of the field TiB2 + liquid at 1450°C
The analyses of the phase equilibria lead to the following conclusions:
- Two binders are possible, the Fe-base solution with 1-5 at %Ti, and the phase
Fe2+xTi (x = 0.2-0.5). The compositions Fe-2 at %Ti and Fe2.4Ti are retained. They
can be easily adjusted in the process, that requires powders as starting materials, by
mixing Fe and Fe2Ti powders. Fe2Ti is brittle and stable [6] enough to be crushed
without undergoing decomposition.
- The TiB2 solubilities in the liquid binders are sufficient to predict the sinterability,
but mainly for composites containing at least 20 vol% binder. The densification is
expected to be easier with the Fe-base binder, a better solvent for TiB2.
- The LPS temperatures must be located inside the (TiB2 + liquid) field, consequently
above respectively 1320 and 1370°C. A T ranging from 1400-1450°C is suitable and
provides a liquid-TiB2 field fully consistent with the 2-phase fields (TiB2 + binder) to
be obtained in the solid state.
Thennodynamic Approach to the Design of New Cennets 269
liq. S+ liq.
B+S+liq.
B+S
B S
Figure 5: Typical vertical sections along the lines TiB2 + Fe 2 at % Ti and TiB2-
Fe2ATi. The temperatures of the equilibria TiB2(S) + binder B + liquid ~ TiB2 +
liquid are respectively 1320 and 1366°C
3-2-2 Actual materials « Fe »-TiB2 and « Fe2Ti »-TiB2
°
Powder metallurgy always involves the surface impurities 0, C, N. Moreover, it is
difficult to find bulk Ti with an content less than 0.2 weight %. Taking into account
the strong free energies of fonnation of the Ti oxides, carbide and nitride,
complementary investigations of the 0, C, N effects son the phase equilibria and
wettability were carried out.
In the composition range (Fe-Fe2Ti-TiB2), the slight amounts ofO, C, N react withTi
and give Ti (0, C, N) particles. The formation of this phase does not significantly
change the Fe-Ti-B phase equilibria but it decreases the Ti content available to fonn
the Fe-rich phases. The behavior is consistent with a rough estimation based on the
free energies of formation. For Ti contents higher than those defined by the line
Fe2Ti-TiB2, a phase with composition Fe3Ti30 is generated and the ° contribution
cannot be simply predicted [5]. The study of the wettability of TiB2 substrates with
°
various contents by Fe-base liquids [7] emphasizes a strong hindrance of the liquid
penetration ascribed to a Ti oxide film on the TiB2/liquid interface. Finally, a simple
approach based on phase stability and phase equilibria concludes that the LPS of TiB2
°
with either Fe 2 at %Ti or Fe2.4Ti as binders should be theoretically possible, but can
be completely inhibited by the effect. At this point, the main problem is to find an
element more oxidizable than Ti, that can be added to free the TiB2 grains from any
oxide films without affecting the Fe-Ti-B phase equilibria. On the basis of binary data,
Rare Earth (RE) elements are selected for the reduction ofTiO; they might not modify
the phase equilibria, at least in the Fe-rich comer of the Fe-Ti-B system: RE borides
[8] are less stable than TiB2, RE-Fe compounds are not very stable [9], REs do not
form solid solutions or binary intermetallics with Ti [10], but they give ternary phases
RE Fe12_xTix [11].
The second problem is to add Ti to balance the Ti amount trapped in Ti(C, N) and
keep the binder content constant.
Two preliminary experiments were attempted to check the predicted effects of the RE
and Ti additions on the phase equilibria. In the domain (TiB2 + Fe-base binder), the
amounts of Fe2Ti and Nd to be introduced were calculated on the basis of the reaction:
Fe + TiB2 + (0, C, N) ~ Fe 2 at %Ti + TiB2

+ Fe2Ti +Nd + Ti (C, N) + Nd203
After reaction at 1400°C and then annealing at 1100°C, the observed final state
°
corresponds to the prediction, the only difference is a small content in Ti (0, C, N).
In the field (Fe2Ti + TiB2), the addition of H02Fel7 did not produce H0203 but
°
HoFe1OTi2, being trapped in Ti (0, C, N).
Finally, the thermodynamic approach proposed for the LPS processing of the cermet
TiB2 + Fe 2 at %Ti suggests the following conditions:
Starting mixture: TiB2 (80vol%) + Fe

Additions: Ti to adjust the binder content and form Ti (C,N) and Nd to
deoxidize as Nd203.
Temperature: 1450°C.
For the cermet TiB2-Fe2.4Ti, the deoxidation problem is not solved by RE additions.
Nevertheless, the strong deoxidation effect ofTi itself suggests attempting the direct
LPS of TiB2 (80vol%) + Fe2Ti mixtures, expecting some Ti of the binder phase to
"clean" the TiB2 surface.
3-2-3 LPS control
The application of the processing schema to the LPS ofTiB2 with Fe2Ti or Fe 2at%Ti
[12] has to take into account two main differences with the phase equilibria studies:
- TiB2 is the major component and provides an impurity level much higher than in the
previous case.
- RE has to be introduced as a powder: NdNi5 can be selected for its brittleness and
chemical stability, but it involves some Ni.
Thennodynamic Approach to the Design of New Cennets 271
For the Fe-base binder, the 0, C, N contents are measured on the starting mixture
TiB2(80vol%) + Fe. Then, the NdNi5 and Fe2Ti amounts to be added are calculated
assuming that:
* °
Nd reacts with 90% and forms Nd203
* Ti reacts with C, Nand 10% 0, giving Ti (0, C, N) and dissolves in Fe, up to
Fe 2 at%Ti.
* Ni substitutes for Fe in the binder
For sake of comparison, two other materials were prepared: the mixture TiB2
(80vol%) + Fe(l) and the mixture identical to the calculated mixture (2) but without
Nd(3). The results (Table 1) confirm all the predictions. With reference to the phase
constitution, the sample (1) contains some Fe2B, beside the main phases TiB2 and Fe,
and ETi; this is consistent with the boundary of the field (TiB2 + Fe solution). The
samples 2, 3 show that the parasitic phases Nd203 and Ti (0, C, N) do not change the
limits of the tie-lines of the TiB2-Fe solution. Concerning the densification, the major
"surface cleaning" role of the Nd is visible in sample (3) densified up to 97%.
At% B Ti Fe Ni Nd 0 C N
(1) 55.6 27.8 15 0 0 1.1 0.2 0.3
(2) 55.35 28.2 12.66 2.38 0.48 0.81 0.09 0.Q3
(3) 55.34 28.9 12.33 2.47 0 0.83 0.09 0.03
Table la: Atomic contents of the elements in the studied samples
Sample Phases Relative

density
(1) calculated Fe.99sTi.oos Fe2B Ti(O.69C.l~.19) 0.82
observed bee Fe solution Fe2B cubic Ti(O,C,N)
(2) calculated Fe.82Ni.16Ti.02 Nd203 Ti(O.43C.43N.14) 0.97
observed bcc Fe.83Ni.14Ti.03 Nd203 cubic Ti(O,C,N)
(3) calculated Fe.82Ni.16Ti.02 Ti(O.88C.09N.Q3) 0.88
observed bce Fe solution cubic Ti(O,C,N)
Table Ib: Predicted and observed phases. The major phase TiB2 is not reported.
Concerning the other binder, starting from the mixture TiB2(80 vol%)-Fe1.9Ti, the
sintered material consisted of TiB2-Fe2.4Ti and some Ti (0, c, N), and its relative
density was 93%.
4 CONCLUSION
In many cases, the simple tools of phase equilibria and phase stabilities enable the
rapid prediction of the feasibility of materials processing. For TiB2 cermets, the study
related to the Fe-base binder was carried out using, in parallel, sintering
experimentation and phase equilibria determination. A correct densification behavior
was reached only by application of the thermodynamic results. In the case of the
Fe2Ti binder, only two sintering experiments, carefully designed from the phase
equilibria data, provided a material with the expected constitution and a significant
densification. In these two cases, the efficiency of the thermodynamic approach is
clearly demonstrated.
KEYWORDS
phase stability, phase diagrams, liquid phase sintering, cermets
REFERENCES
[I] T.F. Fedorov and B. Kuzma, Izv. Akad Nauk SSSR, Neorg. Mat. 3,
(1967), 1498-1499.
[2] R.M. German, Liquid Phase Sintering, Ed. Plenum Press, New-York
(1985).
[3] P. Schwarzkof, R. Kieffer, "Cemented Carbide", The MacMillan Co.,
New-York, (1960), 74-101.
[4] L. Ottavi, C. Saint-loours, N. Valigat and C.H. Allibert, Zeit. Metallk.
83 (2), (1992), 80-83.
[5] P.O. Robert, J.M. Missiaen, c.H. Allibert and H. Pastor, PM'94
proceedings, Ed. Phy,. Paris (1994),1537-1540.
[6] J.L. Murray, Bull. Alloy Phase. Diag., 2, 3, (1981), 320.
[7] N. Gayraud, V. Ghetta and N. Eustathopoulos, Solid State Phenomena,
(1992), 25-26
[8] J.Barin, Thermochemical Data of Pure Substances, VCH Verlag. D6940,
Weinheim (Germany) (1989).
[9] C. Colinet and A. Pasture I, Calphad, 11,4, (1987), 323.
[10] "Titanium: Physicochemical Properties of its Compounds and Alloys"
Atomic Energy Review, Sep. issue N°9, O. Kubaschewski, Ed.Int.
Energy Agency Vienna, (1983).
[11] K.H.J. Buschow, J. Magn. Mater., 100, (1991), 79-89.
[12] L. Ottavi, J.M. Chaix, C.H. Allibert and H. Pastor, Solid State
Phenomena 25-26 (1992),543-550.
Chapter 5
SYNTHESIS AND ApPLICATION OF NEW

MATERIALS
PREPARATION OF THIN FILMS USING A SOL-GEL

METHOD
I.e. PLENET*, e. URLACHER*, F. PAILLE*, e. BOVIER*,

I. SERUGHETTI*, I. DUMAS*, I. MUGNIER**
* Departement de Physique des Materiaux, URA 172, Universite Claude

Bernard Lyon 1, 43 Boulevard du 11 Novembre 1918, 69622 Villeurbanne
cedex, France
**Laboratoire de Physico-Chimie des Materiaux Luminescents, URA 442,
Universite Claude Bernard Lyon 1,43 Boulevard du 11 Novembre 1918, 69622
Villeurbanne cedex, France
ABSTRACT
The different steps of thin film preparation by a sol-gel process are discussed:
preparation of the starting solutions, control of the viscosity of the sol, deposition
methods and thermal treatments. Transmission Electron Microscopy (TEM), Scanning
Electron Microscopy (SEM) and Waveguide Raman Spectroscopy (WRS) are used to
obtain structural characterization of the layers. The option of matrix doping is cited.
Some optical properties of thin films using waveguide techniques and non-linear
properties are underlined.
RESUME
Les differentes etapes d'elaboration de couches minces par Ie procede sol-gel sont
presentees: preparation des solutions de depart, viscosite du sol, methodes de depot et
274 Synthesis and Application of New Materials
traitements thermiques. Des mesures par microscopie electronique a transmission, a

balayage, et par spectroscopie Raman en configuration guidante, ont ete menees pour
caracteriser la structure des couches. Les possibilites de dopage de la matrice sont
rappelees. Quelques proprietes optiques des couches minces utilisant des techniques
de guidage optique et des proprietes non lineaires sont soulignees.
1 INTRODUCTION
The sol-gel denomination derives from the fact that the precursor materials are
prepared in solution. It is probably one of the oldest thin film preparation methods:
the first report [1] on silicate sol-gel films formed by dip-coating was written in 1939.
Sol-gel thin film coatings are intensively studied today for multiple applications such
as optical coatings [2,3], passivation layers [4], sensors [5], high or low dielectric
constant films [6], inorganic membranes [7], electrooptic and non-linear optical films
[8], superconducting films [9] and ferroelectrics [10].
This paper reports studies of sol-gel thin film formation especially by dip-coating. We
first review some important points in sample preparation. We then discuss their
structural characterization by methods well adapted to layer examination and their
optical properties. We finally extract from these results the advantageous
characteristics of the method. The aim of these studies is to establish schemes
allowing generation of controlled film microstructures and their characterization for
specific applications.
2 SAMPLE PREPARATION
2. 1 Starting solutions
Sol-gel chemistry is based on the hydrolysis and condensation of metal alkoxides [11]
• Hydrolysis: M-OR + H20 --? M-OH + R-OH
• Condensation: M-OH + R-OH --? M-O-M + R-OH
Condensed species are formed as these reactions proceed leading to oxopolymers and
then hydrous oxides MOn.xH20 when an excess of water is added. Such a description
of sol-gel chemistry is, however, far too simple and does not explain why chemical
additives (e.g. acid or basic catalysts) have to be added in order to control the growth
of the oxopolymers.
For more details on this chemistry, see for example Ref 12. In the following sections,
results on CdS-doped silica and PbTi03 thin films will be given as examples to
illustrate sol-gel processing and applications. Details of thin film preparation are
shown in Fig. 1.
Preparation of Thin Films a Using Sol-Gel Method 275
stirring during 1 hour
I
storage at the
desired te~perature
viscosity
measurement
dip-coating on Pyrex substrate
I
thermal treatment at 80°C during 10 min
I
I
annealing at 450°C under oxygen
S.E.M. observations
• t
thickness measurement
exposure to H,S
- precipitation of the CdS nanocrystals

in the silica matrix
T.E.M. observations
------optical measurement Crystallized PbTiO, thin films
Figure 1 : Flow charts of thin film preparation
2.2 Viscosity
One of the most important parameters to control thin film microstructure is the starting
solution viscosity [13]. The sol-gel process is a very efficient method to produce a
silica matrix with a required pore size distribution. Such abilities offer the opportunity
to incorporate nanoparticles in order to obtain layers with specific properties. The
evolution of the viscosity of the initial solution (Cd-doped silica) depending on the
storage time at a given temperature is reported in Fig.2.
The measurements have been performed using the capillary method in an Ubbelohde
viscometer. As expected, the viscosity increases with time and temperature. This kind
of experiment allows accurate determination of the best means to deposit the film :
indeed, too liquid a solution results in a too densified network whereas a rough and
inhomogeneous layer is obtained when the viscosity is too high.
6,------------.----------------,-,
g- 5
a
l:' 4
I/)
o
(.)
I/)
3
>
2
o 50 100 150 200

Time (h)
a T=15°C
b T=25°C
Figure 2 : Viscosity of a 60 wt% Cd doped Si02 sol as a function of time at T=15°C

(a) and T=25°C (b)
2.3 Deposition techniques
Among the several coating methods [14] used in the sol-gel technologies (spin-
coating, drain-coating ... ), the dip-coating technique will be described in this paper
because this method is easy to develop and to control. A typical dip-coater scheme is
given in Fig.3. The films are deposited, at a constant withdrawal speed, onto sonically
cleaned, amorphous pyrex substrates (borosilicate glass), in a plexiglass chamber with
a controlled atmosphere.
motor
+
gearbox
cen tral
ax Is
~-
dipping
solution
container
Figure 3 : Typical dip-coater apparatus

2.4 Thermal treatment
The last step of the thin film preparation consists in a heat treatment to densify the
material and to eliminate solvents, water and organic compounds. From room
temperature to about 100°C, the gelled film shrinks and loses weight through the
evaporation of physically absorbed water and most volatile solvents. During the
annealing treatment (from 100°C to about 400 °C or more) under a controlled
atmosphere, organic residues are pyrolyzed and oxidized. The annealing temperature
is fixed taking into account the final function of the layers: porous silica films require
a lower annealing temperature than those which are to be crystallized (PbTi03). For
multilayers, the films are heat treated at 400°C between each coating step to promote
organic burnout and partial densification.
3 STRUCTURAL CHARACTERIZATION
The determination of the microstructure of the films is a very important step to

optimize the material for the required applications.
3.1 Microscopic analysis
Conventional Transmission Electron Microscopy (CTEM), High Resolution

Transmission Electron Microscopy (HRTEM) and Scanning Electron Microscopy
Figure 4: HRTEM and CTEM micrographs of CdS nanocrystals in an amorphous

silica matrix
(SEM) are used to study our samples. High Resolution and Conventional
observations were carried on with a JEOL 200 CX Electron Microscope. FigA gives a
typical example of a CdS nanocrystal in an amorphous silica matrix as visualized by
HRTEM and a greater area of the sample as observed by CTEM.
HRTEM observations are used to confirm the crystallinity of the nanoparticles and to
determine their geometrical shape. CTEM micrographs are conducted to determine the
particle size distribution which, in this case, is centered around 4 nm in diameter.
The films are also observed with a Hitachi S800 Scanning Electron Microscope which
allows assessment of the homogeneous texture of the films and measurement of their
thickness in the perpendicular observation mode. Fig.5 shows a micrograph of a
multilayered sample in which the regular thickness of the film, coated on a pyrex
substrate, can be observed.
Figure 5 : SEM micrograph of a two-layered thin film dip-coated on a Pyrex substrate

from a Si02 - 60 wt% Cd doped sol
3.2 Waveguide Raman spectroscopy (WRS)
In some cases, sol-gel thin films can be used as a waveguide. On the one hand this is a
proof of the good optical quality of the layer. On the other hand it is possible to
examine the structure of the layers by using their waveguiding properties. Details of
the WRS technique have been described elsewhere [15], [16].
Briefly, at room temperature, a krypton laser beam is focused by a converging lens

near the comer of a prism coupler used to launch the light into the film. Light
scattered by the film is analyzed by a Jobin-Yvon model U-I000 spectrograph and a
photon counting system.
The Raman spectrum obtained for pure Ti02 thin film over the range from 4 cm- I to
718 cm- I , as shown in Fig.6, is characteristic of the Ti02 crystalline structure; a
typical Raman spectrum of bulk anatase [17] exhibits the same peaks. Moreover, from
the low frequency part of this spectrum the mean size of the nanocrystals can be
deduced.
~ [I
.
.,, . .:,
,
. : I
.,'.0......- ./ '5- ---
o 200 400 600

(() (em-I)
Figure 6: WRS spectrum of a Ti02 thin film
The WRS technique is a non-destructive method which allows determination of the

structure of very thin films without any effect of the substrate.
4 OPTICAL PROPERTIES
The sol-gel process has proved to be an excellent method for the preparation of many
types of optical coatings (transparent, without cracks ... ) so that waveguides and
highly nonlinear materials can easily be obtained.
4. 1 Waveguide properties
Refractive index and attenuation coefficient determinations are an important point for
waveguide characterization. Refractive indices are determined by an m-line
spectroscopy technique described in Ref 18. The incident light is polarized, either
parallel or perpendicular to the waveguide plane. The optical measurements are made
at a wavelength of 632.8 nm. Optical loss of the film is obtained by measuring the
propagated light scattered from the waveguide as a function of the position. The light
is taken to be proportional to the intensity in the waveguide at that position, thereby
assuming the scattering to be uniform throught the layer. A video camera is set to
observe the light streak of the excited mode in the waveguide and the output video
signal of the camera is sent directly to a microcomputer. The logarithm of the
scattered intensity versus the propagation position is plotted and a linear least squares
fit of the scattering points gives the average optical loss (in dB/cm). Optical
measurements were conducted on a sol-gel derived PbTi03 thin film. The refractive
index value measured for a monolayer was 2.01. As shown on the graph represented
in Fig.7, a coefficient of attenuation of 7.S±0.8 dB/cm was obtained for the TMO
excited mode in the same layer.
25 ~---------------------------------------------------------.
20
(J. = 7.5. dB/em
5 -
o +------r-----+------r-----+------r----~------+_----~----_4
o 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
Propagation length (em)
Figure 7: Optical loss of a monolayer PbTi03 waveguide (632,8 nm)

4.2 Non-linear optical properties
Nanoscale semiconductor particles have gained considerable attention in recent years

because of their enhanced nonlinear optical properties and photocatalytic properties
[18,19]. The observation of a photoinduced blue shift in the absorption spectra and an
exciton peak are evidence of quantum size effects due to the confinement of electronic
excitations inside the nanocrystals. Details concerning optical non-linear
measurements performed on our CdS doped silica xerogels can be found elsewhere
[20]. Nevertheless, Figure 8 shows a typical result like the non-linear coefficient
variation (X 3) with the weight concentration of the nanoparticles. Few measurements
of X3 were made on pure CdS nanocrystals [21,22]. Values ranging between 10-9 to
10-8 were obtained under conditions of resonant excitation. That means one order of
magnitude smaller than our results. In this field of quantum size effects, the sol-gel
technique also seems to be a very promising route.
3~-------------------------,
r--
+ 2
r.:I
*
o+---~--~----~--~--~--~
o 10 20 30
Volumic Concentration of CdS (%)
Figure 8: X3 as a function of the volumetric concentration of CdS (%)
5 CONCLUSION
This paper is focussed on the preparation and the optical properties of sol-gel derived
thin films. We have underlined some advantageous qualities of this method: starting
solutions offer a good control of the purity of the precursors and a high degree of
homogeneity, control of viscosity and microstructure allows incorporation of trace
elements, production of highly transparent films for waveguides. Moreover, the sol-
gel process is a very inexpensive method to obtain thin films used in a large field of
applications.
KEYWORDS
waveguide Raman spectroscopy (WRS), sol-gel process, thin films

REFERENCES
[1] W. Geffcken and E. Berger, Deutsches Reichs Patent 736411, May 6, (1939),
assigned to Jenser Glaswek Schott and Gen., Jena
[2] D.P. Partlow and TW. O'Keeffe, Appl. Optics, 29, (1990), 1526
[3] H.G. Floch, lJ. Priotton and I.M. Thomas, Thin Solid Films, 175, (1989), 173
[4] W.L. Warren, P.M. Lenahan, CJ. Brinker, G.R. Shaffer, C.S. Ashley and
S.T. Reed, "Better Ceramics Through Chemistry IV", Eds. B.lJ. Zelinski,
CJ. Brinker, D.E. Clark and D.R. Ulrich, Mat. Res. Soc. Symp. Proc., vol.
180, Mat. Res. Soc, Pittsburgh, PA (1990) 413
[5] T. Bein, G.e. Frye and C.J. Brinker, J. Am. Chern. Soc.,l1 I, (1989), 7640
[6] CJ. Brinker, A.J. Hurd and KJ. Ward, "Ultrastructure Processing of
Advanced Ceramics", Eds. J.D. Mackenzie and D.R. Ulrich, Wiley, NY
(1988) 223
[7] M.A. Anderson, M.J. Geiselmann and Q. XU, J.Membrane Sci. 39, (1988),
243
[8] S. Hirano and K. Kato, J. of Non-Cry st. Solids, 100, (1988), 538.
[9] S.A. Kramer, G. Kordas, J. McMillan, G.e. Hilton and D.J. Van Harlingen,
Appl. Phys. Lett. 53, (1988), 156.
[10] J. Fukushima, K. Kodaira and T. Masushita, J. Mater. Sci., 58, (1984),595
[11] C.J. Brinker and G.W. Scherer, Sol-Gel Science, Academic Press, New York
(1990)
[12] J. Livage, M. Henry, C. Sanchez, Progress in Solid State Chemistry 18,
(1988),259.
[13] T Mizuno, J. Phalippou and J. Zarzycki, Glass Technology 26, (1985), 9
[14] L.C. Klein, Sol-Gel Optics Processing and Applications, Ed L.C. Klein,
Kluwer Academic Publishers, New York, (1994), 141
[15] Y. Levy, e. Imbert, J. Cipriani. S. Racine and R. Dupeyrat, Opt. Commun.
11, (1974), 66.
[16] J. Mugnier, B. Varrel, M. Bathat, C. Bovier and J.Serughetti, J. Mater. Sci.
Lett. 11,(1992),875-877
[17] T Ohsaka, F. Izumi and Y. Fujiki, J. Raman Spectrosc. 7, (1978),321
[18] Y. Wang, J. Phys. Chern. 95, (1983), 1119.
[19] E. Vogel, MJ. Weber and D.M. Krol, Phys. Chern. of Glass, 32, (1991),
2310.
[20] A.Othmani, J.e. Plenet, E.Bemstein, C. Bovier, J .Dumas, P. Riblet, P.
Gilliot, R. Levy and J.B. Grun, J. of Crystal Growth, 144, (1991), 141.
[21] Y. Nosaka, K. Tanaka and N. Fuji, Appli. Phys. Lett. 62, (1993), 1863.
L.T. Cheng, N. Herron and Y. Wang, J. Appl. Phys 66, (1989), 3417
[22]
AQUEOUS PREPARATION OF CHEMICALLY
HOMOGENEOUS MULTICOMPONENT SILICATE
PRECURSORS.
1. JAYMES and A. DOUY
CNRS, Centre de Recherches sur la Physique des Hautes Temperatures

