Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74

www.elsevier.com/locate/calphad

Applications of computational thermodynamics — the extension from phase

equilibrium to phase transformations and other properties
André Costa e Silva a,∗ , John Ågren b , Maria Teresa Clavaguera-Mora c , D. Djurovic d , Tomas
Gomez-Acebo e , Byeong-Joo Lee f , Zi-Kui Liu g , Peter Miodownik h , Hans Juergen Seifert i
a EEIMVR-UFF, Volta Redonda and IBQN, Rio de Janeiro, Brazil
b Department of Materials Science and Engineering, KTH, Stockholm, Sweden
c Departament de Fı́sica, Universitat Autònoma de Barcelona, 08193-Bellaterra, Spain
d Max-Planck-Institut für Metallforschung, Stuttgart, Germany
e CEIT and TECNUN, University of Navarra, Spain
f Department of Materials Science and Engineering, Pohang University of Science and Technology, Pohang 790-784, Republic of Korea
g Department of Materials Science and Engineering, The Pennsylvania State University, 209 Steidle Building, University Park, PA 16803, USA
h ThermoTech and Sente Ltd, Surrey Technology Centre, 40 Occam Road, Guildford, GU2 7YG, UK
i University of Florida, Department of Materials Science and Engineering, PO Box 116400, Gainesville, FL 32611-6400, USA

Received 14 February 2006; accepted 17 February 2006

Available online 23 March 2006

Abstract

Complex equilibria and phase transformations involving diffusion can now be calculated quickly and efficiently. Detailed examples are
given for cases which involve varying degrees of non-equilibrium and therefore time-dependence. Despite very good agreement between such
calculations and experimental results, many potential end-users are still not convinced that such techniques could be usefully applied to their own
specific problems. Friendly graphic interface versions of calculating software are now generally available, so the authors conclude that the most
likely source of the reluctance to use such tools lies in the formulation of relevant questions and the interpretation of the results. Although the
potential impact of such tools was foreseen many years ago [M. Hillert, Calculation of phase equilibria, in: Conference on Phase Transformations,
1968], few changes in the relevant teaching curricula have taken into account the availability and power of such techniques.
This paper has therefore been designed not only as a collection of interesting problems, but also highlights the critical steps needed to
achieve a solution. Each example includes a presentation of the “real” problem, any simplifications that are needed for its solution, the adopted
thermodynamic formulation, and a critical evaluation of the results. The availability of such examples should facilitate changes in subject matter
that will both make it easier for the next generation of students to use these tools, and at the same time reduce the time and effort currently needed
to solve such problems by less efficient methods.
The first set of detailed examples includes the deoxidation of steel by aluminum; heat balance calculations associated with ladle additions to
steel; the determination of conditions that avoid undesirable inclusions; the role of methane in sintering atmospheres; interface control during the
physical vapour deposition of cemented carbide; oxidation of γ -TiAl materials; and simulation of the thermolysis of metallorganic precursors for
Si–C–N ceramics and interface reaction of yttrium silicates with SiC-coated C/C–SiC composites for heat shield applications.
A second set of examples, more dependent on competitive nucleation and growth, includes segregation and carburization in multicomponent
steels and features a series of sophisticated simulatons using DICTRA software.
Interfacial and strain energies become increasingly important in defining phase nucleation and morphology in such problems, but relatively
little information is available compared to free energy and diffusion databases. The final section therefore demonstrates how computational
thermodynamics, semi-empirical atomistic approaches and first-principles calculations are being used to aid filling this gap in our knowledge.
c 2006 Elsevier Ltd. All rights reserved.

∗ Corresponding author.
E-mail addresses: andre@metal.eeimvr.uff.br (A. Costa e Silva), john@mse.kth.se (J. Ågren), mtmora@vega.uab.es (M.T. Clavaguera-Mora),
djurovic@mf.mpg.de (D. Djurovic), tgacebo@ceit.es (T. Gomez-Acebo), calphad@postech.ac.kr (B.-J. Lee), zikui@psu.edu (Z.-K. Liu),
p.miodownik@btinternet.com (P. Miodownik), hseif@mse.ufl.edu (H.J. Seifert).