1D, Avenue de la Recherche Scientifique, 45071 Orleans Cedex 02, France.
ABSTRACT
Chemically very homogeneous precursors of mu/ticomponent silicate oxides may be

easily prepared from rather dilute aqueous solutions of metal nitrate(s) in which a
silicon alkoxide is hydrolyzed into silicic acid. The transformation into solid
precursors is achieved by different processes. Fine powders are obtained by spray-
drying (examples of mullite and cordierite) and gels by in-situ generation of a base
(examples ofmullite and zircon)
RESUME
Des precurseurs chimiquement tres homogenes d'oxydes silicates peuvent etre

facilement obtenus apartir de solutions aqueuses, relativement diluees, ade nitrate(s)
mhallique(s) dans lesquelles un alcoxyde de silicium est hydrolyse en acide silicique.
La transformation en precurseur solide peut se realiser de differentes far,:ons. On
obtient ainsi des poudres fines par atomisation (exemples de la mullite et de la
cordierite) ou des gels par generation d'une base au sein de la solution (cas de la
mullite et du zircon).
1 INTRODUCTION
Among the areas of ceramic science and technology which have changed the most
rapidly, the use of sol-gel techniques to prepare materials with novel chemistries,
microstructures and properties seems particularly noteworthy and promising [1]. Sol-
gel chemistry is based on the hydroxylation and condensation of molecular precursors,
via the hydrolysis of metal alkoxides in organic solutions, or by changing the pH of
aqueous solutions of metal salts [2,3]. The alumina-silica system has been extensively
studied. It is well known that the silicon and aluminum alkoxides have very different
reactivities towards hydrolysis and condensation, the silicon alkoxides being much
less reactive than those of aluminum. So, if a single-phase aluminosilicate gel is
needed, much care has to be taken during the preparation: the nature of the alkoxides,
solvent, quantity of added water for the hydrolysis and the rate of its addition,
catalysis, pH, temperature, prehydrolysis of the silicon alkoxide, modification of the
aluminum alkoxide to make it less reactive, .. .In aqueous processes the metal
precursors are often sols (alumina and silica) or mixtures of sol and salt; so diphasic
gels are obtained. However, if chemical homogeneity is the aim in the preparation of
aluminosilicate or other multicomponent silicate precursors, powders, or gels, this
may be easily attained by aqueous processing. Aqueous solutions of metal nitrates are
usually acidic (pH - 2-3 for aluminum nitrate). When a silicon alkoxide,
tetraethoxysilane (TEOS) is added to such a solution, under strong stirring, it is slowly
hydrolysed into silicic acid, Si(OH)4. This silicic acid further condenses to oligomeric
species and then to silica gel. In dilute solution, at pH 2-3, the kinetics of the
hydrolysis of the alkoxide is maximum while that of the condensation of silicic acid is
minimum [4], and many weeks may be necessary at ambient temperature for
polycondensation to silica gel. This polycondensation may be accelerated by changing
the pH, the temperature or the concentration. In freshly prepared aqueous solutions of
metal nitrates and silicic acid, silicon and aluminum are mixed at the molecular level.
The transformation of this precursor solution into chemically homogeneous powders
or gels may be performed through different techniques. Among them, spray-drying
and homogeneous precipitation will be considered.
2 SPRAy-DRYING
By spray-drying a solution of aluminum nitrate and silicic acid, and further calcining
to remove completely the nitrate ions, a powder is obtained which crystallizes
completely into mullite at 980°C [5]. This crystallization temperature is a well known
criterion of single phase precursors. By aging the precursor solution at 100°C for
some days, silicic acid polycondenses and after spray-drying a diphasic precursor is
obtained. This powder crystallizes into mullite at higher temperature, via aluminum-
silicon spinel, or y-alumina and aluminum-silicon spinel. This aging of the solution at
elevated temperature is thus a simple means for controlling the chemical heterogeneity
in the precursor, mullite densifying at lower temperature from diphasic precursors.
The spray-drying of a solution of aluminum and magnesium nitrates and silicic acid,
and further calcination, yields a powder which crystallizes into a-cordierite, the stable
... Homogeneous Multicomponent Silicate Preparations 285
phase, via only /l-cordierite [6] (Figs. I & 2). So a chemically very homogeneous
powder is obtained by this simple aqueous process, while by the alkoxides route in an
organic solvent, single phase precursors are not easily synthesised for this ternary
oxide.
974 1018
b
b
800 900 1000 1100 1200

2 8 degrees ([u K cd
TEMPERA TURE (O[)
Figure 1: DSC curves (5°C/min) of the Figure 2: XRD diagrams of the

cordierite precursor powder cordierite powder A, spray-dried without
a) Powder A, spray dried without organic organic polymer
Polymer, annealed at 850°C for 2 H a) heated to 1000°C: J.L-cordierite with a
b) Powder B, spray dried without organic little amount of a-cordierite
Polymer b) heated to 1300 °C : a-cordierite
Since the evaporation of the solvent is very rapid, the synthesized powders form
hollow spheres. It is therefore necessary to break down the particles when they are
used for fabrication of dense ceramics. On the other hand hollow particles are
considered to be suitable for raw materials of porous ceramics. For the spray-dried
cordierite precursors, porous ceramics with very low density are obtained by firing the
compacted samples; the hollow particles swell before crystallizing. When a soluble
organic polymer, such as polyacrylamide, is added to the precursor solution before
spray-drying, the specific surface area of the powder is considerably increased and the
compacted samples sinter completely by a viscous flow before crystallizing, and dense
ceramics are obtained. Even though the swelling of the precursor or the role of the
organic polymer are not well explained, porous or dense cordierite ceramics may be
easily prepared from precursors obtained by spray drying aqueous solutions. Other
examples of multicomponent silicates are lead silicates. Many crystallized phases exist
in the PbO-Si02 system. They may be obtained as single phases more easily by
annealing spray dried powders, from aqueous solutions of lead nitrate and silicic acid,
than from glasses of the same composItions [7]. By spray-drying, powders of

intimately mixed condensed silicic acid species and metal nitrates are obtained. If
chemical homogeneity is the objective of the preparation, this may be easily attained
for many multicomponent silicates by simple spray-drying of aqueous solutions and
calcination of the powder to completely decompose the nitrate ions.
3 HOMOGENEOUS PRECIPITATION
Another way to solid precursors from the aqueous solution, is the precipitation of
hydroxides by the addition of a base. When a base is added to a solution of metal
nitrate and silicic acid, the metal is hydroxylated and polycondenses to make a gel or a
precipitate, while the raising of the pH accelerates the polycondensation of the silicic
acid into silica gel [4]. The addition of the base may be performed by different ways:
by abruptly precipitating the precursor solution into an excess of base, by slow
addition of the base, or by in-situ generation of the base. The latter reaction, a
perfectly homogeneous addition, may be achieved by hydrolysis of urea at 80-100De.
Urea is decomposed into ammonia and carbon dioxide. This reaction had already been
used in the preparation of single oxides and some mixed oxides. When applied to the
preparation of silicates, interesting results may be obtained.
3.1 Mullite
In the case of mullite [8], starting from a solution of aluminum nitrate and silicic acid,
diphasic precursors are obtained by classical addition of a base. By the in-situ
generation of ammonia, at 80-IOO D e, a monolithic silica gel is rapidly formed,
probably due to a catalytic reaction where urea must be involved. Then, while the
hydrolysis of aluminum progresses, the Si-O-Si bonds are broken by the partially
hydrolysed aluminum species which link to the gel by Si-O-AI bonds. The aluminum
atoms are firstly incorporated in tetrahedral sites and then in octahedral coordination.
The gel is slowly digested and a clear colloidal solution is obtained. The size of the
colloidal particles decreases rapidly to a Stokes radius of 2 nm. Fig. 3 shows the 29Si
NMR spectra of the first gel and colloidal solutions for different degrees of hydrolysis
of aluminum. The chemical shift 8 moves from -110 ppm corresponding to the silica
gel to -78 ppm where the silicon atoms are linked to three hexacoordinated aluminum
atoms by Si-O-AI bonds and a hydroxyl group. The local structure around the Si and
Al atoms is very similar to that of natural imogolite. This reaction clearly shows the
complete digestion of a silica gel by partially hydrolysed aluminum atoms and the
formation of very homogeneous aluminosilicate colloids. Upon completion of the
hydrolysis a gel is again obtained by crosslinking of the colloidal particles. The 29Si
NMR spectrum of this gel still shows a single environment for the silicon atoms, at -
78 ppm, and by thermal treatment a strong modification is observed. At 300 D e the
distribution of the sites becomes very broad.
... Homogeneous Multicomponent Silicate Preparations 287
This single phase precursor also crystallizes completely into mullite at 980°C.
b c
-40 -60 -80 -100 -120 -140 -160 -40 ·60 -80 -100 -120 -140 -so -60 -70 -80 -90 -100-110-120-130
ppm ppm ppm
Figure 3: 29Si NMR evolution during the synthesis ofmullite

a) MAS NMR of the first gel, with the degree of hydrolysis h=OHlAI for AI.
b) Static NMR of concentrated colloidal sols.
c) MAS NMR of the second gel, precursor of mullite at 80°C and heat-treated to
different temperatures.
3.2 Zircon
In the case of zirconium silicate, by the same processing method, starting from a
solution of zirconyl nitrate, silicic acid and urea, a gel is obtained at 80°C after some
days_ In the dried gel, crystallized zircon ZrSi04 is clearly identified by X ray
diffraction (Fig. 4) and IR spectroscopy in some preparations [9]. The crystallization
of zircon usually needs high temperatures (> 1300°C) even from gels prepared by the
alkoxides route. The yield of zircon in the low temperature synthesis depends on many
parameters, among them the concentration plays an important role. Further studies, on
the first step of the synthesis, are necessary for a better understanding of the
chemistry_ Thus the homogeneous precipitation by in-situ generation of ammonia
presents unexpected reactions in the synthesis of silicates. However for many cations
which are easily carbonated, this reaction is inefficient, because the hydrolysis of urea
also generates carbon dioxide, and a mixture of silica and metal carbonate is then
produced. Meanwhile by a very slow addition of ammonia under refluxing conditions,
it may be expected to approach the conditions of homogeneous precipitation.
soo·c
so·c I~S=~2S'-'====3'E'S=""'4S;==~S.S
29 de~rees <CuK cd
Figure 4 : XRD diagrams of a gel obtained at 80°C in the synthesis of ZrSi04 and
heat-treated for 1 h at different temperatures, z=zircon, t=tetragonal zirconia
4 CONCLUSION
From these examples it is shown that homogeneous multi component silicate

precursors may be easily prepared from aqueous solutions of metal nitrate(s) and
silicic acid. These precursors may be powders obtained by spray-drying the solution,
which necessitates calcination to remove the nitrate ions, or gels by in-situ generation
ofa base.
KEYWORDS
sol-gel process,spray drying, homogeneous precipitation, multicomponent silicates
REFERENCES
[1] C.J. Brinker and G.W. Scherer, Sol-Gel Science, "The Physics and Chemistry
of Sol-Gel Processing", Academic Press, San Diego, (1990).
[2] 1. Livage, M. Henry and C. Sanchez, Progress in Solid State Chemistry, 18
(1988) 259-341.
[3] L.C. Klein, "Sol-Gel Technology", Noyes, Park Ridge, (1988).
[4] R.K. Her "The Chemistry of Silica", Wiley, New York, (1979).
[5] I. Jaymes and A. Douy, JAm. Ceram. Soc., 75 (1992) 3154-56.
[6] A. Douy, J. Non-Cryst. Solids, 147&148 (1992) 554-58.
[7] C. Bessada, D. Massiot, 1. Coutures, A. Douy, 1.P. Coutures and F. Taulelle, J
Non-Cryst. Solids, 168 (1994) 76-85.
[8] 1. Jaymes, A. Douy, D. Massiot and J.P. Busnel, J Amer. Ceram. Soc. 78,
(1995), 2648-54
[9] A. Douy and I. Jaymes and C. Landron, Fourth euroceramics, vol 1,
Developments in processing of advanced ceramics, part C. Galassi, Ed., faenza
Editrice (1995) 139-144
SYNTHESIS OF BARIUM TITANATE BY REACTION
OF TITANIUM SALTS IN MOLTEN ALKALI METAL
SALTS OF OXOACIDS OF NITROGEN.
V. HARLE*, A. ABOUJALIL **, F. CHASSAGNEUX**,

B. DURAND***, J.P. DELOUME**
Laboratoire d'energetique et de Synthese inorganique, UPRES A n05079, Universite

LYON 1, 69F Villeurbanne
* [R.C., CNRS, 2 avo Einstein, 69626 Villeurbanne Cedex, France
** Univ. of Lyon 1, 43, Bd du 11 Novembre, 69622 Villeurbanne Cedex, France
*** Ec. Nat. Sup. de Chimie, 3, rue A. Werner 68093 Mulhouse Cedex, France
ABSTRACT
The synthesis of a binary oxide BaTi03 from titanium salts in reaction with alkali
nitrates is presented. The different conditions of preparation, chiefly basicity of the
medium, lead to different species of titanium oxides, as shown by physical
measurements.
RESUME
La synthese de l'oxyde binaire BaTi03 apartir de sels de titane reagissant avec des
nitrates alcalins, est presentee. Les differentes conditions de preparation,
principalement la basicite du milieu, conduisent ades composes differents d'oxydes de
titane comme Ie montrent les mesures physiques effectuees.
1 INTRODUCTION
Alkali metal nitrates or nitrites have proven to be powerful liquid media for the
preparation of oxides. The typical reaction in nitrates could be written as :
m m*n
MmXn + (m *n) NO] ~ - M 20 n + (m *n) N0 2 + - - 02 + n X m-
2 4
KERRlDGE and co-workers [1,2,3] have shown that this kind of reaction offers a
large choice of starting salts (MmXn) for a number of elements. More recently,
DURAND et al. [4,5] have demonstrated that this process is very versatile with
respect to the operating conditions, alIowing preparation of zirconium or titanium
oxides with defined textural characteristics. Here, we examine the reaction products of
titanium salts, depending on the conditions of preparation, and extend this method to
the preparation ofa binary oxide: BaTi03.
2 EXPERIMENTAL SECTION
All the compounds used, except titanium oxychloride, are commercially available.
Alkali metal nitrates and nitrites were systematically dehydrated and stored at 100°C.
Metal salts were partially or fully dehydrated at such temperatures that no other
reaction could occur. Titanium oxychloride was obtained by evaporation of a solution
of TiCl4 in water (kindly provided by Thann et Mulhouse). The X-Ray diffraction
pattern of the white powder can be assigned to Ti29042CI32.11H20 (JCPDS file 21-
1237). This fits well with the chemical analysis (SCA CNRS 69F Vernaison) :
In the following, this compound will be named Ti203C12. Alkali metal salts
(equimolar mixtures ofNa and K or K and Li, nitrates or nitrites) and metal salts are
poured into a Pyrex reactor, heated to a specified temperature and maintained for the
appropriate time to react. The shortest duration was determined by the TGA of the
reaction: evolution of the gas phase revealing the progress of the reaction. The cooled
cake is attacked with water (the oxide is the sole insoluble product in water). After
washing, the oxide is oven-dried overnight at 100°C, analyzed and examined by X-
Ray diffraction (Centre de diffractometrie H. Longchambon, Universite Cl. Bernard
Lyon I). Specific surface areas have been determined by adsorption of nitrogen (BET
method).
In reactions with alkali nitrates performed in order to prepare Ti02, the starting
titanium salts are classified in two types, according to whether or not they produce
titanium oxide. K2TiF6, leading to an amorphous phase when reacting at 250°C, and
K2TiO(C204h promoting the formation of alkali metal titanates when reacting at
500°C, belong to the latter class, whereas both TiOS04 and Ti203C12, producing at
250°C mainly pure anatase, come within the first one. The amorphous phase obtained
from K2TiF6 crystallises in the rutile and anatase forms of Ti02 when annealed at
500°C. Though, with the molten media containing lithium, LiF, rather insoluble in
water, is produced, and potassium hexafluorotitanate was consequently left. From the
results obtained for reactions of TiOS04 in nitrate, nitrate plus sodium peroxide and
nitrite media, it is observed, Table I, that the increase of the basicity of the molten
Synthesis of Barium Titanate by Reaction of Titanium Salts 291
medium favours the formation of amorphous phases. Chemical analysis indicate that
these latter are neither alkali metal titanates, nor exactly Ti02 (Table I). They could be
intermediates for further reactions. The anatase samples, synthesized from alkali metal
nitrates, are characterized by large specific surface areas, all the larger as the
temperature is decreased, with however a lower purity (Table I). The large specific
surface area is retained when the powder annealed at 600°C for a few hours. On the
contrary, the large specific surface area of amorphous powders is lowered after
annealing to very small values. HREM examination of anatase samples reveals
crystallites less than 10 nm in size (5). Such powders have proved their efficiency as a
catalyst support in hydrotreating (6). The preparation of BaTi03 was studied carrying
out simultaneous reactions of barium and titanium precursors with molten alkali metal
saIts. Preliminarily, it was checked that, whatever the involved medium, the reaction
with BaCl2 alone never gave rise to a water insoluble phase. In other respects,
TiOS04, leading to insoluble BaS04 when barium ions are present in the molten
medium, could not serve as a proper precursor of titanium. Likewise, K2TiO(C204h,
which reacting alone produces alkali metal titanates, systematically led in presence of
barium ions to mixtures containing significant amounts of BaC03. Consequently,
among the investigated compounds, the only suitable precursor of titanium was
Ti203C12 and the chosen source of barium was BaCl2 (similar results could likely
have been obtained with barium nitrate)
Medium NO;- NO;- NO;- NO;

Alkali met. K-Li K-Li+ Na20 2 K-Na K-Na
Temp.oC 250 250 400 400
Duration h 2 I I I
Aream2/g 305 160 160 180

Product anatase amorphous anatase amorphous
W% Ti* 56.3 49 54.5 45
K O.oJ 1.1 <0.01 3.6
Na 0.3 <O.oJ 3.6
Li 0.06 2.8
NO) 0.9 0.3
SO~- 3.6 2.6

Table 1: (* calculated for Ti02 : 60% - water content of the products 3-5%)
In nitrate baths, whatever the temperature in the range 350-580°C, the reactions
produced only anatase. Changing from nitrates to nitrites, reactions performed above
500°C, led to mixtures of titanates in which BaTi03 could be identified by X-ray
diffraction, possibly the cubic rather than the tetragonal phase. A further increase of
the basicity, by addition of Na202 to the nitrite bath, involved, in reactions carried out
at 500°C for 1.5 hours, the formation of BaTi03 and an amorphous phase. The
presence of this latter was corroborated, on the one hand, by chemical analyzis,
revealing, versus stoichiometric BaTi03, an excess of titanium and a deficiency of

barium and no noticeable amounts of other elements (Table 2) and on the other hand,
by the crystallization of extra phases, among which Ti02 rutile, when annealed at
900°C. The elimination of the amorphous phase was attained by lengthening the
reaction duration at 500°C up to 43 and 60 hours. This was confirmed by finding pure
tetragonal BaTi03 in a powder annealed at 1300°C.
weight % Obs : Ba 37.3 Ti 30.7

BaTiOl Calc 58.9 20.5
impurities: Na 0.7 K 0.25
CI 0.1 N01" 0.8
Table 2
4 CONCLUSION
From all these data, it can be concluded that, in a strongly basic medium (alkali
nitrates + sodium peroxide), the reaction at 500°C of Ti203C12, in the presence ofa
soluble barium species, leads quite rapidly to an amorphous solid, rather close to
amorphous Ti02 obtained by the reaction of a titanium compound alone. Then the
reaction slowly evolves producing several barium titanates with low Ba/Ti ratios, as
shown by the experiments without peroxide. The shift of the heterogeneous
equilibrium, until the stoichiometry of BaTi03 is reached requires several tens of
hours. By varying the composition of the liquid bath, the duration of the reaction, and
the temperature, it could be possible to modify the morphology of the crystals.
KEYWORDS
"soft chemistry", multi component titanium oxide
REFERENCES
[1] D.H. Kerridge and 1. Cancela Rey, J. Inorg. Nucl. Chern., 37, (1975), 2257-
2260.
[2] D.H. Kerridge and J. Cancela Rey, J. Inorg. Nucl. Chern., 39, (1977), 405-407.
[3] J. Tripkovic, R. Nicolic and D.H. Kerridge, 1. Serb. Chern. Soc., 54 (9-10),
(1989), 527-534.
[4] B. Durand and M.Roubin, Mat. Sci. Forum., 73-75, (1991), 663-668.
[5] V. Harle, J.P. Deloume, L. Mosoni, B. Durand, M. Vrinat, M. Breysse, Eur. 1.
Solid State lnorg. Chern., 31, (1994), 197-210
[6] V. Harle, 1.P. Deloume, B. Durand, M. Vrinat, Europacat I September (1993)
12-17th 34 F-Montpellier
NEW MATERIALS FOR {BIO )CHEMICAL
RECOGNITION
N. JAFFREZIC-RENAULT
IFOS-PCL UMR 5621, Ecole Centrale de Lyon, BP 163 69131 Ecully Cedex
France
ABSTRACT
(Bio )chemical sensors allow the direct detection of a the concentration of a

(bio )chemical species by an electrical signal. The device is composed of two parts,
one is bioselective, the other one provides the electrical signal. The challenge is to
conceive a selective (bio )chemical part having a good ability for identification.
The materials used for ionic detection, the process involved and their application in
ionic sensors (ISE, ISFET), the materials chosen for the identification of vapors based
on polymer-gas interactions and their specific applications to optical gas sensors are
presented. In the domain of the biological sensors, the conception of thin membranes
containing biological molecules (enzymes, antibodies) is also presented in relation to
the methods of measurement used (amperometric, potentiometric, conductimetric,
impedimetric ).
RESUME
Les detecteurs (bio)chimiques permettent la mesure directe de la concentration

d'esp(xes (bio)chimiques par un signal electrique. Le dispositij est constitue de deux
parties, l'une bioselective, l'autre de mesure. L 'objectij est de concevoir la partie
(bio)chimique selective presentant une bonne capacite d'identification.
Les materiaux utilises pour la detection ionique, les procedes mis en ceuvre et leur
application dans les detecteurs ioniques (ISE, ISFET),et les materiaux choisis pour
l'identification de vapeurs en utilisant les interactions polymeres-gaz et leurs
applications specifiques dans les detecteurs optiques de gaz, sont presentes. Dans Ie
domaine des detecteurs biologiques, la conception de fines membranes con tenant des
molecules biologiques (enzymes, anticorps) est aussi presentee en relation avec les
methodes de mesures utilisees (par intensite, voltage, conductibilite, impedance).
1 INTRODUCTION
A (bio )chemical sensor allows the direct transduction of the concentration of a

(bio )chemical species into an electrical signal. According to the general scheme
presented in Figure 1, this device consists of a (bio)chemical recognition part coupled
with a transducing device. The challenge is to conceive this (bio )chemical recognition
part in relation to the species to be detected (molecules, ions) and to associate the
proper transducing effect which can be coupled with the recognition process.
SENSOR
sample Electrical
(gas, liquid) Recognition part Transduce
Signal
Filter
Figure 1 : General schematic diagram of a (bio )chemical sensor.
Two basic systems are used for the recognition effect : affinity systems and catalytic
systems. In the affinity systems, the typical equilibrium represents the specific
interactions of the species to be detected X with the affinity recognition site Sa which
allows the formation of the bound species XSa :
X+SaBXSa
This formation leads to a modification of a physical parameter of the recognition part :

mass, electrical charge, dielectric properties, optical properties. The catalytic system is
represented by the typical reaction:
X+ SCBXSCB Sc+P
where X is the species to be detected, Sc the catalytic recognition site, XSC the bound
species and P the product of the catalytic reaction. To sum up, the catalytic
recognition site allows the transformation of the species X into the product P, the
New Materials for (Bio)Chemical Recognition 295
catalytic site being totally restored. The detection of X is performed through the
detection ofP, the transducing effect being defined with this aim. Typical examples of
the affinity and catalytic systems are drawn from biological systems. The antibody-
antigen system is a very selective but irreversible affinity system. The enzymatic
reactions are catalytic systems. These examples will be treated in this paper and the
biosensors conceived with these systems will be described [1] . The advantage of the
biological systems is their selectivity, but their use in biosensor technology is limited
because of their low stability. The biological systems constitute a model for artificial
recognition systems conceived for chemical sensors. In this paper, some artificial
affinity and catalytic systems are presented for the chemical detection of ionic species
and gas molecules as well as the associated transduction modes.
2 BIOLOGICAL AFFINITY SYSTEM: ANTIBODY - ANTIGEN SYSTEM
The scheme of an IgG antibody molecule is presented in Figure 2. The specific

antigen is bound on the Fab fragments through interactions like hydrogen bonds and
Van der Waals forces .
bindingsile binding sile
NH' NH'
tlUY1
C~aiR$
Cootl CooH
Fe
Figure 2: Schema of an IgG antibody molecule
The immobilization of the antibody on the transducer surface has to be achieved by

meeting several criteria : high biological activity, stable covalent binding, and a
sufficient quantity immobilized. The general way is the covalent immobilization of the
antibody molecules in a hydrogel deposited on the surface transducer. The different
types of transduction mode used for the detection of the antibody-antigen interaction
are based on the variation of the dielectric and optical properties of the hydrogel layer
and on the variation of the mass of this layer. Two types of transduction mode will be
exemplified here: electrochemical impedance measurements and surface plasmon
resonance.
2-1 Electrochemical impedance measurements [2]
The transducer consists of Electrolyte/Oxide/Semiconductor structures. An antibody

(ex. a-fetoprotein) is immobilized in a functionalized polysiloxane polymer deposited
on the surface of a thermally oxidized silicon wafer. The equivalent electrical scheme
of the initial structure is described in Figure 3(a), in the accumulation range of the
silicon. The equivalent electrical scheme of the structure with the polymeric
membrane is presented in Figure 3(b). It has been shown that after immobilization of
the antibody in the polymeric membrane, the value of R3C3, remains constant for
several months. This value varies with the antigen-antibody interaction as shown in
Figure 4.
C2
Cl
(a)
----1 RI
R2
(b)
C2 C3
CI
-1 Rl
R2 R3
Figure 3 : Equivalent electrical circuit of Electrolyte/Oxide/Semiconductor structures

(a) the initial structure (b) the structure with the polymeric membrane deposited on the
oxide surface
5500
5000
o Glycine washing
4500 • Ag 1000 nglml
o Ag 20nglml
4000 [ ] Ag 50nglml
• Ag 100 nglml
3500 • Ag 200 nglml
• Ag 200 nglml
3000 f-L---L------r-...L....L......L-=
1sl washing _ 3rdwashing
Figure 4: Variation of the value ofR3C3 with the antigen-antibody interaction

2-2 SPR measurements [3]
Figure 5 shows the schematic drawing of the glass slide, the metal film, the coupling
hydrogel layer and a part of the flow cell used in the SPR measurements. It also
illustrates how the observed reflectance of light changes when biomolecules from the
solution adsorb in the hydrogel. Figure 6(a) shows the resonance angle, during an
analysis cycle for IgE. In 1, the serum sample is injected (antigen interaction), in 2 a
secondary antibody is injected (sandwich structure), in 3 the regeneration of the
antibody is done (acidic washing). Figure 6(b) shows the good correlation between
the real time determinations obtained through SPR measurements and the classical
RIA immunoassays.
o
Figure 5: Schematic drawing of the device used in the SPR-based biospecific
interaction analysis and changes of the reflectance of light when biomolecules adsorb
on the matrix (dashed line)
2000
Resonance Signal
24
1500
~
.Eo
20000 c(
.,
jjj 1000
..'"
2 E
16000 F
500
a:
12
0
400 800
Time (sec) 0 500 1000 1500 2000
a) b)
Pharmacia IgE RIA [ng/mll
Figure 6:
(a) Variation of the resonance angle during an analysis cycle for IgE
(b) Correlation between the real time determinations (SPR measurements) and
classical RIA immunoassays
3 BIOLOGICAL CATALYTIC SYSTEM: ENZYMATIC SYSTEM
The particular example of glucose detection will be treated here. The enzymatic
reaction used is the oxidation of the J3D-glucose molecule catalyzed by the enzyme
glucose oxidase :
~D - glucose + 02 glucose oxidase) gluconic acid + H 20 2
The product of the enzymatic reaction H202 is an electroactive species and can be
detected by amperometry.
A schema of a typical amperometric biosensor using ferrocene as mediator to favor

electronic transfer, is shown in Figure 7 [4]. The immobilization ofthe enzyme on the
working electrode (platinum, carbon) is performed by cross-linking with a
bifunctional reagent such as glutaraldehyde. A semipermeable membrane (ex :
NAFION polymer) covers the enzymatic layer, its role is double: to confine the
reaction product in the neighborhood of the electrode surface and to avoid the
diffusion of interfering electroactive species towards the electrode.
~ '"
@ ~
~
'"
'"
'"
''""
rn glucose
~
ferrocene
m:J ~
~ '"
'"
@
~
~ '"
[]] ~
'"
~
~
''""
fe"ocene '"
m:J ~
'"
@enzyme
@ glucose oxydase
~
~'"
'"
rn
~
fe"ocene ~'"
'"
@ @
~
~'"
~'"
~'"
analyte reaction volume '"
semipermeable working
membrane electrode
Figure 7 : Schema of a typical amperometic biosensor (from (4»

Many types of amperometric sensors for the glucose detection have been realised
following this principle, the geometry depending on the application. For example,
direct in vivo detection in a rat brain has been performed using carbon fibre
microelectrodes. The real time differential normal pulsevoltammetry (DNPV) signal,
when insuline and then glucose are injected, is presented in Figure 8 [5].
Injection of A
'2 insuline (40U)
.c 15 I
r: \.JF17··
c;, .<Po ~ Injections of glucose (2cm'): 0
~ ~ld h<>Po ~ 5% solution aP°oJJIs>o~ho'''P
O+---~~r-~r-~~~~~~~--~~~~~
60 80 100 120 140 160 180 200 220 240 260
Time, min
B
«6
c:
t5
~4
m3Pl~~~P'
Cl.
itz 2
o 1
100 150 200 250 300 350

Time, min
Figure 8 : Direct in vivo detection in a rat brain with a carbon fibre microelectrode :
real time differential normal pulse voltammetry signal when insuline and then glucose
are injected.
4 ARTIFICIAL AFFINITY SYSTEM: DETECTION OF IONS
The detection of ions with ISE (ion selective electrode) and ISFET (ion selective field
effect transistor) is based on the electrochemical equilibria at the interfaces between
liquid electrolytes and membranes made of ionic conducting materials (solid
electrolytes, ionic conducting polymers ... ). An ideal ionic membrane should
exchange only one type of ion, AZ+, this selectivity being fixed by the nature of the
affinity binding sites (fixed ionic sites, mobile ion-exchanger, neutral ionophores).
Solid electrolytes such as glasses, sparsely soluble salts (single crystals or crystals
dispersed in an inert binder) act as an ionic membrane with fixed sites. Special glasses
can exchange H+ ions or alkaline ions, depending on their composition. A typical
sparsely soluble salt is AgCI which can exchange Ag+ and CI- ions. For the detection
of other types of ions, synthetic ion-exchange and neutral ionophores are developed.
Figure 9(a) represents the ion-exchange equilibrium for the ion AZ+ at the interfaces
between two different solutions and an ionic membrane. The distribution of the
electrostatic potential at both membrane/solution interfaces (Donnan potential) is
represented in Figure 9(b). The electrochemical potential of the ion A through the
three phases in equilibrium remains constant: this allows relating the membrane
potential il<1lD to the logarithm of the ratio of the concentration of ion A in solutions 1
and 2 [6].
(A) I
Solution I Solution 2
,
Electrical
Potential
-r:-+------«!>2
«!>I_ _-+...JK.
Figure 9 : (a) ion-exchange equilibrium for the ion AZ+ at the interface between two
different solutions and an ionic membrane (b) distribution of the electrostatic potential
at both membrane/solution interfaces.
The principle of the measurement set-up with an ISE and a reference electrode is
presented in Figure 10. The measured potential E is directly connected to the
membrane potential il<1lD.
Measurement
E system
Solution 2
_f-+--Sensitive Membrane
Figure 10 : Principle of the measurement set-up with an ISE (Ion Sensitive Electrode)
and a reference electrode
The schematic view of an ISFET is presented in Figure 11. The ionic membrane is
directly deposited on the gate insulator surface. The threshold voltage of this device is
connected to the membrane potential ~<l>D and the drain current versus gate voltage
characteristics will be shifted along the voltage axis when the ion concentration
increases.
Reference Electrode
Sensitive Membrane
Encapsulation
(Au)
Solut ion
ChaMel Insulator
Source Drain
VD
Figure 11 : Schematic view of an ISFET (Ion Sensitive Field Effect Transistor)
The sensitivity of ISE and ISFET will depend on the quantity of affinity binding sites
in the membrane, and the selectivity will depend on the nature of these sites. An
example is given concerning ISFET with membranes based on macrocyc\ic thioethers
for the detection of silver. The selectivity coefficient 10gKAg,M represented in Figure
12, is defined through the Nicolsky-Eisenman equation [7]. It appears that the
selectivity of the macrocyclic thioethers towards different cations depends strongly on
the geometry of the molecule.
I
0 - Ao - AO - Ag - Ao - Ag
- , r-
~
:/-.
::s: - K
Ol -J - K
-K
-K
_ K
- Ca
Q - Ca
=C<I"" _ C =
-
Ca""
Cu.Co ~:>o
'-' '-' \...J \...J
Figure 12 : Selectivity coefficient measured with ISFET for membranes based on

macrocyc\ic thioethers
5 ARTIFICIAL CATALYTIC SYSTEM: DETECTION OF GAS
5-1 Semiconductor oxide: [8]
Polycrystalline semiconductor oxides (such as Sn02) behave as combustion catalysts

towards oxidizable species (alcohols, alcanes ... ). During the catalytic reaction, the
density of the species adsorbed is modified, which induces a variation of the surface
conductivity of the semiconductor particles. The detection of the different gases is
based on the variation of resistivity of the heated sintered semiconductor material. A
schematic view of an Sn02 sensor is presented in Figure 13. The selectivity of
detection is controlled by previous surface treatment of the oxide and by the working
temperature (Fig. 14).
G <0-1)
Heating
Resistance
Sintered
Tin Oxide
. ~
Electrodes Temperature
Figure 13: Figure 14 :Variation of the conductivity of the

Schematic view of a Sn02 sensor sensor versus temperature (CORECI France)
5-2 Catalytic metals [9]
Some noble metals such as palladium or iridium act as catalysts towards the
dissociation reaction of molecules such as hydrogen, alcohol, hydrogen sulfide (cf
Fig.15(a». The hydrogen atoms coming from the dissociation of the molecules are
adsorbed on the metal surface, some hydrogen atoms diffuse through the metal layer.
Thin layers of these catalytic metals are deposited on MOS structures (Fig. 15(c» or
on MOSFET structures (Fig. 15(b».
100nm
(a)
100nm
iD1£"'Vo ~y,
.
~' I1V
tthout
H2
11
Vo 11
~ Cbs
'.:
Pd
(b) (c)
Figure 15 : (a) Schematic illustration of a Pd-insulator-semiconductor structure in the

presence of hydrogen (b) The ID V G characteristics of a Pd-MOSFET shift with AV
along the voltage axis due to the hydrogen dipole layer (c) A similar shift is obtained
in the CV-curve of a Pd-MOS-capacitor
The amount of hydrogen atoms at the metal-oxide interface is determined by the

concentration of the molecule (hydrogen, alcohol ... ) in the ambient and by chemical
reactions catalyzed by the metal surface. At the interface, the adsorbed hydrogen
atoms give rise to a dipole layer, i.e. a voltage dropAV. In the MOSFET structure, the
drain current versus gate voltage characteristics will be shifted along the voltage axis
when the molecule concentration increases (Fig. 15(b». Similarly, the capacitance
voltage curve of a MOS structure will be shifted along the voltage axis when the
molecule concentration increases. An example of pulse response to ethanol in air with
a Pd-MOSFET is presented in Figure 16(a). The sensitivity and the selectivity of the
metal surface depends on the nature of the metal and on the working temperature (Fig.
16(b».
200 "C
I
200
. .--""
./
125 150 175 200
>---I Temperature ("C)
2 min
Figure 16 : (a) Pulse response to ethanol in air (with concentrations in ppm) (b)
Response to 8000 ppm of ethanol versus device temperature
6 CONCLUSION
Different artificial recognition systems based on biological systems have been

developed in order to detect chemical species. The characteristics of the affinity
systems and of the catalytic systems are different; the choice of the system will be
made by considering these features: sensitivity, selectivity, dynamic range, response
time, life time, and transduction mode used.
KEYWORDS
chemical sensor, ion selective electrodes, biosensor, ISFET, gasFET
REFERENCES
[1] L. Blum, P.R. Coulet, Ed. Biosensors, Principles and Applications, M.

Dekker, (1991).
[2] H. Maupas et aI., J. Electroanal. Chern., 406, (1996), 53
[3] S. Lofas et aI., Sensors and Actuators B5 (1991) 79-84
[4] W. Gopel, J. Hesse, J.N. Zemel, Ed. Sensors, a Comprehensive Survey,
V.C.H. Vo1.2, (1991)
[5] L.I. Netchiporouk et aI., Analytical Chemistry, 68, (1996), 4358
[6] H.D. Weimhofer, K. Cammann, in ref. (4), p. 159-189
[7] Z. Brzozka et aI., Analytica Chimica Acta, 273, (1993), 139-144
[8] M.J. Madou, S.R. Morisson, Chemical Sensing with Solid State Devices,
Acad. Press, (1989)
[9] T. Seiyama, Ed. Chemical Sensor Technology, Kodansha Ltd, Vol.2, (1989)
IONIC RECOGNITION USING CONDUCTING
CERAMICS
Pierre FABRY, Haftt KHIREDDINE, Marc CRETIN
Laboratoire d'!onique et d'Electrochimie du Solide de Grenoble, CNRS, URA

1213, ENSEEG, BP 75,38402 Saint Martin d'Heres Cedex (France)
ABSTRACT
Three-dimensional (3d) frameworks of fast-alkali conductors have promlsmg
properties for electrochemical sensors. Their conductivity is excellent at room
temperature (about 10-4 to 10-3 S.cm- i ), very much higher than the conductivity of
usual membranes. They are sufficiently stable in water to be proposed as sensitive
membranes in ISE devices. The mobile ions, such as sodium or other alkali ions, move
through the structure from one site to another by 3d tunnels which are very well
calibrated in size. The higher the mobility of an ion, the faster its exchange at the
interface with the analyzed solution.
The selectivity effect is based on this phenomenon. NASICON materials are good
examples from this point of view. The framework can be optimized by suitable cationic
substitutions to adjust the size of the conduction sites and thus improve the selectivity
effect. Recent experimental results in this field on Na+ and Li+ membranes are shown.
RESUME
Des milieux solides conducteurs de reseau tridimensionnel tel Ie NASICON presentent

des propr;etes interessantes pour des capteurs electrochimiques. Leur conductivite est
excellente a temperature ambiante, nettement plus elevee que celles des membranes
habituelles. lis sont suffisamment stables dans I'eau pour etre proposes comme
membranes sensibles dans les dispositifs a electrode ionique selective (ISE). Plus la
mobilite d'un ion est elevee, plus ses echanges al'interface avec la solution aanalyser
sont eleves, ce qui assure la selectivite.
Le reseau peut etre optimise par des substitutions cationiques convenables pour
regler la dimension des sites conducteurs et ainsi ameliorer la selectivite. Des
resultats experimentaux recents sur des membranes aNa+ et a Li+ de ce type, sont
presentes.
1 INTRODUCTION
One of the essential quality criteria of any apparatus required in analytical applications
is their selectivity. Generally, a chemical compound is mixed with others. Selectivity
is the ability to recognize one compound among others and to give an accurate
measurement of its activity. This quality can be considered as a first step of
intelligence for smart sensors, because the treatment of the electrical or mathematical
message is easier. The analysis of several compounds in aqueous solutions can be
made by optical or electrochemical methods or by use of active sensors (e.g.
amperometric or voltamperometric sensors). Such methods require a more or less
sophisticated electrical generator. The main advantage of potentiometric sensors, also
called Ion Selective Electrodes (lSE), is the simplicity of the electrical measurement.
They can be schematized by the following electrochemical chain:
metal/internal reference system / sensitive membrane / ...
The working principle is based on the equilibrium between the membrane and the
analyzed solution by ionic exchange at the interface. A Galvani potential appears
between both phases, and the membrane potential obeys the Nernst law ifthere is only
one compound or if the membrane is very selective, and the Nickolskii relation (or the
extended Nernst law) in the general case:
where EO is a constant which depends on the reference systems (internal and external),
ai and aj are the activities ofi (analyzed ion) andj (interfering ion) andzi and Zj their
charge numbers. Ki,j is the selectivity (or interference) coefficient when aj is
measured in presence of j ions. This coefficient is determined experimentally, several
theoretical models have been proposed depending on the membrane type [I]. T is the
absolute temperature, Rand F are the usual constants. Of course, this law must be
generalized in the case of several interfering ions.
Most ISEs are generally made with an inorganic solid-state ionic conductor as the
sensitive material. The usual membranes can be classified in two classes:
• insoluble salts such as AgX-MXx. They are electrodes of the second or third
kind. The membrane is a Ag+ ion for the conductor and it is sensitive to an anion
or a cation which forms an insoluble phase withAg+ or X-. Several models have
been proposed to explain the selectivity properties, one of which is based on the
ratio of the salt solubility constants(l). LaF3-based membranes for F-
measurements are other examples of such inorganic salts [2].
• glasses used for pH or pNa measurements. For Na+ detection, the sensitivity is
due to a direct ionic exchange between the membrane and the analyzed solution.
It is an electrode of the first kind. Na+ ions can move into the membrane through
Ionic Recognition Using Conducting Ceramics 307
conducting sites between oxygen polyhedra formed around fixed cations (Si 4+ or
AP+ etc.). The material is amorphous and its sites have a variable size. Thus, the
sensor does not have good selectivity performance, for instance for other alkali
ions. For pH-ISE, the working phenomenon is not very well identified. The glass
is not a protonic but an alkali conductor.The sensitivity (and the selectivity too)
can be explained by the presence of superficial OH- groups which give acido-
basic equilibria with the aqueous solution [3]. In this case, the working mode is
rather close to the previous one, but solubility constants must be replaced by
equilibrium constants.
The sensitivity effect of organic membranes can be described as a complexation

equilibrium between an organic molecule (for example a crown-ether kept in a
hydrophobic material) and the analyzed ion in solution. The selectivity effect is then
related to the equilibrium constant ratio, as in the previous model. The valinomycin-
based membrane for K+ analysis is a good example in this field. The selectivity
mechanism is often described by a steric effect in the complex formation between the
ion and the organic molecule [4].
Although Ion Sensitive Field Effect Transistors (ISFETs) work with a different
transducing mode, the basic principle of their sensitivity can be described in this
manner. Organic membranes, which are very selective, are generally more delicate
than inorganic ones and also less stable at temperatures higher than room temperature.
On the other hand, the usual glass materials are poorly selective. Whatever the
membranes may be, they are poor conductors and difficulties can occur during
potentiometric measurements. Our work consists in proposing hard materials also
having a selective effect based on a steric recognition of ions, that is to say which
combine a maximum of the previous advantages.
2 MEMBRANE MATERIALS
During the last twenty years, several solid electrolytes in crystalline phase have been
synthesized, essentially for alkaline battery devices, for instance frameworked fast
ionic conductors. They are formed by polyhedra which are, periodically and at short
distance, linked together by oxide bonds. In this manner, the conduction sites are
uniform in size. The conduction sites in 2d-compounds are planar and generally such
materials are not watertight (p-alumina or CS2Ti6013 are examples [5]). In compounds
of the ld or 3d-type, the conduction sites are formed by tunnels in one or three
dimensions and are more stable in aqueous solutions. The sites are calibrated and such
materials are well adapted for selective properties in ISE of the first kind. The passage
from one grain to another is obviously easier in the case of polycrystalline 3d-
materials than in the case of I d-compounds. The impedance of the membrane is then
reduced and, from this point of view, 3d-materials are more attractive. A typical
example of such material is the NASICON (Na Super Ionic Conductor). It was first
synthesized by Goodenough and Hong [6] and proposed as a sensitive membrane for
ISE or ISFET simultaneously by two laboratories [7,8]. Its general formula is Nal+x
Zr2 Six P3-x 012· Si04 and P04 tetrahedra are linked to Zr06 octahedra by common
oxygens and form a covalent skeleton. Sodium ions are located in interstitial spaces
and can move from one site to another, passing through bottlenecks formed by
triangles of oxygen (Fig. 1). The bottleneck size is slightly narrower than the Na+
ionic radius.
Figure 1 : NASI CON type structure
The conductivity is exclusively cationic and is a function of the stoichiometry factor

(x). The maximum conductivity is obtained for x = 2 and its value is very good (10- 3
S.cm- I at room temperature) compared to usual solid membranes (about 10-5 down to
10-11 S.cm- I). It corresponds to the maximum of the lattice size [9]. Ionic substitution
into the membrane with another alkali ion is very difficult to obtain because the ionic
radius is not mached to the size of the sites: K+ is too big and Li+ too small (the
selectivity of the material is based on this property).
Nevertheless, this structure can be reproduced for lithium ionic conductors, but the
immobilized cations of the skeleton must be chosen to be smaller. LiTi2P3012 can be
an example of a compound in this field but its conductivity is relatively low, about 10-
6 S.cm- I at room temperature [10]. If the structure is contracted by another
substitution (for instance Lil+xAlxTi2-xP3012) the conductivity can be increased, up
to a few 10-4 S.cm-I [10].
3 SYNTHESIS AND CHARACTERIZATIONS
3.1 Synthesis
NASI CON materials can be synthesized by the co-grinding process which is usual for
oxide ceramics. The starting compounds are oxides, carbonates and phosphates (or
hydrogenophosphates). The specific area of the powder obtained in this way is
generally low and the sintering temperature must be high (more than 1000 0C). The
departure of volatile compounds brings about a substoichiometry. The sol-gel route is
based on a reaction of hydrolysis-condensation of alkoxides in an excess of water.
Very fine powders can be synthesized in this way. Thus, the sintering temperature is
reduced (less than 1000 0C) and a pure NASI CON phase can be obtained, with respect
to the previous stoichiometry [11]. The membranes are pressed in pellets and sintered
under air. The quality of the materials is controlled by X-ray diffraction and
microanalysis (SEM microprobe). The conductivity is measured by the complex
impedance method. This method allows measurement of the ohmic part of the
impedance and, if the characteristic frequencies are sufficiently different,
distinguishing the bulk and the grain boundary phase of the sintered pellets.
3.2 Sensor devices
As mentioned above, the conductivity is high for these materials and it is not
necessary to thin down the membranes. The impedance of the sensor remains low (a
few kQ) for a thickness of a few millimeters. Robust sensors can be made with special
devices for specific applications (point ISE, tubular cells for Flow Injection Analysis
[12,13] etc.). Classical ISEs use a membrane pellet assembled on an inert tube with an
aqueous internal solution. Salts containing ions common to the membrane and to the
internal redox system (Ag/AgCl) are dissolved in the internal solution to realize a
reversible electrochemical chain. Solid internal systems can also be used [14,15].
Leonhard et al. have recently proposed a NASICON ionic sensor in thick layer
technology with a mixed solid conductor as an internal reference system [16].
3.3 Detection limit
According to the IUPAC recommendations, the detection limit is the crossing point
between the Nernst asymptote and the horizontal line corresponding to the insensitive
range of the sensor (when the activity ofi ion is too low). It is determined without the
j interfering ions. With NASICON materials, the detection limit is slightly less than
the value obtained with aNa-glass ISE (about 10-4 mol.liter l ) depending on the
stoichiometry [16]. No accurate model has been proposed to explain the chemical
phenomena limiting the detection [16,17]. For a lithium sensitive membrane, the value
is of the same order of magnitude as for Na-ISE based on the NASI CON membrane
[18].
3.4 Selectivity
The Kij coefficient is generally measured by the mixed solution method, in the
presence of only one interfering ion. It consists in adding a solution of the j interfering
ion by successive additions (aj being kept constant) [11]. The voltage is measured for
each addition and the selectivity coefficient is determined from the graph E(log aj}.
An example for a lithium sensor is plotted in Fig. 2.
45
40 au = 10-'
Ul 35 J..
U K1l,K = aLI / a" K
UJ
"- 30
> = 1.8 10-'
E- 18mV
UJ 25
20
15
, . 'f
a"K - 5.6 1O-~
10-3 10-Z 10-1 10° 101

aK
Figure 2 : Example of determination of KLi,K in the case of a Li+ sensitive membrane

(Lil+xAlxTi2-xP3012 , x = 0.3)
For the Na-ISE based on the NASICON membrane, a qualitative correlation has been
observed between the conductivity of the membrane and its selectivity, whatever the
alkaline interfering ion (lithium or potassium) may be. The minimum ofKNa, j is
obtained for about x = 2 or 2.2 in the Nal+x Zr2SixP3-x012 family. The optimal value
of KNa,j is about a few 10-2 (Fig. 3a) or exceptionally 10-3. This coefficient is better
than for Na-glass membranes (close to 10- 1) [11,17]. The lattice size and the
conductivity by the Na+ ion (Fig. 3b) are also maximal for x about 2. We could expect
a maximum of the selectivity coefficient for the K+ ion, and a minimum for theLi+
ion. From these results, one can deduce that the Na+ conductivity is the predominant
factor in the selectivity effect. This is in agreement with the study of exchange kinetics
made by complex impedance spectroscopy [19]. A correlation was observed between
the transfer resistance and the conductivity of membranes [12]. For lithium
membranes, the lattice is slightly more compact and the size of conduction sites is
smaller. The selectivity coefficient for a Lil+xAlxTi2-xP3012 (x = 0.3) membrane is 2
to 5.10-2 for the K+ interfering ion and close to 0.5 forNa+ [18]. The conductivity of
this membrane (a few 10-4 S.cm- 1) is about the same order of magnitude as for
Na3Zr2Si2POI2. With Na3Zr2Si2P012, the coefficient KNa,Li being about 2.10-2, the
inverse value KLi,Na is about 50. All these values show that the decrease of the
conduction site size modifies the mobilities and improves the selectivity towards the
bigger ions.
-2.8
0
•
-3 •
-0.5
~
ui
~ -3.2
.s: • • ~
z
g ~ -1
'" -3.4 '"