0364-5916/$ - see front matter 

c 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.calphad.2006.02.006
54 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
1. Introduction
The last few years have seen a dramatic advance in
computer technology, yielding a tremendous increase in
the calculation power available to the PC user. Over the
same period, CALPHAD (Computer Calculation of Phase
Diagrams) techniques have evolved from just performing
complex equilibrium calculations relevant to materials science
to simulating phase transformations involving diffusion. Both
tasks can now be performed quickly and efficiently and produce
very good results. This has a large effect on the ability to solve
complex problems in several key areas: materials processing,
the prediction of material behavior under industrial conditions,
and supporting the design of new materials.
Since 1997, the series of Ringberg Workshops on
Computational Thermodynamics have produced two reports
on the status and evolution of “Applications of Computational
Thermodynamics” [2,3]. The first report focused on reviewing
applications and highlighting the development needs in each
area of application, whereas the second report, while also
reviewing applications, attempted to formulate the review in
the form of questions and answers in an attempt to improve
the interface between the final user and the providers of
thermodynamic and allied property information.
This reflects the observation that properly translating the
conditions of a “practical” problem into a well-formulated
thermodynamic or diffusion problem (within the limitations of
the CALPHAD technique) is not a trivial question. One source
of difficulties in communication between users and providers
has traditionally been ascribed to the user–software interface,
but it is the opinion of the authors that more fundamental
questions are probably just as relevant as, or more important
than, problems related to the user–software interface. This
has been confirmed in recent years, as much more user-
friendly graphic interface versions of calculating software has
become available. This has made it more evident that the real
difficulties experienced by end-users lie in formulating the
correct questions, as well as interpreting the results of the
calculations.
It is apparent that part of the problem is related to difficulties
in understanding the thermodynamic concepts involved in the
problems of interest. If that is true, the best route to achieving
more efficient utilization of the current generation of novel
techniques lies in paying more attention to the education and
training of the potential users in the relevant areas.
Computational thermodynamics has already been success-
fully introduced as an educational tool in several programs and
schools [4,5]. In addition, user courses are offered by virtu-
ally all the commercial software suppliers. However the avail-
ability of these advanced software tools has not yet produced
much change in the way the thermodynamics, physical chem-
istry and diffusion courses are taught. Although the impact of
such tools on the relevant curricula was foreseen many years
ago [1], change in these curricula has been extremely slow.
The present account is aimed at providing examples from
the background experience of the participants of this group that
may help to rectify this situation. The critical steps in solving
each problem are highlighted: (a) the definition of the “real”
problem; (b) when simplifications are needed, and the rationale
behind the selection of the relevant part of the problem; and (c)
the thermodynamic formulation of the problem. The results are
then presented and critically evaluated.
It is hoped that this form of presenting problems may help
in several different aspects; firstly, to help identify the basic
knowledge necessary for the efficient use of these techniques;
secondly, to accelerate changes in curricula that will make it
easier for the next generation of students to use these tools;
and thirdly to appreciably reduce the time and effort presently
used on teaching how such problems are solved by less efficient
methods.
2. Selected application examples
One of the important aspects when applying computational
thermodynamics to the solution of a real problem concerns
the effect of time. As thermodynamics is concerned with
equilibrium, one must decide how the information on
equilibrium will be used. If one expects the system to come
sufficiently close to equilibrium in the time-frame relevant
to the problem, or if the interest is in evaluating what can
happen in a given system, then time-independent calculations
are sufficient. If, however, the time available for the processes
to occur is not long enough for equilibrium to prevail, either a
time-dependent solution is used or the equilibrium information
has to be considered with additional care. For this reason, the
examples are grouped, taking into consideration the effect of
time on their solution.
2.1. Time-independent problems
2.1.1. Aluminum deoxidation of steel [6]
Practical and experimental results indicate that the
deoxidation of liquid steel using aluminum is a fast process,
where equilibrium is reached in a very short time. Thus,
time-independent equilibrium calculations are sufficient in this
case. Without taking into consideration aluminum losses, the
amount of aluminum required for steel deoxidation is defined
by the initial oxygen content of the steel to be deoxidized and
the acceptable oxygen content at the end of the deoxidation
process. The classical solution to this problem is a two-
step calculation: first, the aluminum dissolved in the steel
at the end of the deoxidation process is calculated, using
the oxide solubility product at the deoxidation temperature
(here, knowledge of the oxide to be formed is necessary);
then the aluminum consumed in forming oxide is calculated
based on the oxide stoichiometry, as indicated in Fig. 1. The
strategy of breaking down the aluminum addition into two
parts is only necessary because of the information used for the
calculation.
Unfortunately, this strategy does not help the understanding
of the equilibrium issue. This is a consequence of the classical
approach to the problem. A different approach can be proposed
if a tool that calculates equilibrium is available. In this case,
the main concepts involved are: (a) the system composed of the
 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
Table 1
Calculation procedure to define the aluminum addition required for steel deoxidation [6]
Conditions to calculate equilibrium
Constituents of the system Fe–Al–O, C = 3
Conditions to be fixed (F = 5 = C + 2): Total size of the system = 106 g (1 ton of steel)
%O total = 600 ppm
%O in solution in steel = 6 ppm
T = 1873 K (1600 ◦ C)
P = 105 Pa (1 atm)
Fig. 1. Schematic presentation of the deoxidation process on the iron-rich
corner of the 1873 K isotherm of the Fe–O–Al system.
steel in the ladle plus the aluminum to be added is assumed to
be a closed system, (b) equilibrium will be reached, (c) the total
oxygen content of the system is given by the oxygen content
in the steel before deoxidation, and (d) the equilibrium amount
of oxygen in the liquid-steel phase should be the acceptable
oxygen content at the end of the deoxidation process.
Furthermore, one must consider that the system of equations
that must be solved to calculate any equilibrium is only
mathematically determined when the number of equations is
equal to the number of variables [7]. Thermodynamically, this
is expressed in the form of the familiar Gibbs Phase Rule:
P + F =C +2 F =C − P +2
where F is the number of degrees of freedom, C is the number
of system components, and P is the maximum number of stable
phases. If no stable phase is prescribed in a calculation, one
has to fix C + 2 conditions to be able to solve the equilibrium
problem [8].
This is sufficient to calculate the total amount of aluminum
in the system, as well as the aluminum in solution in the steel
and the oxide formed and its quantity, as presented in Table 1.
Except for eventual losses associated with the process
of adding the aluminum and reoxidation from the slag, the
calculated values are in accordance with the results found in
industry [9].
55
Calculation result
(a) Phases present: 998.7 kg of liquid steel containing O = 6 ppm
%Al = 0.02% 1.3 kg of alumina (Al2 O3 )
(b) Total amount of aluminum in the system: 875 g
2.1.2. Heat balance — the effect of additions to the steel
ladle [6]
When alloying additions are made to liquid steel in the
ladle, not only composition changes occur, but there is also
an important thermal effect. These changes are due not only
to “sensible heat” needed to bring the alloy to the steel
temperature but also to enthalpy variation associated with the
dissolution of the alloying elements in steel. The traditional
solution requires the knowledge or estimation of the heat
capacities of the alloy to be added and of the liquid steel, as
well as information on the enthalpies of mixing. Furthermore,
if the elements present in the alloy form compounds (as in
the case of Fe–Si, for instance), the enthalpy change related
to the dissociation of the compounds must be considered. To
simplify the calculations, a dilute solution is assumed and a
thermal effect (in ◦ C/kg/t) is derived for any given ferro-
alloy composition (e.g. [10]). Such an approximate value is
frequently adopted for all similar alloys due to calculation
difficulties.
Solving this problem involves two important observations:
(a) both the initial and the final states of the system (before and
after alloying) are equilibrium states, and (b) if the heat losses
occurring during the mixing process are negligible, the process
is adiabatic, i.e. heat is conserved. As the process occurs at
constant pressure, this is expressed as constant enthalpy, i.e. the
total enthalpy is the same before and after mixing. Thus, if one
considers, for instance, an addition of 70 wt.%Si ferro-silicon
alloy to raise the silicon content of the steel to 0.3%, one needs
to know at what temperature the final steel will have the same
enthalpy as the initial steel plus the room-temperature ferro-
alloy. Table 2 shows the steps in this calculation.
2.1.3. Equilibrium calculation for inclusions
Alumina and high-melting aluminate non-metallic inclu-
sions can be detrimental to the fatigue resistance of steels.
Higher-plasticity inclusions are desirable in these cases. A typ-
ical example is steel for engine valve spring applications. In
this case, it is necessary to adjust the chemical composition of
the steel in order to guarantee that the desired inclusions will
be formed. As the precipitation of oxide inclusions in steel oc-
curs close to equilibrium, this is a simple equilibrium problem.
However, it is almost impossible to solve this with the classical
tools available. Although the classical dilute solution formalism
used in steel-making can handle the behavior of the solutes in
the steel well, there is no simple way to describe the complex
56 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
Table 2
Step-by-step calculation of the heat effect of silicon addition to liquid steel [6]
Conditions for calculating equilibrium constituents of the system: Fe–Si, C = 2
(a) First step: steel without silicon. Conditions to be fixed (F = 4 = C + 2):
Total size of the system = 106 g (1 ton of steel)
%Si in solution in steel = 0
T = 1873 K (1600 ◦ C)
P = 105 Pa (1 atm)
(b) Second step: Fe–Si alloy to add 3 kg of Si. Conditions to be fixed (F = 4):
Total size of the system = 4286 g, i.e., the weight of ferro-alloy, calculated as 3000 g
of Si/70 wt.% Si in the ferro-alloy.
T = 298 K (25 ◦ C)
P = 105 Pa (1 atm)
(c) Third step: Si containing steel. Conditions to be fixed (F = 4):
Total size of the system = 106 + 4286 g
%Si in steel = 0.3
Enthalpy = 1.34 × 109 J + (−1.46 × 106 J)
P = 105 Pa (1 atm)
Fig. 2. Calculated equilibrium between steel (0.8% C, 0.6% Mn e 0.3% Si) and
oxide in the MnO–SiO2 –Al2 O3 system at 1823 K. The solid line indicates steel
Al content [11].
behavior of the oxides, even in the simplest acceptable system
in this case: the MnO–SiO2 –Al2 O3 and the CaO–SiO2 –Al2 O3
ternaries. This calculation can be performed using computa-
tional thermodynamics as indicated in Fig. 2 [11]. The calcu-
lation indicates that the aluminum content in the steel is critical
for the achievement of the desired equilibrium, i.e. for the
avoidance of high melting point, undesirable inclusions (indi-
cated by silica and mullite in Fig. 2). By adjusting the ladle
slag composition and controlling aluminum inputs in the refin-
ing steps, the process can be adjusted to maintain the aluminum
content within these narrow limits.
2.1.4. Role of methane in sintering atmospheres
It is generally assumed that species in the gas phase are in
thermodynamic equilibrium; accordingly, their potentials and
Calculation result
(a) Phases present: 1000 kg of liquid steel with enthalpy
= 1.34 × 109 J
(b) Phases present: Solid Si (DIA) and FeSi enthalpy
= −1.46 × 106 J
(c) Phases present: 1.0043 × 106 g of liquid steel
containing %Si = 0, 3T = 1870.31 K (1597.16 ◦ C)
the gas speciation can be deduced with a simple equilibrium
calculation using, as an input, the initial gas composition,