.sl
Jl."
-1.5
'"
!l -3.6
•
ID
-3.8 -2
1.2 1.4 1.6 1.8 2.2 2.4 2.6 2.8 1.6 1.8 2.2 2.4 2.6 2.8
a) x value b) x value
Figure 3: Influence of stoichiometry on the properties ofNa\+xZr2SixP3_x012

a) Variation of conductivity
b) Variation of selectivity coefficients for Li+ and K + interfering ions
From this point of view, the model of Eisenman for glass membranes [I] could be
applied in a first approximation: the KjJ coefficient can be described as the product of
the exchange equilibrium constant (Keq) and the ratio of the ion mobilities:
Kij = Keq . (I-lj* / I-li*)
where I-li* and I-lj* are respectively the electrochemical mobilities of i and j in the
membrane. In the case of Li+ material, the steric effect is clear. For the Na+
membrane, it is difficult to anticipate the relative variation ofKjJ as a function of the
interfering ions (Li+ or K+) because their mobilities in the membrane are unknown_
We can conclude only that, when x is modified, the variation OfI-lK* is lower than for
I-lNa*·
4 CONCLUSION
NASI CON type materials are promising as ISE membranes because they are able to
combine the qualities of different membrane kinds: selectivity, robustness, low
impedance, easy cleaning, fast response [20], the possibility of adapting of the design
to specific applications... Selectivity properties can be modified by changing the
lattice parameters of the structure. Up to now, their disadvantage is the preparation
process, which is certainly more expensive than the glass one. Future developments
would be essentially in the thin or thick layer processes which should be more
attractive. Up to now, one can mention some attempts made in this field using the sol-
gel process [16,21].
KEYWORDS
NASICON, ISE devices, 3d framework conductors
REFERENCES
[1] The Principles ofIon Selective Electrodes and of Membrane Transport, W.E.Morf
Ed., Elsevier Pub. Company, Amsterdam, 1988.
[2] M.S. Frant, J.W. Ross Jr., Science, 154 (1966) 1553-1555.
[3] J.R. Sandifer, Anal. Chern., 60 (1988) 1553-1562.
[4] Ion Selective Electrodes, J. Korita, K. Stulik Eds., Cambridge University Press,
(1979).
[5] v. Peres, P. Fabry, F. Genet, P. Dehaudt, J. Europ. Ceram. Soc., 13 (1994) 403-
410.
[6] J.B. Goodenough, H.P.Y. Hong, J.A. Kafalas, Mat. Res. Bull., 11 (1976) 203-220.
[7] J.E. Engell, S. Mortensen, Radiometer Int. Patent WO 84/01829, (1984).
[8] P. Fabry, J.F. Million-Brodaz, M. Kleitz, Symp. Electrochemical Sensors, Rome,
June 12-14, (1984).
[9] D. Tranqui, J.J. Capponi, M. Gondrand, M. Saib, J.C. Joubert, R.D. Shannon, Solid
State lonies, 3-4 (1981) 219-222.
[10] H. Aono, E. Sugimoti, Y. Sadaoka, N. Imanaka, G.Y. Adachi, J. Electrochem.
Soc., 137 (1990) 1023-1027.
[11] A. Caneiro, P. Fabry, H. Khireddine, E. Siebert, Anal. Chern., 63 (1991) 2550-
2557.
[12] P. Fabry, E. Siebert, in Chemical Sensor Technology, vol. 4, S. Yamauchi Ed.,
Kodansha Ltd, Tokyo, (1992), 111-124.
[13] J. Bartroli, Ll. Alerm, P. Fabry, E. Siebert, in Anal. Chim. Acta, 308, (1995), 102-
108
[14] B.P. Nickolskii, E.A. Materova, Ion Selective Electrode Rev., 7 (1985) 3-39.
[15] P. Fabry, C. Montero-Ocampo, M. Armand, Sensors and Actuators, 15 (1988) 1-9.
[16] V. Leonhard, H. Erdmann, M. Ilgenstein, K. Cammann, J. Krause, Sensors and
Actuators B, 18-19 (1994) 329-332.
[17] H. Khireddine, These INPG, Grenoble (France) (1992).
[18] M. Cretin, P. Fabry, L. Abello, in J. Europ. Ceram. Soc, 15, (1995),1149-1156
[19] O. Damasceno, E. Siebert, H. Khireddine, P. Fabry, Sensors and Actuators B, 8
(1992) 245-248.
[20] M. Attari, P. Fabry, H. Mallie, G. Quezel, Sensors and Actuators B 15-16 (1993)
173-178.
[21] Y.L. Huang, A. Caneiro, M. Attari, P. Fabry, Thin Solid Films, 196 (1991) 283-
294.
SYNTHESIS OF MACROCYCLIC LACTAMS IN
ORGANIZED MEDIA
A. CAPARROS, E. PEREZ, I. RlCO-LATTES and A. LATTES
Laboratoire des IMRCP, Universite Paul Sabatier, 118 route de Narbonne,

31062 Toulouse Cedex, FRANCE
ABSTRACT
Lactamization was studied in a micellar environment using the novel carboxyl-

activating agent, N-hexadecyl-2-chloropyridinium iodide (C]#,yCI, 1-). ())-amino
acids were macrocyclized successfully in various surfactantless microemulsions
containing formamide or traces of water and using the classical Mukayama
reagent(C]PyCI, 1-). In these media, selectivity was attributed to the poor solubility of
the precursors in the continuous phase. The w-amino acids were thought to be
localized at the interface of the molecular aggregates, favoring intramolecular
reactions.
RESUME
La reaction de macrolactamisation a ete etudiee en milieu micellaire en utilisant un
nouvel agent d'activation de la fonction carboxylique, l'iodure du 2-chloro-N-
hexadecylpyridinium(C]#,yCI, r). Apres une activation par Ie reactif de Mukayama
(C]PyCI, l), les acides (l) amines ont ete cyclises avec succes dans des
microemulsions sans tensioactif contenant duformamide ou des traces d'eau. Dans
ces milieux, la selectivite semble corre!ee alafaible solubi/ite des precurseurs dans la
phase continue. Ainsi les acMes (l) amines se localisent au sein de l'interface des
agregats mo!eculaires favorisant ainsi les reactions intramo!eculaires.
1 INTRODUCTION
There is considerable interest in the preparation of novel macrolactams in view of

their antibiotic and antifungal properties [1]. However, as with most macrocyclic
compounds, the intramolecular reaction competes with bimolecular and
polymerization reactions, and so generally requires high dilution conditions.
Furthermore, in contrast to macrolactones, the precursors of lactams are poorly
soluble in most organic solvents, and few methods for their synthesis are currently
available. One method consists of activating a dicarboxylic acid group to a diacid
chloride that in a second step reacts with a diamine [2]. Another possibility is to
transform the amino group into an azide [3] to produce a precursor that is more
soluble in organic solvents. Another method [4] utilizes a carboxyl-activating agent
such as the halogenated pyridinium salts described below. Low yields are obtained in
all these methods as they require conditions of high dilution [5]. This is not suitable
for industrial scale operations in view of the large requirement for solvent, which
increases cost. In order to avoid these difficulties, we developed an accessible route in
a structured micellar or microemulsion medium, which favors a more selective
reaction. For example, Lennox et al. [6] demonstrated micellar catalysis on large ring
cyclization in a cationic micellar environment based on cetyltrimethylammonium
bromide (CTAB). Jaeger et al. [7] have described the preparation oflactones, albeit in
poor yield, in reverse micelles of Aerosol OT (AOT) or didodecylmethylammonium
bromide (DDAB). In the present study, we chose the Mukayama reagent, I-methyl-
chloropyridinium iodide (CIPyCI, 1-) as activating agent. In fact this compound is a
double activating agent, as after anchorage to the carboxyl group the reacting species
are in close proximity to the central pyridinium ion. The condensation reaction is thus
favored entropically [8]
~OOH
(CH2 )n
"-----XH
Q
+
- - O.
+
N CI N 0
I _I I
CH3 CH 3
Furthermore, the Mukayama reagent is readily transformed into a long chain

derivative, which we employed as combined activating and structuration agent [9].
Therefore, in this work, we describe for the first time a macrolactamization in reverse
micelles using the Mukayama derivatives N-methyl 2-chloropyridinium iodide
(CIPyCI, 1-) and N-hexadecyl 2-chloropyridinium iodide (CI6PyCI, 1-) in reverse
micelles.
Lactamization activated by C1PyCl, 1- or C1{)l!yCl, 1-
The medium-sized ring compound, azacyclotridecanone, was prepared from 12-

aminododecanoic acid using either CIPyCI or Cl6PyCI iodide as activator in 1,2-
dichloroethane.
Synthesis of Macrocyclic Lactams in Organized Media 315
One problem is that the activating agent may undergo hydrolysis, thereby inhibiting
the cyciization reaction. This can be avoided by the use of an inert atmosphere [9].
Table 1 shows the yields of lactam obtained in an inert atmosphere
activating agent yield oflactam

C, PyCl, I' 24%
C'6 PyCl, I" 54% (50%)'
Table 1: lactamization ofNH2-(CH2)II-COOH activated by CIPyCl, I-or C16PyCl, I-

at 80 0 C in 1,2-dichloroethane.
* Yields were determined by GPC, except for the value in brackets which gives the
isolated yield ofproduct.
These yields in a micellar medium using Cl6PyCI iodide are consistent with amicellar
catalytic effect. The ill-amino acid was thought to adopt a hairpin-like conformation at
the Cl6PyCI iodide interface of the reverse micelles. This tends to favor the end-to-
end encounters required for the intramolecular reaction (Fig. 1).
S;:'OO~'"~
CCOOH• • HOO~
T~ CLe, 1'-
(1H2)15
eH,
- NH'!. .NH, ----.J
/ DOOH~
eOCH
/ NH,
(/
Figure 1: Cyciization of 12-aminododecanoic acid in a micellar environment
Lactamization in microemulsions
In the micellar medium described above, although the ill-amino acid was satisfactorily
cyciized, the method has some drawbacks. Firstly the Mukayama derivative is not
readily prepared, and secondly the final product is not easily purified. We thus
attempted to improve this reaction using a surfactantless microemulsion like that
employed by Gonzales and Holt [10]. These authors investigated, albeit with little
success, the cyciization of ill-hydroxy acids in ternary systems of toluene, 2-propanol
and water.These systems without a surfactant consist of a dispersion of water droplets
in a hydrocarbon continuum. It was hoped that the ill-amino acid would adopt a
hairpin-like conformation at the interface of such aggregates. In order to prevent
hydrolysis of the activating reagent we employed formam ide, a solvent with a high
cohesive force, which has been shown to favor molecular aggregation [11]. We
investigated the cyclization of 12-aminododecanoic acid in the toluene/2-

propanol/formamide system with different proportions of the various solvents (Table
2).
Yield
micro emulsion without argon With argon
toluene: 56%
2-propanol: 40% (I) / 10%
formamide: 4%
toluene: 58%
2-propanol: 40% (II) 30% 50%
formamide: 2%
toluene: 58%
2-propanol: 41 % (III) 30% 47%
formamide: 1%
toluene: 59%
2-propanol: 40.5% (IV) 47% 47%
formamide: 0.5%
toluene: 59%
2-propanol: 40.75% (V) 65% 70%
formam ide: 0.25%
Table 2: Yields of azacyclotridecanone in microemulsions with formam ide at 100°C
The benefit of the inert atmosphere is readily seen. On the other hand, we found that
the yield of azacyclotridecanone fell with increasing percentage of formamide. This
was attributed to solvation of the Mukayama reagent by formamide, thereby inhibiting
activation of the (f)-amino acid. In microemulsion (V) containing only 0.25%
formam ide, we obtained a good yield of lactam (70%). The poor solubility of this
substrate in this ternary system may account for the efficiency of this medium. There
is thus little substrate in the continuous phase where the intermolecular reactions take
place. In this system, the (f)-amino acid participates in structuration of the
microemulsion, adopting a hairpin-like conformation, which favors head-to-tail
condensation (Fig.2)
Figure 2: Cyclization of 12-aminododecanoic acid in microemulsions with

formam ide.
Synthesis of Macrocyciic Lactams in Organized Media 317
Since low amounts of formamide (0.25%) are sufficient to confer structuration, we

tested a binary system without formamide. It should be borne in mind that very small
amounts of water may enable formation of a microemulsion. This microemulsion
consisted of toluene and 2-propanol along with the traces of water (around 0.2%)
contained in the latter solvent. We investigated the reaction described above
(cyclization of 12-aminododecanoic acid) in this system with different proportions of
the two solvents with both CIPyCI and Cl6PyCI iodides (microemulsion VIII). The
results are listed in Table 3.
microemulsion yield of2-

azacyciotridecanone
(VI) toluene: 40% 70%
2-propanol: 60%
(VII) toluene: 60%
2-propanol: 40% 70%
(VIII) toluene: 80%
2-propanol: 20% 80%(70%t)
(IX) toluene: 90% 75%
2-propanol: 10%
(X) toluene: 100% 42%-18%-25%
(XI) 2-propanol: 100% 45%
Table 3: Yield of azacyclotridecanone in microemulsions without formamide at

100°C
t activation with Cl6 PyCI iodide, * heterogeneous medium throughout the reaction
The results were comparable to those observed in the presence offormamide, and the
efficiency of the new system was also attributed to the low solubility of the substrate,
which enhances structuration of the medium. On the other hand, in medium (XI)
which contained only 2-propanol, the absence of structure led to a marked drop in
yield of the lactam.
In the case of CI6PyCI, 1- the yield was slightly lower than that observed with
CIPyCI, 1- (microemulsion VIII). This was attributed to enhanced micellar hydrolysis
of CI6PyCI, 1-. The micellar structure of the medium was therefore demonstrated in
this case by the determination of the critical micellar concentration (CMC) of
C16PyCI, 1- (Figure 3). The charge transfer band of the complex between 1- and the
pyridinium ring enabled us to determine this CMC. The change in slope was
accounted for by the higher binding of r ions to the micelles than to the monomers
prior to aggregation [9]. The CMC was observed around 10-5 M.
0,4-,-----------------------,
A
b
s ... 0.0 (292 nm)
o • 0.0 (366 nm)
r
b
a
n
c
e
80.0
0,2
0,0 +--=+--+--t----/--+--+--+---t--+----j
0,00000+0 1,00000·5 2,0000.·5 3,0000.·5 4,0000.·5 5,0000.·5
concentration (mol/l)
Figure 3: Plot of absorbance against concentration (M) OfCl6PyCI iodide in

microemulsion (VIII) at 25°c'
The fact that the difference was small between the yields oflactam with CIPyCI and
with Cl6PyCI iodides (microemulsion VIII in Table III) is of interest as it means that a
microemulsion formed from toluene, 2-propanol and traces of water is sufficiently
structured to favor intramolecular reactions.
The phase diagrams of analogous ternary mixtures of hexane/2-propanol/water have

been determined by ultracentrifugation and conductimetry. It has been demonstrated
that only modest changes are observed in the phase diagram after addition of small
amounts of hexadecyl trimethylammonium perchlorate. Furthermore, 2-propanol
appeared to be the predominant structure-giving component [12].
In an attempt to optimize the microemulsion without surfactant, we investigated the

cyclization yield as a function of substrate concentration. The results are shown in
Table 4.
Synthesis of Macrocyclic Lactams in Organized Media 319
concentration (M) Yieldof2-

azacyciotridecanone
3.10-3 M 80%
6.1O-3 M 83%
9.1O-3M 70%
l.21O-2M 70%(60%*)
Table 4: Effect of concentration of 12-aminododecanoic acid in microemulsion

(VIII). *Isolated yield
Here again yields were satisfactory despite the absence of high dilution conditions. To
provide further support for our interpretation we examined the reaction with another
ro-amino acid,8-aminocaprylic acid. The results are listed in Table 5.
microemulsion Yield of capryllactam

(VII') toluene: 30% 45%
2-propanol: 40%
(VIII') toluene: 80% 40%
2-propanol: 20%
(IX') toluene: 90% 60%
2-propanol: 10%
Table 5: Yields of capryllactam in microemulsion without formamide
Yields were not as high as those obtained with 12-aminododecanoic acid, and were
consistent with the higher solubility of this substrate in the continuous phase. This was
thought to lead to dimerization and polymerization prior to incorporation into the
interface. Therefore, the presence of the cyclized dimer was detected by GeIMS,
which was not observed for 12-aminododecanoic acid.
3 CONCLUSION
The cyclization of ro-amino acids was investigated in both micellar and microemulsion
media. Good yields of the lactam were obtained in microemulsions containing toluene,
2-propanol and traces of water. The poor solubility of the precursors in the continuous
phase helped prevent the intermolecular reaction. The slow solubilization of the
substrate at the micellar interface was thought to favor lactam formation. To support
this interpretation, conductimetric and quasi-elastic light scattering studies are now in
progress. Microemulsions thus show promise as media for cyclization from substrates
that are poorly soluble in organic solvents, in particular for formation of
cyclopeptides.
KEYWORDS
(0amino acids, macrocyclization, macrolactamization, microemulsion, surfactant,

aUkylpyridinium.
REFERENCES
[1] H.Schmitt "Elements de pharmacologie", 7eme Ed.,Flammarion(1980), 441-442

[2] Stetter, H., Marx., J., Ann., 607, (1957), 59-66
[3] Bartra, M., Bou, V.; Garcia, J., Urpi, F., Vilarrasa, J., J. Chern. Soc.; Chern.
Comm., (1988), 270
[3] Bosch, I., Romea, P., Urpi, F., Vilarrasa, J., Tetrahedron Lett., 34 (29), (1993),
4671-4674
[4] Bai, D., Bo, Y.; Zhou, Q., Tetrahedron Lett.; 31, (1990), 2161
[5] Ziegler K., Eberle H., Ohlinger H., Liebigs Ann. Chern., (1993), 504-594
[6] Wei, I., Lucas, A.; Vue, J ,Lennox, R.B., Langmuir.; 7, (1991), 1336
[7] Jaeger, D.A., Ippoliti, J.T., J. Org. Chern., 46, (1981), 4964
[8] Mukayama, T., Angew. Chern. Int. Ed. Eng\., 18, (1979), 707
[9] Rico, I., Halvorsen, K., Dubrule, C., Lattes, A., J. Org. Chern., 59, (1979), 415
[10] Gonzalez, A., Holt, S.L., J. Org. Chern., 46, (1981), 2594
[11] Lattes, A., Rico. I., Colloids and Surfaces., 35, (1989), 221
[12] Smith, G.D., Donelan, C.E., Barden, R.E, J. Colloid. Interface Sci., 60, (1976),
488
SYNTHESIS OF CHROMIUM OXIDES FROM AQUEOUS
SOLUTIONS
A. BLEUZEN*, P. BARBOTIX*, F. GARCIA ** AND J. LIVAGE*
* Chimie de fa Matiere Condensee, Universite P. et M Curie, 75252 Paris

** Elf-Atochem, Centre de Recherches Rhone-Alpes, Rue Henri Moissan, 69310 Pierre-
Benite
ABSTRACT
The synthesis of chromium oxide catalyses from aqueous solutions of acetates and nitrates
has been studied. Upon hydrolyses of these solutions, the condensation of chromium
oxides is strongly affected by the presence of complexing anions and kinetic effects related
to temperature. Amorphous gels or crystalline precipitates can be obtained alternatively.
Both the grain morphology and the porosity of the powders obtained after calcination
strongly depend on the synthesis route as shown by adsorption isotherms.
RESUME
La synthese d'oxydes de chrome catalysees apartir de solutions d'acetates et de nitrates a
ete etudiee. Dans l'hydrolyse de ces solutions, la condensation des oxydes de chrome est
tres affectee par la presence d'anions complexants et d'effets cinetiques sensibles a la
temperature. On peut obtenir soit des gels amorphes, soit des precipites cristallins. La
morphologie des grains et la porosite des poudres obtenus apres calcination dependent
du chemin de synthese mis en evidence par les isothermes d'adsorption.
1 INTRODUCTION
Chlorofluorocarbons (CFC) have long been used in many applications requiring inert
gases such as refrigerating systems or propellants in sprays. But they have been recently
recognized as one of the major causes of the depletion of the ozone layer in the earth
atmosphere. They are now replaced by hydrogenofluorocarbons (HFA) which do not have
any deleterious effect on the environment. Low cost synthesis of these materials is a
challenge that can be achieved with difficulty through fluorination of hydrogenocarbons.
This reaction requires large amounts of catalysts based on chromium oxide which must be
prepared at low cost in the form of very active and porous gels. Such gels have already
been obtained by raising the pH of a chromium acetate solution [1,2], adding a base to a
nitrate solution heated at 60°C [1] or via the reduction of a chromate solution [3]. They
exhibit rather high porosity, but the resulting product strongly depends on the processing
conditions and the aging time.
We are presently reinvestigating the conditions for synthesizing highly dispersed

chromium oxides.
2 EXPERIMENTS
The solutions were prepared by dissolving, the appropriate weight ofCr(N03)).9H20 or

Cr(CH3COOh.H20 in distilled water.
State diagrams were studied by adding various amounts of ammonium hydroxide (1 M).
In the case of chromium acetate, the resulting solutions evolve only over a long period of
time (days or weeks) and lead only to clear solutions or elastic transparent gels (Fig. 1).
Gelation is obtained above the ratio OH-/Cr = 3 which, in a first approach, corresponds to
the addition of the stoichiometric amount of hydroxide for the formation of Cr(OH)).
In the case of chromium, the state diagram is more difficult to draw since above the ratio
OH-/Cr precipitates are readily obtained that redissolve only slowly. Moreover, the
results largely depend on temperature.
At high temperatures (above 50°C) gels are obtained, whereas at low temperatures (5°C)
precipitates are formed.
At room temperature, non-reproducible results are obtained since gels or precipitates have
been obtained under similar operating conditions. This is easily explained by considering
the 20-25°C zone as the borderline between the formation of gels and precipitates.
Synthesis of Chromium Oxides from Aqueous Solutions 323
4 °
~ 3.5 °
OJ
~ 3 .0 o
5015 or sol Uli ons

2.5 ° o o o
O+------r----~~----~----~
o 0.5 1.5 2
[er] moll I
Figure 1: State diagram for the hydrolysis of acetate solutions by NH40H
Gels or precipitates have been separated by centrifugation, redispersed and washed two
times in distilled water in order to remove residual cations and anions adsorbed at the
surface of the solid particles. Powders have been obtained after drying at 50°C. Chemical
analyzes indicate that a large amount of residual counter-anions (acetate/Cr=1.2,
nitrate/Cr=0.7) are retained at the surface of the gels whereas the precipitate derived from
nitrates contains a smaller amount of residual nitrates (nitrate/Cr=O.3). Acetate and
nitrate-derivatives are amorphous as shown by their X-ray diffraction patterns (Fig. 2)
whereas the precipitate obtained from nitrates is crystalline. Its X-ray diffraction pattern
can be assigned to the hydrous active monomer Cr(OHh.3H 20 [4].
Prior to adsorption measurements, the powders have been calcined in air for two hours at
280 0C. The nitrogen adsorption curves are given in Fig.3 . For the acetate-derived gel, the
plateau observed above a relative pressure of P/PO=0.2 indicates a microporosity
associated with a large specific area (300 m 2/g). The gels and precipitates derived from
nitrates exhibit an increasing adsorption volume associated with a mesoporosity. In the
case of the precipitates some macroporosity is evidenced by the large adsorption volume
at higher nitrogen pressures. This relates to the different particle sizes and morphologies
observed through a scanning electron microscope [5] .
!J~
.s
20 40 60 80 [°28]
Angle
Figure 2: X-ray diffraction of a gel and a precipitate derived from nitrate
3 DISCUSSION
The reactions that lead to the formation of a gel can be considered as an inorganic
polymerization process schematized bv two steps [6]:
i) the hydrolyses:
M-OH 2z+ + OH- -+ (la)
For a chromium salt in water with no complexing anion, the monomeric precursor is the
solvated Cr(H20)6 3+ cation which acts as an acid. Reaction (1) is more precisely written
as:
3+ 3~
Cr(OH2)6 + x OH- +-+ Cr(OH2)6_x' (OH) + x H20 (I b)
ii) The hydrolysis step (1) initiates the following condensation reaction:
M-OH2 + HO-M -+ M-O-M + H20 (2)
which yields a large amount of oligomeric species in the case of chromium [4]. However,
in the case of M=Cr(III), condensation is very slow since the 3d3 electronic structure of
Synthesis of Chromium Oxides from Aqueous Solutions 325
this cation makes the octahedral Cr06 coordination so stable that nucleophilic
substitutions involved in reaction (2), are very difficult to achieve.
The hydrolyses reaction is always very rapid since it only consists in the deprotonation of
water molecules solvating the Cr3+ cation. Upon addition of 3 OH-/Cr, the neutral species
Cr(OHh(H20) known as the active monomer is obtained. If no other reaction occurs,
these active monomers form hydrogen bonds with the water molecules of similar species
and yield a crystalline precipitate [4].
In order to avoid the formation of this precipitate it is necessary to increase the rate of the
condensation reactions (2) by heating. This explains the gelation at high temperature and
the precipitation at low temperature that are observed for the nitrate solution.
An alternative method to avoid the precipitation of the hydrous hydroxide is to decrease

the rate of the hydrolysis reaction (1). Chromium acetate is known to give the trimeric
species Cr30(OAc h 4+ in the solution [5]. Upon addition of a base, they cannot react via a
fast deprotonation as in reaction (l) but onlu via the very slow nucleophilic substitution of
the acetate groups A (OAc-) by a hydroxyl group (OH-). Therefore, they allow gelation
through a large decrease of the reactivity of the chromium precursors.
100
80 gel (acetate)
......
OJ)
"0
60
.....,
0
>~
~
40
20
0
0 0.2 0.4 0.6 0.8
Figure 3: adsorption isotherms of gels and precipitates obtained from various precursors
KEYWORDS
chromium oxides, sol-gel, powder porosity, grain morphology, crystalline precipitates
REFERENCES
[1] E.H. Bunce, L.S. Finch, J. Phys. Chern., 19 (1913) 769.