total pressure, and temperature. However, sometimes kinetics
play an important role on these reactions, and the equilibrium
calculations have to be taken into account with care.
Some examples of this fact are the CH4 decomposition used
in sintering atmospheres, or in CVD deposition.
During sintering of high-performance and close dimensional
steel components, nitrogen/hydrogen atmospheres are widely
used. Sometimes, small amounts of hydrocarbons are added
to these atmospheres. Among other functions, one of the
roles of the sintering atmospheres during sintering of ferrous
components is the reduction of metallic oxides and the control
of the chemical composition, particularly the carbon content.
However, small variations in atmosphere composition and
furnace temperature can lead to large differences in the
characteristics of the components.
In N2 –H2 atmospheres, the oxygen potential can be related
to the pH2O / pH2 ratio, by means of the chemical equilibrium
H2 + 1/2O2 = H2 O.
In industrial practice, it is common to express the water
content of an atmosphere as its dew point, instead of the water
partial pressure; in principle, the dew point can be calculated as
the temperature for a hypothetical equilibrium between the gas
phase and ice, at constant total pressure. However, it is more
common to use empirical correlations, such as that given by
German [12]:
log10 (V%) = −0.237 + 0.0336 ∗ TDP − 1.74e
− 4 ∗ TDP2 + 5.05e − 7 ∗ TDP3
where TDP is the dew point in ◦ C, and V% is the volume
fraction of water as a percentage (which is equal to its partial
pressure). The set of lines plotted in Fig. 3(a) [13,14] shows
the value of the oxygen activity in several N2 –H2 atmospheres
as a function of the water content. Auxiliary axes for the dew
 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
Fig. 3. Oxygen activity for different N2 /H2 sintering atmospheres at 1100 ◦ C, (a) without and (b) with the addition of 0.1% CH4 , as a function of the dew point of
the initial atmospheres (before equilibrium is established) [13].
point and the pH2O / pH2 ratio have also been plotted in the same
diagram. The calculations have been done using the SGTE pure
substance database (SSUB) [15], at a temperature of 1100 ◦ C,
which is a typical value of sintering temperature.
The abscissa of Fig. 3(a) (inlet pH2 O ) represents the
water content of the atmosphere before entering the furnace,
i.e. before it reaches equilibrium with the remaining species.
However, for these N2 –H2 atmospheres, this value is almost
the same as the actual water partial pressure in the atmosphere
at the temperature of the calculation.
The calculation of these curves has been performed using
the following procedure: it is convenient first to redefine the
components; instead of H, O, N, we use H2 O, N2 , H2 . The
conditions for the calculation are a total pressure of 1 bar,
temperature, a total amount of 1 mole, N2 /H2 ratio (a different
constant value for each curve: 99/1, 95/5, 90/10, 60/40, 20/80
and 1/99), and a certain oxygen activity. The oxygen activity
is varied and the calculation repeated several times, i.e. the
value is used as the “stepping” condition in the calculation.
The abscissa (inlet pH2 O ) is the mole fraction of the component
H2 O which, as mentioned above, is almost the same value as
the actual mole fraction of the species H2 O in the gas mixture
at equilibrium.
Additions of hydrocarbons such as CH4 to the sintering
atmospheres are intended to control the carbon content of
the sintered parts. However, even small quantities of CH4
can change the oxygen potential of the atmosphere. This was
illustrated by Ortiz et al. [13,16] and is shown in Fig. 3(b)
for several N2 –H2 sintering atmospheres with a small addition
of CH4 (0.1%), compared to the same atmospheres without
methane (Fig. 3(a), and the dotted lines in Fig. 3(b)), at the
same temperature of 1100 ◦ C. Several features can be stressed
in this Fig. 3(b): first of all, the abscissa represents the water
content of the gases entering the furnace, i.e. before reaching
the equilibrium; if one represents the equilibrium partial
57
pressure of water in the atmosphere, one could get just the same
set of lines as in Fig. 3(a), giving a false impression that CH4 is
not affecting the oxygen potential of the atmosphere.
Secondly, a breakdown point can be clearly seen in Fig. 3(b),
at a water content that is the same as the CH4 content of
the gas. For sintering atmospheres with water content higher
than that value, this hydrocarbon has almost no effect on
the oxygen potential; hence the reduction capability of these
atmospheres is controlled by the water content, as if no CH4
were present. However, when the water content is lower than
that of CH4 , the oxygen potential is sharply reduced by several
orders of magnitude. For atmospheres with a low H2 content,
saturation is produced due to the carbon activity reaching values
higher than unity (labeled “sooting” in Fig. 3(b)); here, the gas
composition (the CO/CO2 ratio, and hence the oxygen activity)
is controlled by the Boudouard reaction,
C + CO2 = 2CO.
The lines plotted in Fig. 3(b) have been calculated following the
same approach as with Fig. 3(a): the components defined are
CH4 , H2 O, N2 and H2 , instead of C, H, O and N. The conditions
for the calculation are a total pressure of 1 bar, temperature, a
total amount of 1 mole, N2 /H2 ratio (a different value for each
curve: 99/1, 95/5, 90/10, and so on), the CH4 quantity (mole
fraction 0.001), and a certain oxygen activity, whose value is
used as the “stepping” condition in the calculation.
In addition, several horizontal lines have been plotted in
Fig. 3(a) and (b). They represent the oxygen potential for
metal/oxide equilibria, of several metals used in sintering (Fe,
Cr, Mn and the powder Astalloy CrM), at the temperature of
the calculation. They give an indication of the atmosphere’s
capability for the reduction of the metal oxides.
The carbon activity of these atmospheres is represented in
Fig. 4, showing the conditions for methane decomposition with
carbon formation (sooting).
58 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
Fig. 4. Calculated carbon activity for N2 –H2 atmospheres with 0.1% CH4 , at
1100 ◦ C as a function of the water content, represented also as the dew point of
the atmosphere [13].
Finally, this analysis can be done at different temperatures,
as is represented in Fig. 5 for two values of the dew point
(−45 and −15 ◦ C), and for different N2 /H2 ratios, expressed
as N2 partial pressure. According to this, atmospheres that are
supposed to be extremely dry (i.e. with a very low dew point,
−45 ◦ C), are more likely to experience CH4 decomposition and
hence sooting.
Calculations such as those shown here allow the control
of both the oxygen and the carbon potential in sintering
atmospheres, thanks to changes in the gas composition.
2.1.5. Interface control in PVD of cemented carbide
Today, about 60% of cemented carbide cutting tools are
CVD coated [17] including an Al2 O3 layer for excellent wear-
resistance. There are typically two forms of Al2 O3 phases,
i.e. the stable α- and meta-stable κ-Al2 O3 phases. Although
the α-Al2 O3 phase shows excellent high-temperature stability,
it is difficult to form and has relatively poor adhesion to the
inner non-oxide layer compared with the κ-Al2 O3 phase. To
promote the formation of α-Al2 O3 and improve its adhesion to
the inner non-oxide layer, a bonding layer was deposited before
the deposition of the Al2 O3 [18,19]. In order to fully understand
phase stability in this bonding layer in the CVD coating
of cemented carbide cutting tools, detailed thermodynamic
calculations were carried out to investigate the effects of
various processing parameters [20]. Feeding gases flowed
upwards in the chamber at 60 torr pressure with a temperature
of 970 ◦ C at the bottom and 1000 ◦ C at the top of the
chamber [20]. The input gas mixture consisted of H2 (86%
volume), CH4 (4%), CO2 (1.7%), N2 (8%), and TiCl4 (0.3%).
These experimental conditions were used as initial conditions
in the present thermodynamic calculations using the Thermo-
Calc program [21] and the SGTE substance database [22]
combined with the FEDAT database of TCAB [23]. As a first
approximation, the Gibbs energy, G fcc TiO , for the end-member
of TiO in the Ti–O fcc phase and the interaction parameter
between oxygen and vacancy were estimated from those of the
hcp phase in the Ti–O binary system [24].
The effects of individual processing parameters, i.e. gas flow
ratios, temperature, and pressure, and their combinations, on
the phase stability were investigated by systematically varying
their values. Equilibrium calculation resulted in three-phase
equilibrium of gas, fcc, and graphite, with the composition of
fcc being Ti(C0.016 N0.984) with little oxygen, typically called
the TiCNO phase in the literature, and the CH4 concentration in
the gas phase being 0.07%. It shows that over 98% of methane
has been consumed. If graphite is assumed to be difficult to
form, as one does usually, the formation of the fcc-TiCNO
phase would be observed, in agreement with the suggested
phase in the literature [19,25].
However, in the experimental investigations, it was found
that, under typical CVD processing conditions for the
bonding layer, four types of titanium oxides, i.e. TiO2 ,
Ti4 O7 , Ti3 O5 , and Ti2 O3 , were observed from the X-ray
diffraction (XRD) analysis by extending the deposition time
for the bonding layer instead of the fcc-TiCNO phase [20].
To understand the difference between the calculations and
experimental observations, the thermodynamic driving force
for the formation of graphite, defined as Dgra = − G RT with
G being the Gibbs free energy change for the formation of
graphite, was evaluated. It was found that only the flow ratios
of CH4 and CO2 change the sign of Dgra , as shown in Fig. 6.
If the flow ratio of CH4 is higher than 1.8%, the driving force
for the formation of graphite will be positive, which means that
the graphite will form from the gas phase. On the other hand,
graphite will not form if the CH4 flow ratio is lower than 1.8%.
For CO2 , the zero driving force point is around 3.7% with the
higher CO2 flow ratio preventing the formation of graphite.
Consequently, the phase diagram of the CH4 flow ratio and
temperature was calculated and plotted in Fig. 7. It should
be noted that there is no stable phase region for the Ti2 O3
compound in Fig. 7 to explain the formation of the Ti2 O3
compound in one of the samples at the top of the CVD chamber.
This suggests that the formation of the mixtures of titanium
oxides is not only influenced by the flow ratio of CH4 but also
by other factors, which are discussed in detail in Ref. [26].
To investigate the decomposition of CH4 , Fulcheri and
Schwob [27] considered the following chemical reaction
CH4 → C+2H2 . This reaction is endothermic and the standard
decomposition enthalpy is: H 0 = 74.6 kJ/mol. Fulcheri and
Schwob plotted the energy supply needed for the above reaction
as a function of temperature and concluded that the temperature
should be between 1000 ◦ C and 2000 ◦ C for the reaction to take
place. Moradov mentioned that the processing temperatures for
this decomposition reaction is 1400 ◦ C or higher without a
metal catalyst [28].
2.1.6. Sintering of Si3 N4 –SiC ceramics
Ceramics based on non-oxide compounds such as Si3 N4 and
SiC are suitable candidates for high-temperature engineering
 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
Fig. 5. Calculated carbon activity (ref. state: graphite) for N2 –H2 mixtures containing different quantities of CH4 ((a) 1%; (b) and (c) 0.1%) and H2 O (dew points
of (a) and (b) −45; (c) −15 ◦ C), as a function of temperature [16].
applications. SiC-reinforced Si3 N4 composites are fabricated
by addition of whiskers, fibers and platelets of SiC to Si3 N4 .
Also, the use of precursor polymers has attracted wide attention
as an alternative approach to produce Si3 N4 –SiC ceramics and
offers a number of advantages compared to classic powder
technology [29]. With the synthesis of Si–C–N ceramics from
precursor polymers, one can control the materials composition,
structures and properties on an atomic scale. To predict and
control the sintering conditions for all types of Si3 N4 –SiC
ceramics, thermochemical calculations can be used.
The stability and decomposition of silicon carbide–silicon
nitride (Si3 N4 –SiC) ceramics during the sintering process were
investigated by thermodynamic calculations. Thermodynamic
descriptions for the Si–C and Si–N systems were accepted
from the literature [30,31]. The data for C–N gas species were
taken from the database of the Scientific Group Thermodata
Europe (SGTE) [15]. Isothermal sections were calculated by
59
extrapolation from the binary subsystems [32]. Fig. 8 shows
the isothermal section in the Si–C–N system applicable for
temperatures 1757 K < T < 2114 K and a total pressure
of 1 bar. The composition of a precursor-derived Si–C–N
ceramic (PHMS) is indicated for discussion in the following
sections. The isothermal section shows a silicon nitride–silicon
carbide–nitrogen gas (Si3 N4 –SiC–N2 ) phase field indicating
the stability of Si3 N4 –SiC ceramics. At temperatures lower than
1757 K, SiC and nitrogen react to form Si3 N4 and graphite. At