[2] R.L. Burwell, H.S. Taylor, J. Am. Chern. Phys., 58 (1936) 697-
[3] 1. Turkevich. H. Fehrer, H.S. Taylor, J. Am. Chern. Soc., 63 (1941) 1 129.
[4] L. Spiccia and W. Marty, Inore. Chern., 25 (1986) 266.
[5] A. Bleuzen, These d'Universite, Universite Pierre et Marie Curie, (1994)
[6] M. Henry, J.P. Jolivet and 1. Livage, Structure and bonding, 77 (1992) 153.
[7] M.K. Johnson, D.B. Powell, R.D. Cannon, Spectrochim. Acta, 37A (1981) 995.
Chapter 6
MATERIALS STRUCTURES AND BEHAVIOR

MODELING
DEFECT INTERACTIONS: ELECTRONIC TRANSPORT AND

STATISTICAL THERMODYNAMICS IN NONSTOICHIOMETRIC OXIDES
R. TETOT* and G. BOUREAU**
*CNRS-URA 446. Laboratoire des Composes Non-Staxhiometriques, Bat 415,

Universite Paris-Sud, 91405 Orsay Cedex, France
**Laboratoire de Chimie Physique, Universite Pierre et Marie Curie, 11 rue
Pierre et Marie Curie, 75321 Paris Cedex 05, France
ABSTRACT
The effects of defect interactions on the thermodynamic properties and electronic

transport of non-stoichiometric oxides are presented. Two limited thermodynamic
behaviors can be distinguished depending on whether the oxide has a metallic type
electronic conduction or a hopping electronic conduction.
This paper is limited to this last case, exemplified mainly by MI_xO (M = Co, Mn, ..)
cubic oxides (x = departure from stoichiometry). The two approximate methods
usually used in this field, the ideal mass action law method and the Debye-Huckel
theory, are analyzed.
They are both insufficient to accurately describe these compounds. By means of Monte
Carlo simulations applied to a simple model in which point defects interact through a
unique dielectric constant, an account of the main features of the thermodynamic and
electronic transport properties of these oxides is obtained.
328 Materials Structures and Behavior Modeling
RESUME
Les effets des interactions de defauts sur les proprihes thermodynamiques et de
transport electronique des oxydes non st<Echiometriques sont presentes. Deux
comportements thermodynamiques limites peuvent etre distingues suivant que l'oxyde a
une conduction electronique de type metallique ou ionique. Cette contribution est ne
traitera que de ce dernier cas et particulierement de celui des oxydes cubiques M(J-x) 0
( M= Co, Mn, ..) (x= ecart a la st<Echiometrie). Les deux methodes, approximatives,
habituellement utilisees dans ce domaine: la methode de la loi d'action de masse ideale,
et la tMorie de Debye-Hiickel, sont analysees. Elles sont to utes deux insuffisantes pour
decrire avec precision ces composes. A l'aide d'une simulation de Monte Carlo
appliquee a un modele simple dans lequel les defauts ponctuels interagissent a travers
une seule constante dielectrique les principales caracteristiques concernant les
proprietes thermodynamiques et de transport electronique de ces oxydes sont obtenues.
1 INTRODUCTION
The most important thermodynamic functions for nonstoichiometric oxides (NSO),

are LlG(OV and LlH(02), respectively the molar free energy and enthalpy of mixing of
oxygen. As a matter of fact, these quantities can generally be experimentally
determined as functions of both composition and temperature [I]. LlG(02) is
determined from the measurement of the equilibrium oxygen partial pressure Po2 with
which it is related through the relation: LlG(02)= RT Log PO.2 LlH(02) can be
determined either by differentiation of LlG(02)/T with respect to inverse temperature
at constant composition or directly by high temperature microcalorimetry.
At thermodynamic equilibrium, the nonstoichiometry is generated by the presence of

atomic point defects (we do not consider here extended defects such as shear planes in
W03 for example). These defects have a charge balanced by the presence of
electronic defects of opposite charge. Two extreme behaviors may then be considered:
either the electronic defects are immersed in a large conduction band (TiO, YO, solid
solutions of oxygen in transition metals, .. ) or, they are localized on the cations which
then change their valence (CoO, MnO, FeO, Ce02 , V02 .. ). In the first case, due to
the screening of conduction electrons, the interactions between atomic defects are
limited to short range. One can often assume that, at least for first neighbors, the
interactions are much greater than kT (blocking site scheme). LlH(02) is then constant
for small x (x = departure from stoichiometry) and then decreases when more distant
interactions are acting at large values of x (see Figure la). This behavior is observed
particularly in solid solutions of oxygen in transition metals [2,3].
In the second case, one has principally to handle long range Coulomb interactions
between two types of defects (atomic and electronic) of opposite charges. Let us note
Defect Interactions: Electronic Transport ... in Nonstoichiometric Oxides ... 329
that the dielectric constant is small (I:: =13 at room temperature forCoO) [4]. For small
values of x, the Debye-Htickel theory [5] shows that the first significant correction of
the total energy relative to the ideal solution is proportional to x3/2.LlH(02) therefore
varies as xll2 (see Figure lb). This is what is observed for a number of partially ionic
oxides (see references 1,6 and references therein). Only this case will be considered in
the following.
(a)
(b)
DEPARTURE FROM STOICHIOMETRY
Figure 1: Schematic variations of LlH(02) vs. departure from stoichiometry

a) metallic system, b) ionic system
The direct conclusion of this brief analysis is that, in partially ionic oxides, the
interactions have an important effect even and particularly, for small ranges of
nonstoichiometry, which goes against preconceived ideas.
2 ApPROXIMATE METHODS
Two analytical methods are usually used for the study of the nonstoichiometry and
related properties in ionic oxides: Kofstad's [7] the ideal mass action law (lMAL)
method and the Debye-Htickel (DH) theory [5]. From the foregoing, the DH model
seems well adapted for this purpose. Unfortunately, this method has to be confined to
very small departures from stoichiometry « IxIO-3 in CoO) [8]. The IMAL method is
the most often used. In this formalism, several varieties of defects are simultaneously
considered and are assumed non-interactive and randomly distributed, one type being
predominant in a particular Po 2 range. Some of these defects are complex, made of
the association of elementary point defects. In the case of M,-x 0 cubic oxides, metal
vacancies in different states of ionization are usually invoked. Thus, a single ionized
vacancy, V', is made up of a vacancy with two minus charges, V" with an electronic
hole, h", in its immediate vicinity, and may be represented by the cluster {V", hO}. In
the same way, a neutral vacancy, VX, may be represented by {V", 2h·}. This clustering
is a way to partly take into account the attraction between vacancies and free holes of
opposite charge. On the contrary, repulsive interactions between vacancies on the one
hand and free holes on the other are ignored. Some authors also consider the existence
of vacancy clusters such as the so-called 4: 1 cluster predicted by theoretical
calculations [9]. In fact, there is much evidence against the existence of these clusters
at least in the vicinity of stoichiometry [10].
The reliability of the IMAL formalism has been investigated very recently [11]. It has
been shown that its range of application is limited to the case where the interactions
are not too large, therefore E not too small (typically E >17) and for moderate
departures from stoichiometry, i.e. neither too small nor too large. As a matter of fact,
close to the stoichiometry there are not enough charged defects to screen the
interactions and too far from it, the interactions between vacancies begin to play a
noticeable role. In conclusion, neither of these two approximate methods is really
satisfactory. The only way to rigorously handle Coulomb interactions is to perform
Monte Carlo simulations. This is the subject of the next section.
3 MONTE CARLO SIMULATIONS
3.1 Thermodynamic
The numerical methods used in our calculations have been exhaustively described
elsewhere[12] and, therefore, are not reported here. The important point is that we
only consider elementary interactive point defects: metal vacancies with two minus
charges and electron holes localized on cations. Within a nonstoichiometry range
sufficiently small, say x:5: 5.10-3, Coulomb interactions strongly prevail, whereas for
greater departures short-range interactions have to be added to take into account
covalent effects.
The dielectric constant E is taken as an adjustable parameter for a given oxide. Figure
2 reports the dependence of log Po2 and AH(02) on x calculated in a pure electrostatic
model with various values of E. Let us note that our results are known to contain an
indeterminate constant term and that only the variations of these quantities are
significant. We have also reported some experimental data related to CoO and MnO.
Qualitatively, one can see that the experimental behavior of these oxides is well
reproduced with our model, with E=20 corresponding to CoO and E=17 to MnO.
However, it can be shown that the agreement is less good for AH(02) than for log
P02 •
The reason is that AH(02) is more sensitive to short range interactions which have to
be added to improve the model. This is illustrated in Figure 3 which shows results on
"0 1273K
.§ 1273K
.i!.
0
00 0
~ "-
.
2HFOR-"1
"'- 00
~ 0 £::=20
'"
.£ cO
:;J £.=17
'0 '0 0 0 £=13
CoO experimental [6]
:!l
.
~
0 0
C 0
0
A 00 MnO o:pcrimenl.al (14]
.~ ~
.::
.~
~ ;
> > A
~
°
.
0
% ° (=20
A £=17
0
0 £=13
8
j
I 0
0 /I
• CoO c:.:pcrimcntal (H]
I
• \inOexpt'rimcnwl[14]
0
"-
100
reference
o 0
a) 1000 X b) 1000 X
Figure 2: The oxygen pressure and the partial molar enthalpy of oxygen as functions
of the departure from stoichiometry and the dielectric constant
CoO. Here, a short-range attraction of -2.5 kJ mol- i between vacancies and holes as
first neighbors has been added in the calculations. The agreement is now very
satisfactory for both the thermodynamic functions.
.£
~
'"
. Monte Carlo
o Bransky and Wimmer [151
220
.
1273K
• o.
1673K 200
.
0
o •
0
~
1 1 g
180
o· •
g t'
. '"
1413K
)60
<i
0
140
1273K
o· '" 120 • Picard and Gcrdanian [6J
'0
• 0 o Purclyelcclrostatic
)\fonleCario
6. With a small \' -h altraction
100
a) -" -5 -4 -3 -2 -I
b)
0
IogP02 1000 X
Figure 3: log x as a function of log Po2 and the partial molar enthalpy of oxygen as a
function of the departure from stoichiometry for Col-XO.
3.2 Electrical conductivity

The interaction parameters evaluated from the previous thermodynamic analysis were
used to study the electronic conductivity of CoO in the frame of a simple hopping
model [16]. Our model consists of assuming that electronic holes are trapped in
potential weBs, the height of which is the sum of two terms: one is unknown but
composition- and temperature-independent, and another is equal to the opposite of the
interaction seen by the trapped hole. This interaction is of course different for every
polaronic site. Thus, even before performing any calculation, it may be easily
understood that the strong increase of electrostatic interactions as the departure from
stoichiometry increases causes both a decrease of the hole mobility and an increase of
the related activation energy. As we will see further, these features are in agreement
with experiments. The electrical conductivity is calculated by Monte Carlo
simulations from the relation: cr= AL(12 - L)ex (E int )

N I\RT
h
The sum runs over the number of holes. L is the number of cation sites surrounding a
hole and already occupied by a hole (therefore not accessible to a new hole). Eint is the
interaction energy on the polaronic site. The coefficient Atakes the form :
A =cste/T x exp(-EIRT)
where E is a constant. At a given temperature, the composition dependence of the

mobility is caused by the variation of the factor:
f =L (12 - L)exp(E int )

Nh RT
The activation energy has been evaluated by using the Arrhenius law. The results of
the calculations, compared with some experimental data, are reported in Figure 4.
210 Mobllily 50 Activation energy in me"
200 D.
o
180
~D. ·50
o X
1.0
lI1 lIE
X
140 D.
X lIE
lIE
-ISO
no 0 lIE
lIE
lIE
100
0
0 234561
a) lOOOl!: b) IUOOx
Figure 4: Comparison of calculations with experimental determination of the

electronic mobility and the activation energy as functions of the departure from
stoichiometry for Co1_XO.
*: Reference 17, x: Reference 18, : Reference 19, il: Reference 20, -: calculations
As our calculations provide only relative values, we use a reference value. We have
chosen at x=7.10-3 the value 100 for the mobility and 0 for the activation energy.
Despite the scattering of experimental results, the trend is unambiguous: the mobility
strongly decreases, while the activation energy increases as x increases, which is
perfectly rendered by our model.
3 DISCUSSION
In Mj_xO cubic oxides (M = Co, Mn, .. ) (as also in Ce0 2_x [21]), the nonstoichiometry
and related properties can be explained by considering a very simple point defect
model. The key point is to accurately handle the interactions. Only Monte Carlo
simulations allow us to do that satisfactorily. As far as small departures from
stoichiometry are concerned, these interactions are essentially Coulombic. As and
when the departure increases, short-range interactions must be added: first, attractive
between atomic and electronic defects and then repulsive between atomic defects
essentially. The only disadvantage of the Monte Carlo method is its difficulty in
application. It is therefore useful to return to the already mentioned approximate
methods which are, on the contrary, very simple to use. This is all the more interesting
because "exact" results are now available. As already reported, the IMAL formalism
was analyzed recently [8,11]. Conceptually, taking into account the several types of
vacancies, which is the basic idea of the method, can be justified by the observation of
the radial distribution functions calculated by Monte Carlo techniques [12]. In fact, the
clustering between vacancies and holes at first and second neighbors appears quite
preponderant over that at more distant neighbors.
We have also shown clearly that the mass action constants must be evaluated by
considering both enthalpic and entropic contributions, which are generally omitted in
a number of works and lead to erroneous results. Unfortunately, the IMAL formalism
fails when the dielectric constant of the compound is too low, which prevents the
study of MnO for example. It fails also for very small departures from stoichiometry,
which is not a serious drawback as experiments are generally not available in this
range where impurities play an essential role. More serious is the fact that the
formalism fails also for departures greater than, say 7.10-3, because it is impossible to
introduce vacancy-vacancy interactions (other than to consider vacancy clusters).
Contrary to the IMAL method, the DH theory is appropriate to the study of small
departures from stoichiometry. Unfortunately, its applicability is reduced to very small
concentrations of charges. The physical reason is that the ratio 1D la, where ID is the
Debye length (representing the order of magnitude of the radius of the ionic cloud
around a particular ion) and a, the mean separation between two ions, must be much
greater than I. Then, this ratio is equal to I for x=4.10-3 in CO I _x [8].°
Nevertheless, contrary to the case of liquid electrolytes, in defective solids the method
seems to work and is often used beyond this physical limit. However, let us note that
the values of the slope Ux =[ 810gx

81ogPo
J- 1
calculated by this method are rather
2
different from the ones obtained by the Monte Carlo method [8]. Moreover, this
method does not allow us to introduce short-range order interactions.
4 CONCLUSION
One can say that a suitable analytical method aimed at supplanting the cumbersome
Monte Carlo ca!9!lations is not yet available. One direction may be to adapt the
cluster variation method (CVM) [22] used in the case of short-range interactions [23]
to long-range Coulomb interactions.
KEYWORDS
nonstoichiometry, binary metal oxides, Monte Carlo simulations, statistical

thermodynamics, defect interactions
REFERENCES
[1] R. Tetot, C. Picard, G. Boureau, P. Gerdanian, Advances in Ceramics Vol. 23 (1987)

[2] G. Boureau, P. Gerdanian, J. Phys. Chern. Solids 45, (1984), 141
[3] R. Tetot, C. Picard, G. Boureau, P. Gerdanian, J. Chern. Phys. 69, (1978), 326
[4] K. V. Rao, A. Smakula, J. Appl. Phys. 36, (1965), 2031
[5] J. O. M. Bockris , A.K.N. Reddy, Modem Electrochemistry. Plenum Press, New
York, (1970)
[6] C. Picard, P. Gerdanian, J. Phys. Chern. Solids 50, (1989), 383
[7] P. Kofstad, Non-Stoichiometry, Diffusion and Electrical Conductivity m Binary
Oxides (Wiley-Interscience, New York, 1972)
[8] R. Tetot, B. Nacer, G. Boureau, J. Phys.Chem. Solids, 55, (1994),717,
[9] S.M. Tomlinson, C.R.A. Catlow , J.H. Harding, J. Phys. Chern. Solids 51, (1990),
477
[10] D. Schuster, R. Dieckmann, W. Schweika, Ber Bunseqes. Phys.Chem. 93, (1989),
1347
[11] R. Tetot, G. Boureau, J. Phys.Chem. Solids 55, (1994), 357
[12] R. Tetot, B. Nacer , G. Boureau, J. Phys. Chern. Solids 54, (1993), 517
[13] U. Ha1sher, H. Schmalzried, Z. Physik. Chern. Neue. Folge 139, (1984), 69
[14] C. Picard, P. Gerdanian, J. Sol. St. Chern. 11, (1974), 190
[15] I. Bransky, J.M. Wimmer, J. Phys. Chern. Solids 33, (1972),801
[16] G. Boureau, o. Masmoudi, R. Tetot, Solid State Comm.87, (1993), 417
[17] B. Fisher, D.S. Tannhauser, J. Chern. Phys. 44, (1966),1663
[18] N.G. Error, J.B. Wagner, J. Phys.Chem. Solids 29, (1968), 1597
[19) F. Morin, R. Dieckmann, Z. fur Phys.Chem.N.,F. 129, (1982), 219
[20] G. Petot-Ervas, P. Ochin , B. Sossa, Solid States lonics 12, (1984), 277
[21] G. Boureau, O. Masmoudi, R. Tetot, Solid State Comm.79, (1991), 299
[22] R. Kikuchi, Phys. Rev. B 81, (1951), 988
[23] R. Tetot, C. Giaconia, A. Finel, G. Boureau, Phys. Rev. B 48, (1993),10090
MECHANICAL RESPONSE OF AMORPHOUS
POLYMERS: a + ~ MECHANICAL RELAXATIONS,
PLASTIC DEFORMATION, CREEP TEST AND
STRESS RELAXATION
J. PEREZ, L. LADOUCE, R. QUINSON
* Lab GEMPPM-UMR. CNRS 5510 - INSA Villeurbanne 69621 Cedex, France
ABSTRACT
The results of both dynamic mechanical and large stress plastic deformation
performed on amorphous polymers below and through their glass transition
temperature were interpreted in a common theoretical frame. Nevertheless, some
secondary features remain rather poorly understood The theory mentioned above is
then extended by taking into account both the details of the dislocation dynamics
(nucleation and propagation of shear microdomains) and molecular mobility
described in terms ofhierarchically constrained conformational changes.
RESUME
Les resultats de spectrometrie mecanique dynamique et de deformation plastique sous
forte contrainte obtenues avec des polymeres amorphes, sous et a leur temperature de
transition vitreuse, avaient ete interpretes dans un cadre tMorique unique. Cependant,
quelques faits secondaires res tent incompris. La tMorie mentionnee est alors etendue
pour prendre en compte tous les aspects du comportement dynamique des dislocations
(nucleation, propagation de microdomaines de cisaillement) et de la mobilite
moleculaire decrite en termes de changements hierarchises des conformations.
1 INTRODUCTION
The dynamic mechanical response of various polymers below and through their glass
transition temperature Tg have been successfully described on the basis of two
assumptions:
• the existence of quasi-point defects (QPD) corresponding to positive or negative

nanofluctuations of specific volume [1 ] (concentration Cd).
• the hierarchically constrained nature of molecular dynamics [2,3].
Under the application of a stress, some QPDs are accordingly activated into shear
microdomains (SMD), which, in tum, reversibly expand (anelastic strain) until they
ultimately merge irreversibly with one another (viscoplastic strain).
On the basis of these simple arguments the time-dependent, shear compliance was
expressed as:
Gu 1
J(t)=_1 + .ll_exp_(_t)X]+A(_t)X'
'tmol 'tmol
A is a constant increasing with Cd, 'tmol is the time for a translational molecular
motion and is given by
'tI3)I/X
'tmol =to( ~
with 't(3 : the time characterizing the elementary molecular motion (conformational
change) assumed to be responsible for the secondary or 13 relaxation; to is a scaling
parameter and X is a measure of the degree of hierarchical constraint of the correlated
molecular motions; X, increases with Cd between 0 (fully constrained situation) and 1
(constraint-free situation).
The corresponding complex shear modulus was then obtained by taking the Fourier
transform of J(t)-1 such that
where Gr is the relaxed modulus for the primary relaxation which corresponds to the
value of the modulus at the rubbery plateau; the parameter X' (0< X< x'<I) decreases
with the length of chain segments between entanglements or cross-linking nodes; Q is
a constant of the order of unity.
Mechanical Response of Amorphous Polymers: 337
~8
C)
'51i
." 2
---i ••
~
d 7
~'" I •• • ~ r0- e-
e:: til
l'~::-:-, :~:'_"-,:'.__.~.- -: c(b_)~

~O.t 7 'C)
..
_I .,
"0° " 1-
'51i C)
Cl)' ... ' .: <> "." ." .... ."0<>·: .2 '51i6
,- ~:I_I:_:i~; _;:_: _"_'