temperatures higher than 2114 K, silicon nitride decomposes
and forms liquid silicon and nitrogen. A detailed analysis of
the system thermodynamics shows that the nitrogen partial
pressure has to be changed simultaneously with the heating or
cooling of the furnace during the sintering process to stabilize
the microstructure of the ceramic materials. The calculated
“ pN2 -temperature” potential diagram in Fig. 9 provides general
guidelines for the correct sintering conditions. The stability area
60 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
Fig. 6. Effect of gas flow ratios on the driving force of graphite.
Fig. 7. Calculated phase diagram using temperature and CH4 flow ratio.
of Si3 N4 –SiC ceramics is indicated in the diagram. It shows
that, during temperature decrease from a sintering temperature
of, e.g., 2173 K (1900 ◦ C) to room temperature, the nitrogen
pressure has to be decreased in a well-defined and continuous
way to avoid any phase reactions. If the nitrogen pressure
is kept constant during cooling, silicon carbide and nitrogen
gas react to form free carbon, deteriorating the good materials
performance. The next step of such a thermochemical analysis
has to consider the influence of the most common sintering aids
such as Al2 O3 and Y2 O3 on the phase reactions. Generally, the
sinter process for technical ceramics and composites requires a
very careful analysis of the partial pressures of the gas species
and their interaction with condensed phases. Thermochemical
calculations efficiently support this approach.
Fig. 8. Isothermal, isobaric (1 bar) section in the Si–C–N system valid for
1757 K < T < 2114 K. The composition of an amorphous PHMS precursor-
derived ceramic (see Fig. 9) is indicated.
Fig. 9. Potential phase diagram for the Si–C–N system valid, for example, for
PHMS-derived ceramics with C:Si < 1.
2.1.7. Prediction of the high-temperature stability and decom-
position of Si–C–N ceramics derived from precursors
Precursor-derived Si–C–N ceramics are X-ray amorphous
up to temperatures of about 1773 K (1500 ◦ C). At
higher temperatures, the materials crystallize, decompose
and cannot be used as an engineering material. Precursor-
derived amorphous Si–C–N ceramics of varying composition
can be produced by polymer thermolysis. It is, however,
too expensive and time consuming to investigate the high-
temperature behavior of all possible ceramic compositions just
by experimental methods. Thermodynamic simulations can
support efficient materials characterization. It is, for example,
possible to simulate the thermal gravimetrical analysis (TGA)
of Si–C–N materials by means of calculated phase fraction
diagrams, as shown in Fig. 10 [32]. This diagram shows
a Si–C–N precursor ceramic (PHMS) phase reaction at a
temperature of 1757 K, where silicon nitride reacts with
carbon to form SiC accompanied by the formation of nitrogen
gas. A mass loss of 13.7 wt.% is expected. The simulation
shows an expected second mass loss of 15.1 wt.% at 2114 K
due to the decomposition of silicon nitride forming silicon
 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
Fig. 10. Calculated phase fraction diagram in the Si–C–N system for PHMS-
derived ceramics (C:Si < 1).
and nitrogen gas. These simulated weight losses are in good
agreement with the results of the thermal gravimetrical analysis
Fig. 11. However, the TGA shows that the first reaction
occurs at significantly higher temperatures than expected
from the simulation. The deviation can be explained by
considering the amorphous microstructure of precursor-derived
ceramics. However, no thermodynamic data is available for the
amorphous Si–C–N materials. Therefore, all thermodynamic
calculations are performed for materials assuming crystallized
microstructures composed of silicon nitride, silicon carbide
and graphite at temperatures below 1757 K. Nevertheless,
important quantitative information on expected TGA results
can be derived from the calculations. Similar calculations were
also made for Si–B–C–N precursor-derived ceramics to analyze
their high-temperature stabilities [33].
Fig. 11. TGA/DTA measurement of PHMS precursor-derived ceramic (BN crucible, nitrogen atmosphere, heating rates: RT–1000 K, 10 K/min; 1000–2000 K,
5 K/min).
61
2.1.8. Simulation of the thermolysis of metallorganic precur-
sors for Si–C–N ceramics
The simulation of the thermolysis of metallorganic
precursors to produce amorphous Si–C–N ceramics requires
the calculation of the reaction paths in the Si–C–N–H system.
A database was developed for this quaternary system by
thermodynamic optimization [33]. Gas species descriptions
were accepted from the database of the Scientific Group
Thermodata Europe (SGTE) [15]. Various gas species form
during the thermolysis of Si–C–N–H precursor polymers, e.g.
Si, Si2 , Si3 , N2 , Si2 C, SiC2 , SiN, Si2 N, CN, (CN)2 , H2 ,
CH4 , and NH3 . The thermolysis is usually carried out in an
open system reactor and flowing gas atmosphere, whereas
the calculations are performed for a closed system and static
atmosphere conditions. Nevertheless, the composition of the
final amorphous ceramic Si–C–N reaction products could be
derived in good accordance with the experimental results. The
decomposition of metal-organic precursor polymers containing
50 wt.% of hydrogen was simulated. The calculated isothermal
section for 573 K and 50 wt.% hydrogen is shown in Fig. 12.
The polymer compositions are indicated. An extended gas
phase–silicon nitride field is detected. At this temperature, the
gas phase mainly consists of methane. The composition of the
gas phase forming with progressing precursor decomposition
(increasing temperature) was simulated. During thermolysis, a
continuous change in the condensed material composition, as
well as of the gas phase composition, occurs. The consequence
of these reactions are curved reaction paths due to the
continuous change in the ratio of the gaseous species, starting
in the space of the Si–C–N–H concentration tetrahedron and
ending on the tie-lines graphite–silicon nitride or the tie triangle
carbon–silicon nitride–silicon carbide. For the given example,
the carbodiimide-based PHMS precursor, Fig. 13(a), shows
the fractions of the condensed phases. Fig. 13(b) presents
the corresponding gas phase composition. At temperatures
higher than 773 K, methane and, additionally, hydrogen are
formed. At a thermolysis temperature of 1323 K, hydrogen
is the dominating gas species. The precursor materials with
silicon deficits (with respect to the Si:N ratio of 0.75 for
Si3 N4 ) additionally form small amounts of nitrogen and
62 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74