2
2 '_'_(a_) --11 6
_ ,," ••• 0.
-4 -2 0 -4 -2 0
a) log(flHz) b) log(flHz) c) ]og(aT·f/Hz)
Figure 1: For the a relaxation process in PMMA isothermal spectra (a) G', (b) Gil at
several temperatures: (0) 385.0K; (A.) 390.0K; (V) 392.5K; (.) 395.0K; (0) 397.0K;
(*) 400.0K; (*) 41O.0K (c): the master curves giving the frequency dependence of
the dynamic shear modulus at 385K, the theoretical curves (-) are also shown for
comparison (from Reference 6).
At high stress, the response of amorphous polymers is non-linear: a molecular theory

for the sub-Tg plastic mechanical behavior of those materials was presented [4,5]
considering:
-a thermomechanical activation of f3 process yielding:
with 0'0: stress involving jumps over barriers at 0 K
- a non-conservative movement of dislocations bordering a SMD, thus provoking an

increase of disorder, i.e. of Cd. Inversely, when Cd increases, the molecular mobility
increases allowing, for structural relaxation and subsequent decrease of Cd. In short,
the plastic flow could be viewed as a stationary regime resulting from a balance
between QPDs produced by mechanically forced displacement of dislocations and
QPDs annihilated through structural relaxation.
The whole theory was shown to successfully describe both low (mechanical
spectroscopy) and high (plasticity) mechanical stress tests [6] (see Figure 2).
Nevertheless, secondary features have to be noticed such as
• the occurrence of a large anelastic component with the plastic response of
amorphous polymers.
• the amplitude of stress relaxation is higher than that modeled with the theory
recalled above [7].
• the non-linear creep behavior and the rate of strain recovery which is more rapid
than the rate of creep (or the so-called Turner effect [8]).
Thus the theory needs further development.
t=1.4*10'" S·I
(b)
(a)
t=7*10·J S·I
t=7*10·4 S·I
=1.4*10'" S·I
20 40 20 40
a) Strain % b) Strain %
Figure 2 : Compression stress plotted against deformation of PMMA at various

temperatures and for a speed of 14.lO-5 s-1 (a) and for various speeds at a temperature
of293K (b); the theoretical curves (-) are also shown for comparison (from
Reference 6).
2 DISLOCATION DYNAMICS
We propose to represent the energy profile corresponding to the energy state of a local
region in which a SMD is nucleated and expands. For that purpose, the usual
calculation [9] of the energy of a dislocation loop (radius R, shear vector b) is shown
considering:
Gb (2 R)
2
• the elastic energy of the strain field of the dislocation: 27tR--1n r;:;-
47t ",,3 b
• the work done by the applied stress 7tR20"shearb(with O"shear: shear component of
the applied stress)
Let us apply both results to the Somigliana dislocation loop bordering a SMD: the
energy profile obtained for several stresses is shown in Figure 3a. Up to this point,
such size dependence of the energy of a SMD could be compared to that calculated by
Bowden and Raha [10]. In addition we must consider:
• for SMD with a radius smaIIer than a certain value of about .J3b / 2 ,
corresponding to the core of the associated dislocation, there is no elastic energy.
• the average size of SMDs just before their coalescence is equivalent to the
distance between two activated QPDs, so that it can be estimated to lie between 2
and 3 nm, i.e. R close to 4b; beyond this critical size, the annihilation of the
dislocation elastic energy ought to occur over a distance more or less comparable
to the core of this dislocation.
• superposed on this energy profile, we must add a succession of barriers

corresponding to conformational changes in agreement with the assumption of
the growth of SMDs thanks to hierarchicaIIy correlated molecular movements;
the height of elementary barriers is taken equal to U /3.
20
o MPa (only line energy) 4.: I o iYlPa
15
3.5 ....
i
I
10
o~" 2
50MPa
~5
><U
1
'-'
f 1.5
~'
50 IvlPa
00 RIb
1-
-5
0.51
100 IvlPa
·10 100 MPa o.
a 2 4 RIb
a) ·15 - (with work of applied stress) b)
Figure 3 : (a) Energy of a SMD vs its radius; (b) same as (a) but with (i) limitation of
line energy due to SMD coalescence and (ii) barriers for conformational changes.
Then, the curves presented in Figure I b have to be considered. Such a representation

is semiquantitative since realistic values of the different parameters have been used.
However, the distance between two successive barriers and their number are arbitrary;
besides, with only one spatial coordinate, this simplified view does not take into
account that molecular motions leading to the SMD growth in the stress direction can
only be obtained with hierarchicaIIy correlated processes.
3 STRAIN RESPONSE: DISCUSSION AND CONCLUSIONS
In any case, with the preceding representation, the energy state of an inactivated
defect corresponds to the first well. Every other well corresponds to a possible energy
state for an activated SMD. Moreover, the height of the barriers determines the
amount of thermal energy necessary for the passage from one state to another, i.e. the
kinetics of such a change.
In Figure 3b, it is pointed out that the whole energy profile falls down with increasing
applied stress. The resulting consequences are:
* The equilibrium population of each well is modified; then, to obey the new
equilibrium several defects must be activated and some of the preexisting SMDs
must grow.
* The passage from one energy state to a more activated one (growth of SMD) will
be faster, the applied stress is high since the height of barriers is decreased.
Consequently, increasing the stress results in non-linear behavior corresponding to

both an increase of the response amplitude and a faster kinetics for occupying new
states. Such a picture could justify the common description [7] of:
(i) the main or a mechanical relaxation (low stress, thermally activated jumps over the
highest barrier)
(ii) plasticity (thermally activated jumps over barriers which have become lower when
the stress has been increased).
Moreover, it could explain:
* The increase of the anelastic component of the response with stress, since more
numerous activated states are occupied: this results in higher amplitude of
relaxation or anti-relaxation stress (11) (see Fig. 4).
* Increasing anelastic creep compliance [12] and Turner's observations [8]: the
energy barriers to be crossed for a SMD growth are higher than that required to
return after stress removal (Figure 3b); consequently, the rate of recovery of
anelastic strain is higher than the rate of anelastic deformation (see Figure 5).
* The low temperature shift of a relaxation when the stress is increased until a and
~ relaxation merge together [11] since, for high stress, the main barrier is
completely smeared out while the elementary barrier only decreases a bit (see
Figure 6).
1\
I'!
~t:8
I:
.._C!. 8 : tl ~ I DOMPa
o ; ... o
~ [ ......... . ~b .{ '\
~:.... .................
~ 4/··············· .............. - g4! \
1
~! \
:
: \........................
2 4 (b) 2 4
(a) time/( 1000 s) time/(lOOO s)
Figure 4: Stress relaxation from a deformation ratio of2 (a) and anti-stress relaxation
(b) at 295 K on PMMA at 295 K;(---) experimental curves (from Reference 7),
(-)theoretical curves with new considerations.
35MPa
500 time/s
Figure 5 : Theoretical creep curves on PMMA (------ ) curve given by the

Boltzmann's superposition principle at 35MPa, (-) curves obtained at various
stresses from new considerations. See Reference 12 for similar results on PET.
20
llOMPa
16
•
~12
~
~
~ 8
J
4
0 I • •
150 200 250 300 350 400
TIK)
Figure 6 : From anti-stress relaxation test on PMMA, ratio of anti-stress on applied

stress versus temperature for various applied stresses (from Reference 11); the
theoretical curves with new considerations (-) are also shown for comparison.
Our group is now improving this analysis for a quantitative description of

experimental data related to the non linear behavior of amorphous polymers submitted
to high stress.
KEYWORDS
polymers, dynamic modulus, plasticity, molecular theory.
REFERENCES
[1] Perez J, Rev. Phys. Appl.21 (1986) 93

[2] Perez J, Cavaille J Y, Etienne S and Jourdan C, Rev. Phys. Appl. 23 (1988) 125
[3] Cavaille J Y, Perez J and Johari G P, Phys Rev B39 (1989) 2411
[4] Cavaille J Y, Perez J and Mangion M B, Proc 8th Int Cong on Def. Yield and
Fract. Polym., Cambridge (1991)5/1
[5] Mangion M B, Cavaille J Y and Perez J, Phil Mag 66 (1992) 73
[6] Ouali N, Mangion M B and Perez J, Phil Mag 77 (1993) 827
[7] Ouali N, thesis INSA Lyon (1992)
[8] Turner S, The Physics of Glassy Polymers, Ed: Haward RN, Appl Sci Pub,
London, (1973)
[9] Hirth J P and Lothe J, Theory of Dislocations, McGraw Hill New York, (1968)
[10] Bowden P Band Raha S, Phil Mat 29 (1974) 149
[11] Quinson R, Perez J, Germain Y and Murracciole JM, Polymer, 36 (1995), 743
[12] Ladouce L, Perez J, VassoilIe R, Vigier G, J Mat Sci 29 (1994) 5399
MODELING OF ANISOTROPIC COALESCENCE OF
y' IN SUPERALLOYS
J.L. VALLES and D. J. ARRELL
Institute for Advanced Materials, Joint Research Centre, European

Commission 1755 ZG Petten, The Netherlands
ABSTRACT
Progress in the industrial design of structural components for high temperature

applications very often depends on the knowledge of the mechanical behavior of the
advanced materials which are employed An anisotropic coalescence modeling of r'
nickel-base superalloys usedfor aircraft engine blades, is presented This method, based
on microstructural information defined by a calculated anisotropic coarsening criterion
for the (r') phase in the (11 phase matrix, and then introduced in a Monte Carlo
simulation with Kawasaki dynamics, is able to reproduce experimental rafting behavior,
even more accurately than the previous too costly Monte Carlo-Finite Element
approach. This rapid computation allows for incorporation of further refinements to
simulate more complex situations, thermomechanical fatigue, for example.
RESUME
Les progres dans la determination de composants structurels industriels pour des
applications a haute temperature reposent sur la connaissance du comportement
mecanique des nouveaux materiaux envisages. Une modelisation de la coalescence
anisotropique de superalliages abase de nickel utilises en aubes de turbines d'avion, est
presentee. Cette methode est fondee sur la connaissance de la microstructure conduisant
a la definition d'un critere calculable du grossissement anisotropique de la phase (y J
dans la phase (11 constituant la matrice, qui, introduit dans une simulation de Monte
Carlo utilisant la dynamique de Kawasaki, permet de decrire Ie comportement de
coalescence observe experimentalement, meme plus precisement que la precedente
approche, tres couteuse, associant la technique de Monte Carlo et les elements finis. Ce
type de calcul rapide permet d'introduire d'autres rafjinements conduisant a simuler des
situations plus complexes, la fatigue thermomecanique, par exemple.
1 INTRODUCTION
In applications requiring optimum mechanical properties even at high temperatures, as

in the case of aircraft turbine blades, modern nickel-base superalloys are the preferred
materials. Their excellent strength and creep resistance rely on a complex
microstructure, which is the product of a sophisticated aging process. In the latter
stages, particles of the ordered r' phase are precipitated from the initially solidified r
phase by further cooling, in order to act as an obstacle to the dislocations traveling
through the disordered matrix. When, in addition, components made of a superalloy
are grown as single crystals, the damage mechanisms which would operate at grain
boundaries are suppressed, and this results in an extension of the high temperature
lives. Progress in the industrial design of structural components for high temperature
applications very often relies on the knowledge of the mechanical behavior of the
advanced materials which are employed. Since thorough testing at all loading and
temperature conditions of interest is clearly not feasible, a reliable way to predict the
behavior of these materials under service conditions is required. Ideally, such an
approach should be based on a knowledge of the mechanisms which are responsible
for microstructural evolution, deformation and damage.
2 MODELING OF MICROSTRUCTURAL EVOLUTION
The incorporation of the relevant microstructural information into a predictive

approach is illustrated by our recent work [1-4] on the anisotropic coarsening or
rafting phenomenon in nickel-base superalloys. The morphological changes associated
with the high temperature coalescence of r' under load produce extended directional
precipitates (rafts), which result in a significant modification of the creep or fatigue
life. As knowledge of the rafting behavior is therefore highly desirable, an attempt
was made to predict the formation of plates or needles, based on the most
energetically favorable shape for a r' inclusion [5]. The basic disadvantages of this
method were that only a finite number of shapes could be considered and that the
energy comparison could only be evaluated for a few experimental conditions.
Further, temperature effects were not explicitly incorporated. A combined Monte
Carlo-Finite Element approach to simulate anisotropic coarsening in a lattice model
succeeded in reproducing the general trends of the previous predictions, but the costly
calculations were clearly impractical even for the small lattice sizes considered.
3 NEW CRITERION ApPROACH
The new criterion which we present overcomes the limitations of the earlier
approaches, improves the prediction maps and, moreover, is simple enough to be
incorporated into a purely Monte Carlo algorithm which provides the evolution of a
Modeling of Anisotropic Coalescence ofy' in Superalloys 345
two-dimensional anisotropic lattice model associated with the superalloy. The

morphologies which develop at the different temperature and stress conditions are
explained on the basis of the anisotropy of the dislocation arrays which appear at the y
- y' interfaces [7] in order to relieve the stresses generated by the mismatch 8 = 2(ay'-
ay)/( ay+ay) between the lattice parameters (see Fig. 1). This anisotropy arises from
the non-symmetrical effects of a combination of temperature and external load on the
mismatch in mechanical properties of the two phases.
0 Matrix (rJ
cr ., -
~ Precipitate (r')
1.
1
Misfit Dislocation
Figure 1 : Schema of the anisotropy in the dislocation distribution around a y' particle
under tensile load.
A quantitative formulation can be established [1] on the basis of the elastic energy
associated with these N= I ay'- La{ 11 misfit dislocations (per unit length of interface
and per unit length of dislocation),which can be expressed by
(1)
where E is the elastic modulus and k is a numeric constant. The dimensionless

quantity R, defined as the ratio of the directional energies at surfaces parallel and
perpendicular to the load axis,
o 0 ( 1+ crjEy )
Upara (l+ajEy) a y,-aY (I+ajE y')
R - - - - +----'---'-'-;-1----;---'----'--',,....1
- U perp - (1- vajE y) 0 0 ( 1 - vajE y)
ay' -ay
(1- vajEy')
reflects the anisotropy in the strains alE and -valE, produced in the directions parallel
and transverse to the load respectively, upon the initial value aD of the lattice
parameters, and it can be taken as a measure of the tendency to produce anisotropic

morphologies. Specifically, since the surfaces with lower energy are expected to grow
at the expense of those with higher energy, values of R larger than one, indicating that
upara > uperp, will predict an anisotropic coalescence extending the interfaces
perpendicular to the applied load, and thus plates will be produced. The driving force
will instead favor the formation of needles parallel to the load axis when upara <
uperp , or equivalently R< I, while for R=1 isotropic coalescence is expected. A
three-dimensional plot of the value of R versus temperature and applied stress,
calculated using material parameters for the single crystal superalloy NASAIR 100, is
shown in Fig. 2. From this diagram, it can be seen that at high temperatures this alloy
would form plates under tensile stresses and needles under compressive ones, which
agrees with the morphologies found experimentally [8]. Thus, the criterion described
above provides a significant improvement in the prediction capabilities of the most
favorable microstructural morphology at different temperatures and loads. Similar
rafting prediction maps have also been developed for several other single crystal
superalloys [4] . Furthermore, the anisotropic coarsening criterion developed as
described above has been incorporated into a lattice model, and a Monte Carlo
simulation allows one to mimic the microstructural evolution during rafting [2] . Our
two-dimensional lattice model accounts for the anisotropy by adopting the ratio R of
the directional y- y' interfacial energies as the ratio between the coupling constants in
the two principal directions. The system evolves through the exchange of pairs
_ .3
1600
·1000
Figure 2 :Three-dimensional prediction map for NASAIR 100. The values of R <0.9
are taken as predicting needle formation (one dimensional structure), the
regions with R> 1.1 as predicting plate formation (two-dimensional structures)
and the intermediate values as isotropic coarsening.
of particles corresponding to the y and y , phases which are occupying neighboring

sites, using Kawasaki dynamics. The initial configurations are taken to be arrays of
Modeling of Anisotropic Coalescence of y' in Superalloys 347
units consisting of a round-cornered square precipitate embedded in the corresponding

part of the surrounding matrix channels, in accordance with the experimental volume
fractions.
to .------------~----------____r
08
Q
0.6
co
()
<l.l
Q
</) OA
co
0.2
1000 MCS 5000 MCS 10000 MCS
o~-------------------------~
o 0.5x104 1.0x10 4 1.5x104 2 .0x104
MCS
Figure 3 :Evolution of the aspect ratio during a simulation of the rafting behavior of
NASAIR 100 under a tensile stress of200 MPa at 1123K
A number of tensile and compressive applied stress values and a range of

temperatures have been explored, providing information regarding the evolution of the
aspect ratios, which are calculated as the quotient of the interfacial lengths in the
horizontal and vertical directions, and other time-dependent quantities. A typical
evolution can be seen in Fig. 3, where the aspect ratio reflects the formation of an
anisotropic metastable structure in which the influence of the initial configuration still
persists, in agreement, qualitatively and also quantitatively to a large extent, with the
rafting morphology which develops experimentally for similar conditions [8]. In order
to compare with the experimental behavior at longer times, the model would require
the incorporation of damage mechanisms such as precipitate cutting by dislocations.
4 CONCLUSION
The results seem to reproduce the observed rafting behavior even more accurately
than the previous combined Monte Carlo-Finite Element approach, yet demanding
much shorter computation times. This rapid computation allows for the incorporation
of further refinements, for example to account for the anisotropy in the diffusion
constants or to perform evolutions under non-isothermal conditions. The long term
aim of this project is to be able to simulate the material behavior under more complex
loading and temperature conditions, particularly in the case of thermomechanical
fatigue. The success of this study shows that the incorporation of microstructural
information into an approach to predict the mechanical behavior of real materials is
not only a desirable goal but also an achievable one.
KEYWORDS
coarsening, rafting, anisotropic criterion, Monte-Carlo simulation, finite element,

Kawasaki dynamics, nickel-base superalloys.
REFERENCES
[I] DJ. Arrell and J.L. Valles, "Interfacial dislocation based criterion for the prediction of
rafting behavior in superalloys", Scripta metallurgica et materialia, 30, (1994), 149-
153.
[2] J.L. Valles and D.J. Arrell, "Monte Carlo simulation of anisotropic coarsening in
nickel-base superalloys", Acta metallurgica et materialia, 42, (1994), 2999-3008.
[3] D.J. Arrell and J.L. Valles, "A model for microstructural evolution in superalloys
subjected to an applied stress", in Localized damage III: Computer-aided assessment
and control, ed. by M. H. Aliabadi et aI., Computational Mechanics Publications,
Southampton, U.K., (1994), 279-285.
[4] J.L. Valles, D.J. Arrell and J. Bressers, "Misfit dislocations and anisotropic coarsening
in superalloys", Archives of Mechanics, 47, (1995), 601-615.
[5] A. Pineau, "Influence of uniaxial stress on the morphology of coherent precipitates
during coarsening - elastic energy considerations", Acta metallurgica, 24, (1976), 559-
564,.
[6] J. Gayda and D.J. Srolovitz, "A Monte Carlo - Finite Element model for strain energy
controlled microstructural evolution: 'rafting' in superalloys", Acta metallurgica, 37,
(1989),641-650.
[7] M. Feller-Kniepmeier and T. Link, "Correlation of microstructure and creep stages in
the <100> oriented superalloy SRR99 at 1253K, Metallurgical Transactions, 20A,
(1989),1233-1238.
[8] M.V. Nathal, R.A. MacKay and R.V. Miner, "Influence of precipitate morphology on
intermediate temperature creep properties of a nickel-base superalloy single crystal",
Metallurgical Transactions, 20A, (1989), 133-141.
DATABASE-RELATED STANDARDIZATION TO
DESCRIBE EXPERIMENTAL RESULTS ON THE
THERMOPHYSICAL PROPERTIES OF SOLIDS
G.JAROMA-WEILAND, G.NEUER
Institut fur Kernergetik und Energiesysteme (IKE), Universitat Stuttgart,

Pfaffenwaldring 31, D-70550 Stuttgart, Germany
ABSTRACT
Thermophysical data have complex correlations between the measurement values and
supporting information on material characterization and description of experiments. In
order to find an easier mode of data entry, the CODATA task group EXPERIDAT, is
commissioned to convince publishers to present their papers in a form ready to enter a
database. This report is expected to contribute to finding an intemational agreement for
a standardization in the domain ofthermophysical properties of solid materials:
A special PC input program is proposed in conjunction with the THERSYST database

for storage, evaluation and representation of these data. Scientists are invited to
participate in building the final description system.
RESUME
Les donnees thermophysiques presentent des correlations complexes entre les valeurs
mesurees, les bases d'informations sur les caracteristiques des materiaux et la
description des experiences. De far;on a rendre plus aisee l'entree dans une base de
donnees, Ie "task group" de CODATA, EXPERIDAT, a pour mission de convaincre les
auteurs de presenter leurs publications sous une forme toute prete a entrer dans une
banque de donnees. Cette article espere contribuer a trouver un accord international
pour une standardisation dans Ie domaine des proprietes thermophysiques des
materiaux solides:
Un programme PC special de rentree est propose, en liaison avec la banque de donnees

THERSYST pour Ie stockage, Ie contr6le et la representation des ces donnees. Les
scientifiques sont invites aparticiper ala construction finale du systeme de description.
1 INTRODUCTION
The computerization of all possible aspects of science and technology is one of the
reasons for increasing interest in computerized material databanks. Thermophysical
data are distinguished by complex correlations between the measurement values and
supporting information on material characterization and description of experiments.
This causes difficulties in database building and a high cost of data entry. Data
collection, even collection of already published data, is very expensive, especially
because of the need to evaluate the input. Therefore there are efforts to introduce
electronic publishing of experimental results parallel to the usual form of written
papers.
The intention of the CODATA task group, EXPERIDAT (Database for Experimental
Data and Telepublishing) is to convince publishers of related scientific papers that
papers should only be accepted if the description of the data is presented in a form
which can be more or less directly used as an input into a database. The most
important prerequisite for that purpose is the availability of an internationally accepted
form of presentation. Chemical databases are the most advanced with respect to the
standardization of the material nomenclature and the sample description. Also for the
representation of the data some standards have been developed, e.g. V AMAS standard
for reporting surface science data[l]. For engineering materials the situation is more
complicated because they rarely have unique compositions and the production process
drastically affects properties. Hence research on systems for these materials is
important.
This paper should contribute to finding an international agreement for standardization

in the domain of thermophysical properties of solid materials. A special PC program
has been developed which enables entering the description of a material and an
experiment. This information can be transferred together with the measured property
data into THERSYST, the database with a program system for storage, evaluation and
representation of thermophysical properties of solids[2].
2 DESCRIPTION OF THE INPUT PROGRAM
In the database THERSYST it is possible to store a great number of material and

experimental parameters. Contrary to other thermophysical databanks like
POLYMATE [3] or ALUSELECT [4], in THERSYST the given information can be
traced back to the original source and the user can handle the experimental data by
means of different moduli, e.g. intercomparison, recalculation, regression, etc. It was
achieved by using a classification concept. The relevant information is converted into
a standardized form given by a categorization scheme and it is stored in the form of
data-sets. The categorization scheme is divided into five classes. In each class the
information is stored by descriptors and their number is given in parenthesis:
Database-Related Standardization .. on Thermophysical Properties of Solids 351
class-I: material designation and typical constants (14)

class-2: characterization of the specimen to be studied (51)
class-3: description of experiment (11)
class-4: description of the thermophysical property and the property data (22)
class-5: bibliographic information on the literature source (7).
Classes 1 to 4 are hierarchically structured. The bibliographic information is not

included in the hierarchic structure, but it is linked to the corresponding data-set by
the document number. The main part of the information is stored in a numerical or
coded form. It guarantees the proper operation of retrieval in the database because
each descriptor can be used as a search criterion. Textual descriptors are also available
for additional information which can not be classified. The structure and the content of
THERSYST are described in detail in [2,5]. For the input of the descriptive data a
special PC program has been developed. It operates by means of a window technique.
Classes 1, 3, 4 and 5 use one input window each; for class 2 three windows are
necessary. Fig. 1 shows, as an example, one of the input windows for class 2 (material
characterization). An asterisk indicates those fields in which a code should be typed. If
a cursor is placed on such a field, by pressing the FlO-key the selection window is
opened and the pop-up window displays the possible inputs for this field. In the
demonstrated example the cursor is placed on the field "crystal structure".
class: MATCHAR.2
structure: POLC (*) crystal str: @ (*) Solid Solution: (*)
microstructure:
lattice parameter: 5.6787A, grain size: l2micro-meter;
preparation: CAST HOMO (*)

sample treatment - preparation
mechanical: POLl (*)
chemical: CHET (*)
thermal: AGED (*) temperature: 430.00 [l1J time: 2.000 [582J
atmosphere: air
pressure: 1 [569J field: [650J
kind of irradiation: (*)dose: [600J temp: [ 10]
further treatments: (*)
INPUT CORRECT (YIN) N
ADD NEW DATA TO EXISTING DATA
Figure 1 : Input window for material characterization (class 2)
In the pop-up window the codes for the chosen descriptors are listed (Fig. 2). The
selected input is transferred automatically. The same procedure is used for unit-codes.
These fields normally have default-values which are coded in SI-units. The list of
codes can be extended by each program user. This input program inserts the data into
a dBase-databank. From this database the data are exported together with measured
property data by means of ASCII-files, either to THERSYST installed on the
VAX-mainframe or into PC-THERSYST.
class: MATCHAR.2
triclinic
TRCL
structure: POLC (*) Cr MONO
monoclinic (simple)
microstructure: MOBA
monoclinic (base centered)
lattice parameter: 5.67 ORTH
orthorhombic (simple)
ORBA
orthorhombic (base centered)
ORBO
orthorhombic (body centered)
ORFA
orthorhombic (face centered)
preparation: CAST HO TETR
tetragonal (simple)
sample treatment - prep ~O tetragonal (body centered)
mechanical: POLl ~ cubic (simple)
chemical: CHET BCC cubic (body centered)
thermal: AGED (*) FCC cubic (face centered) 000 [582]
HEX hexagonal
HCP hexagonal (close-packed) [650]
kind of irradiation: TRG trigonal [ 10]
further treatments: RHOM rhombohedral
INPUT CORRECT (YIN) SCHE scheelite
ANFL anti fluorite
ADD NEW DATA TO EXISTING DATA
Figure. 2 : The same window as Fig. 1, however, with additionally displayed codes
for the descriptor "crystal structure".
3 ACTIVITIES TOWARDS THE STANDARDIZATION OF THE

THERMOPHYSICAL DATA
The need for standards for reporting and presentation of the data from tests and from
their evaluation has been commonly accepted. The THERSYST scheme of
categorization with standard descriptors to describe the experiment and the material
can be a contribution to such standardization in the field ofthermophysical properties.
The list of descriptors is the result of numerous discussions of experts in the German
task group "Thermophysik". The database is installed at present at four German
institutes, where the storage of thermophysical property data is subdivided into the
following material groups:
metallic elements and alloys: IKE'
actinides and their compounds: ITU2
Institut fUr Kemenergetik und Energiesysteme, Universitlit Stuttgart, contact person: Dr.
G. Neuer, Dr. G. Jaroma-Weiland
2
Europliisches Institut fUr Transurane, Karlsruhe, Prof. J. Fuger
Database-Related Standardization .. on Thennophysical Properties of Solids 353
ceramics: IMF 3
heat insulation materials: P1 4 •
Although the categorization scheme has proven to be well suited for all these types of
materials, it shall not be thought of as a rigid system: the list of descriptors in each
class can be enlarged. In order to involve experimenters in the discussion about the
content and the mode for the presentation of thermophysical data, the above
mentioned input program was demonstrated during the 12th Symposium on
Thermophysical Properties 5 and some copies were distributed to selected
participants[6]. It was proposed there to organize an International Thermophysical
Properties Database Club. The participants of the Club submit their data - after these
are ready for publishing - via the input program to THERSYST and in that way it can
be proved whether the categorization scheme is sufficient to characterize the studied
materials and the experimental conditions. The suggestions of the participants for
modifying the description system will be taken into consideration and implemented
into the program. Updates will be sent regularly to all users because it is an urgent
requirement that a uniform input program be used, otherwise the data will not fit
together in the database. By actively making use of this procedure, an international
standard for reporting the data for thermophysical properties will be automatically
achieved.
4 CONCLUSION
The described input program has been installed in several European laboratories. The
experimenters who send their data to THERSYST are entitled to get data of interest to
them from the pool. This form of data exchange offers a good opportunity for a new
kind of communication between measurement laboratories. Furthermore, it will
contribute to the discussion on standards for the reporting and the presentation of
thermophysical property data.
ACKNOWLEDGEMENT
The described work was financially supported by the Bundesministerium fur

Forschung und Technologie within the framework of the project COST507 and by the
European Community represented by the European Institute for Transuranium (ITU),
Karlsruhe.
Institut fUr Materialforschung, KtK, Karlsruhe, Dr. B. Schulz

4
Physikalisches Institut fUr Materialforschung, KtK, Karlsruhe, Dr. B. Schulz
19-24 June 1994, Boulder, Colorado, USA
KEYWORDS
therrnophysieal properties, database, THERSYST
REFERENCES
[1] W.A. Deneh, L.B. Hazell, M.P. Seah; NPL Report DMA(A) 164, National
Physical Laboratory, Teddington, July (1988)
[2] G. Neuer, R. Brandt, G. Jaroma-Weiland, G. Pflugfelder; Int. J. Thermophys.
10, (1989), 749
[3] N. Herrlich; Swiss Materials 3a, (1990),12
[4] P. Sehonholzer, R. Sandstrom; Swiss Materials 3a, (1990), 25
[5] R. Brandt, K. Loffler, G. Jaroma-Weiland, G. Neuer, and G. Pflugfelder;
Report IKE 5-229, Institut fur Kemenergetik und Energiesysteme der
Universitat Stuttgart, November (1987), 75
[6] G. Jaroma-Weiland, G. Neuer, M. Tisehendorf; Int. J. Therrnophys., 17,
(1996),223
MATERIALS DATA FOR THIN INTERLAYERS BY AN
INVERSE METHOD: THE CASE OF A CONSTITUTIVE
LAW OF BRAZES
G. LOVATif, F. MORET, G. CHAUMAT, G. CAILLETAUDb,

P.PILVI"
a CEAICEREM - Section de Genie des Materiaux, C.E.N G. 17 rue des Martyrs

38054 Grenoble Cedex 9, France
b Ecole des Mines de Paris, Centre des Materiaux P.M Fourt, URA CNRS
866, BP 87,91003 Evry Cedex, France
ABSTRACT
Soft layers are of great interest for the joining of dissimilar materials like beryllium,
tungsten or carbon base refractory tiles for plasma interfaces and cooled structures
made of copper or molybdenum in TOKAMAK thermonuclear fusion reactors. Soft
layers reduce the residual and in-service stress/strain levels without reducing the
thermal capability. Thin, soft layer interfaces are produced during the brazing or HIP
bonding cycles. However, the numerical modeling of the mechanical effect of such soft
layers remains largely inaccurate. The camber of [CFC tiles (AD5, NI-l NI-12)lAg-
Cu-Ti filler metal, OFHC or TZM substrate assemblies is recorded during the whole
brazing thermal cycle and subsequent thermal fatigue cycles using a special vertical
dilatometer. An inverse method based on Finite Element modeling of the samples is
used to determine the joint constitutive law. Then, by comparing experiments and
FEM calculations, the effects of distributed damage of the CFC and of the strain
hardening and thermal softening of OFHC on the in-service stress/strain state of the
component are observed.
RESUME
Les lois constitutives de fines brasures ou de couches compliantes liant des materiaux
dissemblables sont necessaires pour la conception mecanique de tels ensembles.
Pourtant, leur determination est difficile voire impossible par des mesures directes en
tension ou en cisaillement. Une procedure speciale a ete etablie, basee sur Ie suivi de la
cambrure d'un echantillon bimetallique en fonction de la temperature. A I'aide d'une
modelisation en elements finis de l'echantillon et l'utilisation d'une methode inverse, les
proprietes susvisees ont pu etre determinees. L'application de cette etude it quelques

couples de materiaux est presentee.
1 INTRODUCTION
Due to CTE mismatch between refractory materials (Be, W, CFC) and structural
alloys (Cu alloys, TZM-Mo, SS), residual stresses are generated during joining and in-
service thermal cycling of first wall and divertor components in TOKAMAK
thermonuclear fusion reactors [11. Prediction of these stress fields is necessary to
avoid immediate cracking and to expand in-service life of such bonded parts.
Numerical models currently used for the calculation of such stresses are commonly
inaccurate by a factor of two (or more) due to several unresolved problems, mainly the
knowledge of material constitutive laws from room to joining temperature and
especially for the joint, e.g. interlayers and filler metal.
After bonding, the joint is the result of complex physico-chemical reactions which
occurred between the filler metal, the refractory and the metallic substrate in the liquid
and solid states. Its thickness (10-100 /-lm) does not enable any accurate direct
measurement of its mechanical properties.
To overcome this problem, experimental and numerical methods have been

developed. An inverse numerical method has been applied to camber vs. temperature
records of simple assemblies. This method is applied to the study of CFC components.
2 EXPERIMENTAL
2.1 Materials and preparation
Three materials have been considered in the studied assemblies:
-The substrate :
OFHCCu: polycrystalline pure copper, or
TZMMo: Mo-0.5%Ti-0.1% Zr from PLANSEE;
-the filler metal:

TiCuSil : Ag-26.7%Cu-4.51%Ti from WESGO, or
CuSiIABA: Ag-35.25%Cu-1.750%Ti (WESGO);
-the tile is a carbon fiber-carbon (CFC) composite with ex-PAN fibers. The
densification is done by CVD of pyrocarbon by a pitch impregnation.
A05: 2D (felt-type material with the fibers randomly distributed in the plane) from
Materials Data for Thin Interlayers by an Inverse Method ... Law of Brazes 357
CARBONE LORRAINE.
NI-l: 3D needled in the Z direction, from S.E.P.
NI-12: same as NI-l but with more CVD steps.
For brazing operations, the main fibre planes of both composites are oriented
perpendicular to the plane of the joint. Before the brazing operation, substrates such as
copper or TZM and the filler metal were cleaned. A dust removal treatment was
applied to the CFC materials. The thickness of the filler metal foil was 100 J.l.m for
TiCuSil and CuSil ABA.
2.2 In-situ recording of camber
A vertical dilatometer is used for in-situ measurement of the camber of flat bi-material
specimens during the whole brazing thermal cycle (Figs. 1& 2).
Figure 1: View of the specimen and of Figure 2: Principle of in-situ measurement

the alumina probes out of the in the dilatometer of the camber of bi-
dilatometer furnace . material specimens.
A computer-controlled differential dilatometer with a graphite furnace has been

modified to work on large specimens under vacuum (10- 6 mbar). The displacement
accuracy is better than 0.2 Ilm. Numerical records of temperature and displacement
vs. time are obtained (Fig. 3). During heating up to the melting of the braze, the
dilatometric signal corresponds to the thermal expansion of the materials and to the
flattening of the filler metal foil. The beginning of the melting of filler metal is
observed at 780°C, which corresponds to the Ag-Cu eutectic temperature. During
melting, the braze thickness decreases from 100 Ilm to 50 Ilm. This thinning is
enhanced by filler capillarity and fillet formation due to the reactivity of the titanium
in the filler metal. During the cooling down, two phenomena are superimposed:
-inverse thermal expansion ofthe substrates,

-camber formation due to the CTE mismatch.
Displacement [11m)
20 Melting
Thermal
10 expansion
Plate!'ing of
0 fillermela
-10
-20
-30
-40 elting
-50 Camber Solidification
-60 formation
-70
-80
0 100200300400500600700800900
Temperature [OC)
Figure 3: Dilatometric record of a brazed joint CFC NI-12/CuSil ABAlOFHC Cu.
A change in the slope of the dilatometric records is observed near 450°C. Above
450°C, camber formation is lower than inverse thermal expansion, and below 450°C
the magnitudes of both effects are inverted. Moreover, subsequent heating shows that
this effect is partially reversible.
3. IDENTIFICATION OF JOINT CONSTITUTIVE LAW BY AN

INVERSE METHOD
3.1 Thermomechanical modeling
Stresses generated during the brazing process are estimated from 2D plane strain
thermo-elastoviscoplastic analysis by the finite element method (FEM) using the
software ZeBuLoN [2], with 8-nodal point axisymmetric elements. The deformed
structure after cooling down from 780°C to RT is shown in Fig. 4.
Figure 4: FEM mesh ofthe dilatometric specimen.
3.2 Principle of the inverse method
After the building of a numerical model of the physical problem, as was described in
3.1, the identification of the coefficients (discretized flow stress of the joint vs.
temperature) is made by solving an "inverse problem", which consists in finding the
parameter set realizing the best fit between experimental data and the model response
[3].
This is performed with a code acting together with ZeBuLoN, called SiDoLo. SiDolo
and ZeBuLoN are linked by an interface, which has three tasks: I-Read the new
coefficients proposed by the optimization code; 2-Update the data file for the external
code and make the run; 3-Read the results of the simulation code and compute the
new values of the "observable" variables to be used by the following optimization
procedure.
3.3 Identified joint constitutive law
In another work [4], we carried out the identification of a joint constitutive law by an
inverse method on TZM-Mo/InCuSil ABA/AISI 316L specimens. Fig. 5 shows the
joint yield stress vs. temperature compared with the one given by Levy [5] for the
initial foil. This result indicates that the joint material is softer than the initial filler
metal. This effect is due to the coarsely solidified microstructure of the joint and to the
reaction of the components (especially titanium) with the bulk materials. This large
difference in flow stresses is responsible for large errors in the final stress/strain fields
when the Levy law is used.
Flow [MPa]
250
I entified law
20
15 Levy
10
50
o
o 100 200 300 400 500 600 700 800
Temperature [0C]
Figure 5: Flow stress vs. temperature of an InCuSiI ABA soft joint determined by the
inverse method compared with the one given by Levy [5] for the initial foil.
4 MECHANICS OF CFC BRAZED JOINTS
Figs 6 and 7 show comparative results with the considered CFC and substrate
materials. These results are correctly described by adequate FEM modeling. In Fig. 6,
the differences in CTE and elastic properties between the three CFC materials induce
significant variations in final camber (and consequently stress level) in the following
order NI-l>A05>NI-12. Comparison between Fig. 6 (a) and (b) shows the effect of
the substrate material (high CTE, low YS for OFHCCu, and low CTE and high YS for
TZM).
In Fig. 7, the thermal cycling of the specimens exhibits large differences in behavior
between the two substrates. The viscoplastic behavior ofOFHCCu (creep) even at low
temperatures induces a rapid loss of camber when the specimen is reheated, while
strain hardening occurs during cooling down. On the contrary, the high yield stress
and the high stiffness of TZM induce high stresses which promote distributed damage
in the CFC material, reducing the stress level.
5 Displacement [flm] -->- Nll-eFe 5 RO Displacement [flm]
-t--- A05-eFC S
0
--+- NI12-CFC S
0
5
5 -10
-15
-10
-20
Temperature [0C] Temperature [0C]