Fig. 12. Isothermal section (573 K) at 50 at.% hydrogen in the Si–C–N–H system with compositions of different precursor materials indicated.

(a) Phase fractions of the solid products. (b) Gas phase composition.

Fig. 13. Results of thermodynamic calculations for the PHMS precursor (11.5 Si, 15.7 C, 10.5 N, 62.3 H; at.%): (a) phase fractions of the solid products; (b) gas
phase composition.

ammonia. All precursors completely lose hydrogen during the

thermolysis. The resulting amorphous materials compositions
are located in the Si–C–N subsystem, as indicated for the
decomposition of the PHMS precursor material Fig. 14. The
materials composition is located on the carbon–Si3 N4 tie line.
The experimentally derived ceramic thermolysis product is
X-ray amorphous, but the bulk composition is similar to the
calculated composition.

2.1.9. Oxidation of γ -TiAl materials

The oxidation of γ -TiAl based alloys in air and various
other atmospheres has been extensively studied experimentally
over the past few decades. The reaction kinetics and
character of the developing oxide layers and subscale zones
are influenced by many alloy properties such as grain Fig. 14. Compositions of solid products of PHMS precursor thermolysis
size and surface roughness. To clearly separate the effects calculated for temperatures 298–1323 K, displayed together with the phase
of the thermochemical conditions during oxidation from equilibria in the Si–C–N system for 1687 K < T < 1757 K.
 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74 63