-15
(a) 0 100 200 300 400 500 600 700 800 (a) 0 100 200 300 400 500 600 700 800
10 Displacement hun] 10 Displacement [J.lm]
-t-NII-CFC
RO
~A05-CFC
8 8
' \ 6
--+- N 112-CFC
6
4
4
\:~~:~
2
2
\ ~/s
0 S
0 -2
-4 CI
-2
-6
~~~cmperaturc
-4 C2
-8
[0C) Temperature [0C]
-6 -10
(b) 0 100 200 300 400 500 600 700 800 (b) 0 100 200 300 400 500 600 700 800
Figure 6: Dilatometric records of the Figure 7: Dilatometric records of the

cooling down from the solidification cooling down from the solidification
(point S) to RT during brazing with (point S to RO) then during two
CuSil ABA of the three CFC materials subsequent thermal cycles from RT to
onto (a) OFHCCu and (b) TZMMo 500°C (RO to Cl to Rl to C2 to R2) of
substrates. NI-l CFC material onto (a) OFHCCu
and (b) TZMMo substrates with CuSil
ABA filler metal
KEYWORDS
mechanical properties, inverse thermal expansion, compliant layers, thin braze

REFERENCES
[1] G. Lovato, G. Chaumat, F. Moret, Proc. HTCMCI, 20-24 Sept. 93,

Bordeaux, pp. 785-792, Woodhead Publishing Limited (1993).
[2] H. Burlet, G. Cailletaud, Proc. ColI. Greco-CNRS "New Advances in
Structural Calculations"; Giens (France), 15-18 mai (1991)
[3] G. Cailletaud, P. Pilvin, Proc. ColI. National de Calcul de Structures,
Giens (France), 11-14 mai 1993, pp.770-787, Vol.2, Hermes, Paris
(1993).
[4] G. Lovato, F. Moret, P. Le Gallo, G. Cailletaud, P. Pilvin, Proc. Euromat
93,8-10 June 1993, Paris, Ed. de Physique (1994)
[5] A. Levy, J. Am. Ceram. Soc., 74 (9), (1991), 2141-47.
RELATIONS BETWEEN FRACTAL MODELS OF SOME
OXIDE SURFACE SHAPES AND THEIR OPTICAL
PROPERTIES
L. CHAGROUNE(*), G. MAURICE(*), A. THOMAS(**)

Ph. PIGEAr(*), B. WEBER(*)
(*) Laboratoire de Science et Genie des Surfaces - Ecole des Mines, Parc de
Saurupt, 54042 Nancy Cedex, France.
E-mail: maurice@mines.u-nancyfr
(**) Laboratoire de Modelisation des Structures Minerales, L.E.M- C.R.P.G-
Ecole de Geologie (C.R. V.M), 54500 Vandreuvre les Nancy, France.
ABSTRACT
By using a scanning electron microscope and an image analyzer, the relief of an oxide
layer surface is analyzed on tungsten samples. The oxide layer is assumed to be a
series offine layers or films. The outer, being non-homogeneous, outlines the rough
oxide surface. The Effective Medium Theory (E.M T.) is used to determine the
dielectric constant of this layer using some geometric approximations. We suggest
improving this analysis by using suitably tested fractal models of the surface oxide
morphology. The problem may be posed as: can the roughness of an oxide surface, be
modeled by afractal and an accurate model related to the optical properties? If so,
what is the law between the fractal dimension and the major optical properties: the
emissivity and the depolarizingfactor g?
RESUME
Le relief de la surface d'echantillons d'oxyde de tungstene est analyse a l'aide d'un

microscope electronique et d'un analyseur d'image. On suppose que Ie depot d'oxyde
est constitue d'une serie de fines couches dont la plus exterieure est non homogene du
fait de la rugosite de la surface. La tMorie des milieux effectifs est utilisee pour
determiner la constante dielectrique de cette couche en utilisant quelques
approximations geometriques. Nous suggerons d'ameliorer cette analyse en utilisant
des modeles fractals de la morphologie de la surface d'oxyde. Le probleme est ainsi
pose: La rugosite d'une surface peut-elle etre modelisee par un modele fractal relie a
ses proprietes optiques? Si oui, queUe est la loi qui relie la dimension jractale aux
plus importantes proprietes optiques: I 'emissivite et Ie Jacteur g de depolarisation?
1 INTRODUCTION
At the present time, the optical properties of rough surfaces are analyzed with the
dispersed medium theory. This theory does not really take into account the specific
random structure of surfaces. The fractal model provides us with a simple and
accurate tool to describe the surface roughness. Since the description relies on very
simple procedures and few parameters, the surface relief becomes easy to relate to the
optical properties.
2 EXPERIMENTAL DEVICE
The oxidation of tungsten ribbons heated by the Joule effect is performed in an

infrared spectrometer[l] under a controlled pressure (10-2 torr of oxygen). The
radiance intensity of the emission from the heated surface for a wave length of A = 2.3
Jlm is registered while the oxidation process is performed at a controlled temperature
Tox (Tox> lOOO K). After the oxidation, the surface sample is scanned in an electron
microscope (Fig. la), then stored and treated by a specific analysis sequence on an
image analyzer (from E.I.A. Soc. with the card GIPS25, a very efficient hardware of
mathematical morphology and an external software [2]). A fractal analysis is then
performed on the vectorized profiles. (Fig. Ib).
b)
Figure 1 : a) Scanning electron microscope view of a tungsten oxide sample section.

b) Seized and treated profile by an image analyzer (the scale is different).
3 OPTICAL MODEL
Obviously, the oxide surface exhibits various degrees of roughness which are assumed
to induce variations in the optical properties.
Fractal Models of Some Oxide Surface shapes and their Optical Properties 365
To model the optical properties of the rough surface, the oxide layer is divided into
two thinner layers A and B (Fig. 2). A is the external layer involving the whole depth
of the roughness, thus considered as an inhomogeneous layer, formed partly of empty
space and partly of solid oxide. B is the inner homogeneous film touching the metal
surface and is assumed to be characterized by the specific optical constant of the oxide
(here W03). Usually the Effective Medium Theory [3] (E.M.T) is used to determine
the dielectric constant of layer A.
The theory requires the determination of the ratio between S 1, the area of the oxide,
and S2, the empty area on the section of the layer A which contains the roughness.
The parameters are the "concentrations":
h 2.5
C.Um ) 2 I::-:----=--:-:::--=-----:-""T"""&"""""""""""""'-s+---,:----::--
. .., .. . . .
. :';.' ; ;: .. . .. ' ~ ~
l5~ ..-
CI tsJ
d c-J
X C.U m )
Figure 2 : A and B oxide layers on the tungsten surface C.
3.1 Computation of an average dielectric constant for the

heterogeneous layer A
The layer B (of thickness hb) is considered to be an homogeneous film, where the
dielectric constant is known. For layer A (of thickness ha), the computation requires
the definition of an optically equivalent medium. Such a one results from the Ql and
A A
Q2 values and from the known dielectric constants 1>1 of the oxide and 1>2 of the
empty medium according to the following expressions [4] :
(1)
(2)
where g is the depolarizing factor expressing the influence of the "virtual particle"
shapes in each set characterized by Ql and Q2 [3} The determination of the factor g is
performed by filling the space either with spheres or with ellipsoids as shown III
Figure 3.
The dielectric constant Eh allows a calculation of complex indic~s of refraction for

the homogeneous layer A' optically equivalent to the heterogeneous layer A. The
emissivity EPS of this homogeneous pile of sheets (A'+B) is determined from the
homogeneous thin films theory [5] .
Most likely the variables Qi and g should be related to fractal parameters

characterizing the surface relief. The main aim of this research is to confirm such an
assumption.
a) r;;v;;:;;~
b)~
Figure 3 : Filling the lower surface outlined by profile (a) with ellipses (b).
4 FRACTAL TOOLS USED
Two fractal concepts are used hereafter. The fractal dimension, and the fractal
interpolation according to one of Bamsley's methods.
4.1 Fractal dimension determination of oxide profiles
A fractal is a mathematical structure suitable for accurately describing some

geometrical structures, especially self-similar (by scale changes) structures. Obviously
the oxide surfaces cannot be modeled by random functions, but by regionalized
functions (in the geostatistical sense), and the observed similarity through a scale
analysis suggests a fractal model, even if it is only accurate over a limited scale range.
The calculation of the fractal dimension is performed by the Richardson-Mandelbrot
[6] method (constant moving step) applied to the stored polygonal outline. The length
of profile is computed for a series of decreasing steps until the resolution of the screen
is attained. If N(11) is the integral number of steps 11 used to cover the profile, the
fractal dimension is given by [7]:
D (/)= lim log (N(1])

f 1J40 Ilog( 1])
(3)
4.2 Fractal interpolation
When the accuracy of the fractal model for the oxide surface morphology is verified
(with reference to a scale range), the problem is then to study the relation between the
fractal dimension and the optical properties. One must then be able to compute
simulations of the surface shape with a varying fractal dimension, in order to improve
the prediction of the optical properties.
Different methods allow such simulations. The one selected here is Barnsley's [8]
method based on the Iterative Function System (I.F.S.), which converge towards a
geometric object called the attractor of the I.F.S. The I.F.S. is a series of affine
transformations on 91 2, thus defined:
G denotes the attractor of the I.F.S :

N
G = UWn(G)
n=!
G is the graph of the continuous function on 91 2 which interpolates the data Yi (or Fj)
collected on a discrete set of points Xi E 91. The real coefficients an, bn, en' fn and dn
satisfy a system of linear equations:
(5)
dn is a free parameter called the vertical scaling factor, related to the fractal
dimension by the following expression:
(6)
Here, it may be considered that dn is constant over all the profile, making the
computation of Df quite simple. Thus, the graph of the attractor G(Df' N, dn) is a
function of three variables, two of them being dependent.
5 RELATION BETWEEN THE FRACTAL DIMENSION USED AS

THE ROUGHNESS FACTOR AND THE OPTICAL EMISSIVITY
In order to determine this relation, under the above experimental conditions, our
possibilities are limited. A data set of emissivity values is computed from an optical
device through a couple of theoretical models involving an oxide layer (A) filled
either by spheres or ellipsoids. Since there is no other suitable way for computing the
emissivity, this is obviously our reference.
Then the problem becomes to fill the inner part of the oxide outline by integration of
the IFS (since pure fractals do not allow integration) and to observe the relation
between the fractal dimension and the parameters currently used in the optical models
such as g (depolarizing factor) or even directly with the emissivity EPS, both in cases
of g constant [9] (sphere filling), or calculated from ellipsoid filling. Fig. 4 shows the
experimental results of EPS values versus fractal dimension computed on five samples
respectively with circular and elliptical planar model.
0,72
t EPS EPS 8lS
TABLE
(nn) (E>cpermertaQ wlh g=1!
Of
with calcl/ae I 0,70 (2)
Sanple 1 3 .637 .636 .638 1.096
0,68
Sample 2 7 .701 .7011 .7019 1.1705 (1 )
Sample 3 29 .705 .6991 .7101 1.2313 0,66
Sample 4 38 .69 .6701 .6992 1.2828 0,64
Sample 5 50 .69 .670 .6994 1.3277
0,62 +----.-.....--r-__--,r--...-1-4
1.0 1,1 1,2 1,3 1,4
Figure 4: Variation of the emissivity EPS with the fractal dimension Dfin two
emissivity models (1) g=1I3 spherical particle model, (2) ellipsoidal particle model.
It can be seen that the filling by ellipsoids induces a more characteristic variation of
EPS with the fractal dimension than the approximation g=1I3 (filling up with spheres).
This result also appears on Figure Sb obtained from a series of simulations of the
profile by fractal interpolation, with increasing dimension Df (Fig. Sa).
EPS
Df = L3067 0.71
Df = 1.3274 :--------(2)
0,69 -------(1)
Df = U328
Df = l.ZStil 0.67
Df = LZ39'
OBi
Df = LZZ13
Df = LZ015 0.1>3 ~-~--~-~--~
Df = 1.1785 m
"!
Df = 1.0"1
Fig. 5 : a) series offractal interpolations of an oxide surface

b) results ofEPS calculation (1) with spherical model, (2) with ellipsoidal model.
6 CONCLUSION
This paper examines the applicability of a fractal model to tungsten oxide surface
relief. Coupled with the Effective Medium Theory, it allows the calculation of some
optical variables, especially the emissivity of rough surfaces.
Of course the accuracy of this method lies in the verification of the basic assumption:
the suitability of the fractal model to characterize the surface complexity over the
scale range of the morphological measurements.
KEYWORDS
fractal, emissivity, optical properties.
REFERENCES
[1] P. Pigeat, N. Pacia, B. Weber, Applied Surface Science 27 ( 1986) 214.

[2] A. Thomas, P. Therme, Logiciels C.R.V.M, Nancy ( 1988).
[3] L. Landau, E. Lifshitz, Electrodynamique des milieux continus, Mir ed.

Moscou ( 1969 ).
[4] D.A.G. Brugmann, Ann Phy Leipzig 24 ( 1935) 636.
[5] O.S. Heavens, Optical properties of thin solid films, Butterworths, London
(1955).
[6] B.B. Mandelbrot, Les fractals, Flammarion, Paris, reedition, (1989).
[7] J.F.Gouyet, Physique et structures fractales, Paris, (1992).
[8] M.F. Barnsley, Fractals everywhere, Academic Press, (1988).
[9] G. Maurice, A. Thomas, P. Pigeat, L. Chagroune, B. Weber, Fractals,.2, N°6,
( 1994 )183.
TEMPERATURE DISTRIBUTIONS IN ADIABATIC
SHEAR BANDS IN STEEL
Vincent PINA and Philippe HERVE
Laboratoire d'Energetique et d'Economie d'Energie - Universite de Paris X 1 Chemin

Desvallieres - 92410 Ville D'Avray, France
ABSTRACT
Adiabatic shear bands appear on materials subjected to high strain rates. Up to now
heat-exchange mechanisms have not been very well known. In order to determine the
temperature distribution and the phase-change within the shear band we have
developed a method of optical pyrometry using two wavelengths. Torsion tests have
been carried out, and a temperature of 750°C has been measured within the shear
band.
RESUME
Des bandes de cisaillement adiabatiques apparaissent sur des materiaux soumis a des
grandes vitesses de deformations. Jusqu 'a ce jour les mecanismes d'echange de chaleur
ne sont pas bien connus. Dans Ie but de determiner la distribution des temperatures et Ie
changement de phase dans les bandes de cisaillement nous avons elabore une methode
en pyrometrie optique adeux longueurs d'onde. Des tests de torsion ont he effectues et
une temperature de 750°C a he mesuree dans la bande de cisaillement.
1 INTRODUCTION
Adiabatic shearing is a strain mechanism which most often appears at large strain
rates and generally leads to rupture of the material. The first adiabatic shearing
phenomena were observed at the beginning of the century, but it was not until 1944
that they could be interpreted by Zener and Hollomon [1]. Since then, several analyzes
of the phenomenon have been offered and new directions of research, both theoretical
and experimental, are being developed, aimed at various industrial applications, such
as high-speed machining, problems involved in the impact of a projectile on a target,
steel-sheet tightening in a rolling-mill.
The study offered here essentially deals with the problems involved in dynamic
shocks. Its purpose is first to determine, by means of optical pyrometric methods, the
temperature distribution induced by the appearance of a shear band and then, to locate
a possible change of phase within the band during the shock. The originality of our
research is to offer two simultaneous measures at two different wavelengths, in order
first to obtain the temperature distribution, and second, to determine the nature of the
phase change.
2 PRESENTATION OF AN ADIABATIC SHEARING
In dynamic processes, the shear bands are the result of an intense plastic strain. When
the latter takes place within a material, a large part of the work is converted into heat,
about 90% of it according to Taylor and Quinney[2]; thermal softening results from
the local rise in temperature. If the strain ratio is high, the temperature may rise in
considerable proportion over a small area, which then induces a drop in the strain rate
and, consequently, the appearance of a local shearing band, called an adiabatic shear
band. The term adiabatic is not used in its thermodynamic sense. It has been
introduced only because a small quantity of heat generated by the strain process is
considered to be transmitted to the surrounding environment during the strain.
Adiabatic shear bands within a steel are characterized by an easily noticeable thin
white strip (see Fig. I), whose composition is not very well known so far. It should
result from a strain within the material which has not yet been identified.
Figure 1: An adiabatic shear band in steel 35 NeD 16 [5] - width 20 !lm

Temperature Distributions in Adiabatic Shear Bands in Steel 373
3 METHOD OF MEASUREMENT
The extreme thinness of the band (0.1 to 100 fim width [3]) as well as its very short
time of occurrence « 200 fiS) are the main difficulties involved in the study of
adiabatic shear bands. That is why we have chosen an optical pyrometry method.
Surface temperature measurement techniques by detecting the emitted radiation offer

lots of advantages, compared to classical sensors:
- they can be put to use from a distance, thus without any interaction with the medium
- the response time is very short « 1fis)
- the spatial resolution can be very good since it is determined by the optical device
used and is only limited by diffraction.
However, the main disadvantage of optical temperature measurement techniques

comes from the fact that the temperature and emissivity are directly related, hence the
difficulty in interpreting the signal given by the detector. Therefore we are going to
use a measurement technique with two distinct and largely spaced wavelengths in
order to disconnect temperature- and emissivity-related problems. The measurement at
a very short wavelength (0.9 fim) is not very sensitive to emissivity variations, and
gives us the real surface temperature. Conversely, a measurement in the far infrared
range (4.8 fim) is sensitive to emissivity radiations, and allows us to identify the phase
change [4]. Actually, a phase change within a given material appears as a sharp
variation in the curve of emissivity versus temperature. The basic experimental set up
is presented in Fig. 2. Its purpose is to enable us to carry out, with a single aiming of
the pyrometer, measurements at two given wavelengths, simultaneously, on a metallic
sample submitted to a large mechanical strain.
CCD camera
O.86/-lm
Sample
Lens
32 InSb detectors
4.8/-lm
Figure 2: Basic experimental set up

4 EXPERIMENTAL PROCEDURES
4.1 Mechanical devices
4.1.1 Dynamic torsion system
The operating principle of dynamic torsion bars is relatively simple (see Fig. 3). A test
tube (16 mm diameter - 40 mm long) is positioned between two 3 m long bars. the
incident bar being blocked by the brake, the part of the bar between the brake and the
motor is then elastically pre-stressed in rotation. The sudden release of the brake
induces the propagation of a torsion wave along the incident bar. When it reaches the
sample, a fraction of the wave is transmitted to the bar after shearing the test-tube.
Sample Engine
~--~, ~~e--/_/--~
Figure 3: Dynamic torsion bars of the Hopkinson type
4.1.2 Stamping system
A stamping device is more convenient to use than a torsion system, and stamping test-
tubes are far easier to make than torsion ones. The operating principle of the system is
simple (see Fig. 4); the sample is locked between the jaws of the stamping vice and
stamp-sheared. The stamp is accelerated by means of a projectile subjected only to
gravity forces. The set-up using a free-falling projectile allows us to study adiabatic
shearing at low speeds. For higher speeds, the same set-up can be used and an
increase of projectile speed is obtained by means of compressed air.
[},~~"
t
Figure 4: Stamping system

Temperature Distributions in Adiabatic Shear Bands in Steel 375
4.2 Detection device
The measuring apparatus is made of two separate optical benches. The temperature
measurement is carried out by means of an IP800T Philips camera with a low light
level capacity within the 0.4-1 flm spectral range. The emissivity measurement is
carried out by a Cincinnati bar composed of 32 independent InSb detectors cooled by
liquid nitrogen. The spectral range of such detectors is I-S.S flm with a peak at 4.8
flm. The response time for these two types of detectors is lower than 1 microsecond.
The data acquisition is done through a transitory multichannel Nicolet MultiPro type
analyzer. The calibration is carried out on a black body.
5 EXPERIMENTAL RESULTS
The purpose of the first tests was to validate the chosen materials. Thus we tested
them separately. The tests over the InSb detector bar were carried out during dynamic
torsion tests. The bar used for these experimental procedures had 16 detectors (size:
2S0 flm x 2S0 flm). With these detectors we were able to measure (after calibrating
the system) a temperature value of 7S0°C within the shear band. Fig. S shows the
signals recorded by two detectors of the series. However this temperature value
remains approximate because this system of measurement did not allow for a
distinction between temperature and emissivity. Moreover, the large size of the sensor
elements compared to the band width leads us to think that the temperature thus
measured is not that of the band only, because the sighting area also takes the un-
stressed part of the test-tube into account. However, from the value obtained, we are
induced to assume that the temperature within the shear band is greater than 700°C,
since the strained zone is not heated up by this local straining phenomenon. Moreover,
the ultra-fast CCD camera has been tested on a black body and enabled us to measure
its temperature in I flS for temperatures over SOO°C. The equivalent wavelength was
0.86 flm . We have thus been able to verify that its detectability threshold is smaller
than the minimum temperature obtained within an adiabatic shear band.
750 °C ..
o 0.4 0.8 1.2 1.6 2.0

Time (ms)
Figure 5: -Temperature measurement in dynamic torsion test (steel3S NCD 16)

6 CONCLUSION
The results obtained during our tests are satisfactory and encourage us to use smaller
sized detectors in order to better locate the shear band. That is why we are going to
use a 32 sensor bar-detector (size: 43 Jlm x 43 Jlm).
Furthermore, in order to make our two wavelength pyrometric method operational, we

are developing a computer program which is to analyze the signal obtained with our
ultra-fast intensified CCD camera.
ACKNOWLEDGMENTS
I wish to thank B. Deltort of D.G.A., Arcueil, because the results presented in this
paper were obtained with him in the course of the research.
KEYWORDS
adiabatic shear bands, temperature, fast pyrometry, phase change
REFERENCES
[1] c. Zener, lH. Hollomon, Transactions ofthe ASM, 32, (1944),111-120

[2] G.!. Taylor, H. Quinney, Proc. Royal Soc. (London), A143, (1934), 307- 326
[3] M.A. Meyers, G.L. Wittman, Metallurgical Transactions, 21A, (1990), 3153-3164
[4] P. Herve, P. Tobaly, J.M. Lirhmann, J.P. Petitet, UTC 11, 13 mai 1992, 23 e Joumee
de Calorimetrie et d'Analyse Thermique. Caracterisation de la temperature et des
changements d'etat par voie optique, (1992).
[5] B. Deltort, These: Etude experimentale et numerique du cisaillement adiabatique
dans un acier martensitique, Ecole des Mines de Paris, (1993)
SUBJECT INDEX
A
adiabatic shear bands 371
agility 183
AI 251
Al 151
alkali metals 71
alkylpyridinium 313
anisotropic criterion 343
autocorrelation method 85
B
binary metal oxides 327
biosensor 293
C
calorimetry 115
Car-Parrinello 129
cationic surfactant 143
CBLM 39
ceramic matrix composite 189,243
cermets 263
chemical sensor 293
chromium oxides 321
cluster variation method 39
CMCs 243
coarsening 343
coating 161
complex formation 143
compliant layers 355
computer software 79
conductivity 143
Coniglio-Rauzy 21
378 Subject Index
cooling process 161

CPA-GPM 39
critical evaluation 95
crystalline precipitates 321
D
damage 189
damage creep 243
damage mechanics 225
database 33,349
defect interactions 327
deformation 189
density 53
density functional theory 129
design process 189
design tools 225
divided materials 135
DSC 143
dynamic modulus 335
E
emissivity 363
energy 109
enthalpy 115
enthalpy of vaporization 21
environmentally conscious manufacturing 183
equation of state 1,21,33
estimation 71
experimental measurements 11
expert thermodynamic 109
F
fast pyrometry 371
finite Element 343
fitting equation 95
fluid propagation 53
formation enthalpy 71
fractal 363
G
gasFET 293
global competition 183
Subject Index 379
grain morphology 321
H
halogen 71
heat capacity 1,53, 71
high pressure 53
high speed steels (HSS) 255
high temperature 53
homogeneous precipitation 283
I
inorganic compounds 79
internal variable creep model 243
inverse gas chromatography 135
inverse thermal expansion 355
ion selective electrodes 293
ISE devices 305
ISFET 293
K
Kawasaki dynamics 343
killed steels 151
knowledge model 109
L
laminated composite 225
light alloys 169
liquid phase sintering 263
LMTO 39
London and Lewis forces 135
M
macrocyclization 313
macrolactamization 313
MAM 85
manufacture 189
mass transfer 115
material design 251
material selection 251
mechanical modeling 233
mechanical properties 355
380 Subject Index
methanol 11
micro-composite model 243
microemulsion 313
microstructure 161
mixtures 33
molar volume 53
molecular theory 335
Monte Carlo simulations 327,343
multicomponent silicates 283
multicomponent titanium oxide 289
multiple emulsions 115
multiple equilibrium 151
N
n-alkanes 21
NASICON 305
nickel-base superalloys 343
non-equilibrium 1
nonpolar gas 1
nonstoichiometry 327
0
co-amino acids 313
optical properties 363
optimized selection 189
organic compounds 85
p
particles 161
particulate composite 233
percolation 233
phase change 371
phase diagram 255,263
phase stability 263
phenol 143
plasma spray 161
plasticity 335
polar gas 1
polymers 335
powder metallurgy processing 255
powder porosity 321
process 109
PVTdata 11
Subject Index 381
Q
quantum dynamics 129
R
rafting 343
refractory coatings 169
reservoir oil 53
rupture mechanics 225
S
salt-systems 95
semi-killed steels 151
SGTE 33, 169
simulation 189
site acidity 129
slag model 151
soft chemistry 289
software calculation 169
sol-gel process 273,283
sol-gel 321
solidification-melting 115
solubility 95
spray drying 283
spraying 161
standard entropy 71
statistical thermodynamics 327
structural parameters 129
substances 33
substituted offretite 129
super-solidus liquid phase sintering (SLPS) 255
surface properties 135
surfactant 313
T
temperature 371
theoretical calculation 1
thermochemical mimicry 71
thermodynamic 33
thermodynamic data 169
thermodynamic properties 79
thermophysical properties 349
THERSYST 349
thin braze 355
382 Subject Index
thin films 273

3d framework conductors 305
tomography 225
topological method 85
toxic emission 169
U
UNIF AC group contribution method 85
V
vapor pressure 85
virtual organization 183
viscoelastic behavior 233
W
waveguide Raman spectroscopy (WRS) 273
AUTHORS
A
Aboujalil A. 289
Afeefy H. 71
Alberola N. 233
Alemasov V. E. 109
Allibert C.H. 263
Ansara I. 33,255
Arrell D. J. 343
B
Barbotix P. 321
Barreau A. 53
Batthias C. 225
Behar E. 53
Berro Ch. 11
Bienvenu Y. 255
Bleuzen A. 321
Boureau G. 327
Bovier C. 273
Busserolles K. 143
C
Cailletaud G. 355
Campana L. 129
384 Authors
Caparros A. 313
Chagroune L. 363
Chassagneux F. 289
Chastrette M. 85
ChavretM. 21
Chaumat G. 355
Chehimi D. 95
Chehimi M. M. 135
Clausse D. 115
Cohen-Adad M.-Th. 95
Cohen-Adad R. 95
Colinet C. 39
Cretin D. 85
Cretin M. 305
D
Deloume J.P. 289
Douy A. 283
Dregalyn A. F. 109
Dumas J. 273
Durand B. 289
Durand-Charre M. 255
E
Eriksson G .. 169
F
Fabry P. 305
FauchaisP. 161
G
Garcia F. 321
Gatellier C. 151
Gaye H. 151
Goursot. A. 129
Authors 385
H
HarleV. 289
Hayhurst D.R. 189
Hemptinne J.-C. de 53
Herve P. 371
HocqH. 11
HuangG. -So 79
J
Jaffrezic-Renault N. 293
Jaroma-Weiland G. 349
Jaymes I. 283
Jose J. 21
K
Khireddine H. 305
L
Ladouce L. 325
LamourouxF. 243
Lattes A. 313
Lehmann J. 151
Lemoisson E. 255
Liebman J. F. 71
Livage J. 321
Lovato G. 355
Loughlin S.P. 251
M
Marrouche A. 95
Mascarenhas J. 255
MauriceG. 363
MeleP. 233
MoretF. 355
MugnierJ. 273
N
Nazyrova R. R. 109
NeuerG. 349
0
OliveiraM. 255
p
Paille F. 273
386 Authors
PapaiI. 129
Pasquarello A. 129
Pastor H. 263
Pasture1 A. 39
Perez E. 313
Perez 1. 335
Pezron I. 115
Pigeat Ph. 363
PilvinP. 355
PinaV. 371
PlenetJ.C. 273
Potier L. 115
PotterE 225
Preiss K. 183
Q
Quinson R. 335
R
Rauzy E. 11
Raynal S. 115
Rebufa C. 11
Richthofen A. von 169
Rico-Lattes I. 313
RouxA. H. 143
Roux-Desgranges G. 143
S
Selloni A. 129
Serughetti 1. 273
Shen J.-Y. 79
SmithEJ. 251
Spencer P.J. 169
Steen M. 243
T
Tetot R. 327
Thomas A. 363
U
Ungerer P. 53
Urlacher C. 273
Authors 387
V
Valles J. L. 243,343
Vardelle A. 161
Vardelle M. 161
Viton C. 21
W
WeberB. 363
WeberJ. 129
WenH. 79
Winstanley A.C. 251
WrightC.S. 255
Wronski A. S. 255
WuD. 225
X
XuZ. 79
Z
Zhang K.-W. (Ke-Wu Chang) 1
Colour Plates
PENG·ROBINSON CHAIN·OF·ROTATORS g
C-
~
"tl
III
"i:" Cp"'(EOS) • Cp'''(E.Y) x 100
III ~
Cp""(E-Y)
--e'" e
1000 1:1
.~.
III
...0
III
fi fi
0.
Above 50.0
'" 0.
'" 20.0 - 50.0
10.0 - 20.0
5.0 - 10.0
2.0 - 5.0
0.0 - 2.0
Temperature (K) -2.0 - 0.0
-5.0 - -2.0
SBRJ LEE·KESLER -10.0 - -5.0
-20.0 - -10.0
-50.0 - -20.0
Below -50.0
:I'
.j
.1
j f
i
'(
.,l'
200 SOD '00 GOO 800

Temperature (K) Temperature (K)
Residual isobaric heat capacity. Comparison error maps for methane (high pressure). ~
PENG·ROBINSON CHAIN·OF.ROTATORS ~
,..... Cv "'(EOS ) . Cv "'CE-Y) x 100

...«I Cvr"(E.Y)
.e
...@
fIPI
fIPI
tI Abov~ 50.0
... 20.0 - 50.0
"-
10.0 - 20.0
5 .0 - 10.0
2.0 - 5.0
eoo 250 SOO ,GO 400 450 0.0 - 2.0
Temperature (K) -2.0 - 0.0
-5.0 - -2.0
SBRJ LEE·KESLER -10.0 - -5.0
-20.0 - -10.0
-50.0 - -20.0
B~lo... -50.0
I:'
«I
.e
-=
.;;o
tl
ct
g
C'
200 250 SOD ,GO ,0C) 450
200 no soo 9GO 400 450 ~
Temperature (K) Temperature (K)
Residual isochoric heat capacity. Comparison error maps for ethane. I

g
0-
~
Creep Rupture in a butt welded O.5Cr O.5Mo 0.25V Ferritic steel pipe with a 2 2
. 5Cr 1Mo: O.5Cr. 5Mo 0.25V mUlti-pass weld subjected to a constant
internal pressure of 45.5 Mpa at 565°C, the heat affected zone (HAZ) is denoted by AB: (a) micrograph of diametral section of weld, the base-
line of the figure coincides with weld center-line, and the left hand and right hand edges of the figure denote the inner and outer walls
of the pipe respectively, (b) computed damage field superimposed on Finite Element mesh at a life fraction of t/tf=l, failed regions have
damage 0»0.8 as defined in legend, and (c) micrograph of diametral section of weld showing damage at failure.
w
::B
w
~~ ~ 3.18xlO-s • 4.09xlO- 2 'i
2.91xlO-3 • 3.85xlO- 2
2.65xlO-s • 3.41xlO-2
• 2.38xlO-s • 3.07xlO-2
• 2.12xlO-s .J 2.73xlO-2
1.85xlO-s 2.39xlO- 2
1.59xlO-s .2.04x10-2
• 1.32xlO-s • 1.70xlO-2
• l.06xlO-s . 1.36xlO-Z
• 7.94xlO- 4 • l.02xlO-2
5.29xlO-· 6.82x10-s
• 2.65xlO-· • 3.41xlO-a
• 4.42xlO- 1 • 9.23xlO-1
• 4.05xlO- 1 • 8.46x10- 1
• 3.68xlO-1 • 7.69xlO-J
3.31xlO- 1 6.92xlO- 1
2.94x10- 1 6.15xlO-j
2.58xlO- 1 5.38xlO- 1
2.21x10- 1 4.62xlO-)
• 1.84xlO-1 • 3. 85 l.c:lO- 1
• 1.47x10- 1 • 3.08xlO- 1
• l.lOxlO- 1 • 2.31xlO-1
. 7.36xlO-2 • 1.54x10-) g
· 5.80xlO-3 • 7.69xlO- 2 C'
~
Field distributions of the damage variable w over a diametral section of the weldment determined using the optimized i
materials data sets for the weld and HAZ materials: (a) tltf=O.OOOS, (b) t/tf=0.109, (c) tltf=0.863 and (d) t/tf=1 .0.
Colour Plates 395
Theoretical predictions of the shear damage parameter ~SDP field in a region close to the
edge of the hole (bottom left hand corner of figure). The base line of the figure coincides with
the horizontal axis of symmetry of the plate. The yellow region denotes shear damage failure
~SDP=l, the dark blue region denotes virgin material and intermediate colors denote linearly
interpolated values.
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Thermodynamic Modeling and Materials Data Engineering: P. Caliste A. Truyol H. Westbrook

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J.- P. Caliste · A.

With 150 Figures and 48 Tables

Scientific Editorial Board

M. Antoninetti (Italy) P. Masclet (France)

J.-P. CALISTE, A. TRUYOL AND J. WESTBROOK

The Series, "Data and Knowledge in a Changing World", exemplifies CODATA's

The present book "Thermodynamic Modeling and Materials Data Engineering"

Articles were selected for their pertinence in three areas.

Complex data leading to interesting developments and tools such as:

2 Complex system dynamics and recent progress in:

• materials surfaces and interfaces,

The importance of design strategies that integrate various types of information, in

Highlighted results are:

CHAPTER 1: NEW DEVELOPMENTS IN STATE

PVT MEASUREMENTS OF METHANOL AND ITS SPECIFIC EQUATION OF 11

ENTHALPY OF VAPORIZATION OF N-ALKANES (FROM NONANE TO 21

AIMS AND ACHIEVEMENTS OF THE SCIENTIFIC GROUP THERMODATA 33

FIRST PRINCIPLES CALCULATIONS OF BINARY ALLOY PHASE DIAGRAMS 39

EVALUATION OF EQUATIONS OF STATE AT HIGH PRESSURE FOR liGHT 53

CHAPTER 2: PREDICTIONS AND VALIDATION OF

COMPUTER-AIDED INORGANIC PROPERTIES ESTIMATION SYSTEM 79

ESTIMATION OF PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS. 85

MODEL FOR THE CRITICAL EVALUATION OF SOLUBILITY DATA IN SALT 95

ON THE EXPERT THERMODYNAMIC ANALYSIS OF POWER ENGINEERING 109

LIQUID-SOLID TRANSITIONS WITHIN MULTIPLE EMULSIONS. ENTHALPY AND 115

CHAPTER 3: UNDERSTANDING COMPLEX SYSTEMS

INVESTIGATION OF THE STRUCTURAL AND ACIDIC PROPERTIES OF BULK 129

SURFACE THERMODYNAMICS OF SOLID MATERIALS BY INVERSE GAS 135

DIFFERENTIAL SCANNING CALORIMETRY (DSC) AND TEMPERATURE 143

THERMODYNAMIC MODELS FOR MONITORING DEOXIDATION TREATMENTS 151

A TECHNIQUE FOR STUDYING THE PARTICLE IMPACT PHENOMENA IN 161

THE ApPLICATION OF THERMODYNAMICS TO THE DEVELOPMENT OF 169

CHAPTER 4: COMPUTER-AIDED-DESIGN AND NEW

MATERIALS DATA REQUIREMENTS FOR COMPUTER SIMULATION IN DESIGN 189

MICROCOMPUTER - AIDED - TOMOGRAPHY OF COMPOSITE MATERIALS 225

MODELING OF THE VISCOELASTIC BEHAVIOR OF NON-HOMOGENEOUS MATERIALS 233

MODELING STUDIES OF THE UNIAXIAL CREEP OF A BRITTLE MATRIX COMPOSITE 243

THE INTELLIGENT SELECTION OF MATERIALS FROM A DESIGN SPECIFICATION 251

THERMODYNAMIC ApPROACH TO THE DESIGN OF NEW CERMETS PROCESSED 263

CHAPTER 5 : SYNTHESIS AND ApPLICATION OF NEW

AQUEOUS PREPARATION OF CHEMICALLY HOMOGENEOUS MUL TICOMPONENT 283

SYNTHESIS OF BARIUM TITANATE BY REACTION OF TITANIUM SALTS IN 289

NEW MATERIALS FOR (BIO)CHEMICAL RECOGNITION 293

IONIC RECOGNITON USING CONDUCTING CERAMICS 305

SYNTHESIS OF MACROCYCLIC LACTAMS IN ORGANIZED MEDIA 313

SYNTHESIS OF CHROMIUM OXIDES FROM AQUEOUS SOLUTIONS 321

CHAPTER 6 : MATERIALS STRUCTURES AND BEHAVIOR

MECHANICAL RESPONSE OF AMORPHOUS POLYMERS: a+~ MECHANICAL 335

MODELING OF ANISOTROPIC COALESCENCE OF y' IN SUPERALLOYS 343

DATABASE-RELATED STANDARDIZATION TO DESCRIBE EXPERIMENTAL 349

MATERIAL DATA OF THIN INTERLAYERS BY AN INVERSE METHOD: THE CASE 355

RELATIONS BETWEEN FRACTAL MODELS OF SOME OXIDE SURFACE SHAPES 363

TEMPERATURE DISTRIBUTIONS IN ADIABATIC SHEAR BANDS IN STEEL 371

SUBJECT INDEX 377

AUTHORS INDEX 383

NEW DEVELOPMENTS IN STATE

THE EXTENDED ApPLICATION OF A TENSG, VI.

Ke-Wu ZHANG (Ke-Wu CHANG)

Department o/Chemistry, Northeast Normal Universty, Changchun 130024,

2 BASIS OF THE PRESENT EQUATION

In essence, it is a problem of the rate of /-Li with T.

An important assumption in this development is that we introduce two parameters ko

This method is evidently different in principle from empiric regression, because we