such alloy characteristics, thermodynamic calculations were

carried out. These calculations serve as a reference for a
deeper understanding of the reaction kinetics and phase
development [34].
Using the thermodynamic database for the Ti–Al–O system
developed by [35,36], it is possible to calculate potential
phase diagrams and compare them with results from TEM
investigations of the surface of oxidized γ -TiAl materials.
As known from experiments, oxygen and aluminum are the
main diffusing components during the formation of a sub-scale
zone below an oxide layer on the alloy surface. Therefore, the
chemical potentials of the diffusing components Al and O were
used as axes for the calculated potential diagram at 1173 K.
Phase equilibria are composed of γ -TiAl, α2 -Ti3 Al, Al2 O3 and
the ternary X-phase. Based on this diagram, the qualitative
oxidation behavior of γ -TiAl in air can be derived. The
formation of the sub-scale zone can be described by assuming
time-dependent changing μAl /μO ratios. The nitrogen effect
was neglected as a first approximation (Fig. 15). This approach
can be used as a first step in the analysis of the phase evolution
of the diffusion-controlled process of γ -TiAl oxidation for two
reasons: (1) chemical potential gradients are the driving forces
for diffusion, and (2) local equilibrium at the interfaces of the
phases can be assumed. For the sake of simplicity, a linear
variation in the chemical potentials along the diffusion zone can
be assumed. The change in the chemical potentials of aluminum
and oxygen through the diffusion zone can then be described by Fig. 15. Light optical images of the γ -TiAl oxidation zone and the Ti–Al–O
the iterative formulae μi+1 (Al)(t) = μi (Al) + μ(Al)(t) and potential diagram (1173 K, p = 1 bar) with indicated diffusion paths.
μi+1 (O)(t) = μi (O) + μ(O), respectively, with μ(O) > 0
and μ(Al) < 0, where the index i is equivalent to a distance Y-silicate coatings. To simulate the phase reactions, a
within the alloy. Oxygen is a fast-diffusing component, and quaternary Y–Si–C–O database was developed and used
the time dependence of the step value μ(O) was neglected. for application orientated calculations [37]. The isothermal
The step value for aluminum can then be related to μ(O) potential diagram in the Y–Si–C–O system was calculated
by a time-dependent model parameter q(t): μ(O)/μ(Al)(t) using CO- and SiO-partial pressures as axes Fig. 16.
= q(t) with ∞ < q(t) < 0. The parameter q(t) defines the Preliminary calculations had shown that CO and SiO are
paths indicated in the potential phase diagram in Fig. 8 at a the main gas species formed from interfacial reactions. The
time t. It defines the slope of a straight line which starts at three-phase equilibrium field for gas, SiC and Y2 SiO5 was
ref
μ, assuming very small oxygen impurities in γ -TiAl. With calculated (by fixing them as stable phases). This three-phase
these assumptions, the oxidation process of γ -TiAl can be field exists between lines of four-phase equilibria: (a) gas, SiC,
described as a series of successive local equilibrium states t1 Y2 SiO5 , Y2 Si2 O7 ; and (b) gas, SiC, Y2 SiO5 and graphite. At
to t4 . Path t4 defines the start of the oxidation with γ -TiAl(O) the intersection point of these four phase lines, the five-phase
and Al2 O3 in equilibrium. Path t2 predicts the evolution of the equilibrium of gas, SiC, Y2 SiO5 , Y2 Si2 O7 and graphite exists,
interfaces Al2 O3 /X and γ -TiAl(O)/X in good accordance with representing the heat shield coating system under investigation.
the surface layers found after 100 h of oxidation. The oxidation The gas phase consists mainly of carbon monoxide, and its
experiments show that, after 250 h, α2 –Ti3 Al has additionally pressure increases significantly with temperature, as shown in
formed, which is simulated by path t3 . Path t4 predicts the final Fig. 17. Blister formation and spallation of the coating can be
state of oxidation at which the X-phase disappeared completely explained by the interface reactions and the accompanied gas
after extended time periods of oxidation. phase formation and pressure increase.

2.1.10. Interface reaction of yttrium silicates with SiC-coated
C/C–SiC composites in heat shield applications
Yttrium silicate coatings are potential candidates for
the oxidation protection of SiC-pre-coated C/C–SiC heat
shields for space shuttle systems. Plasma wind tunnel tests
showed that they can withstand temperatures of 1650 ◦ C,
but at temperatures higher than 1750 ◦ C the coatings fail
because of blister formations and subsequent spallation of the
2.2. Time-dependent problems
When the time available for the processes to occur is not
long enough for equilibrium to occur, either a time-dependent
solution is used or the equilibrium information has to be
considered with additional care. This section discusses some
examples of the application of computational thermodynamics
to time-dependent problems.
64 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
Fig. 16. Potential diagrams in the Y–Si–C–O system for 1853 K, 1903 K, and
2000 K.
Fig. 17. Temperature-dependent vapor pressure in equilibrium with SiC,
Y2 SiO5 , Y2 Si2 O7 and carbon.
2.2.1. Segregation in steel
Solidification rarely occurs in equilibrium conditions in
industrial processes. The way that solute redistributes during
this process is very important in defining the properties of
steels. The first kind of information that can be obtained,
using computational thermodynamics, is the equilibrium phase
and phase fraction. Actual industrial results frequently deviate
from this, due to non-equilibrium solidification. Algorithms
for the calculation of segregation, assuming that complete
homogenization occurs in the liquid (Scheil model) and no
diffusion occurs in the solid, have been implemented in
computational thermodynamic software (e.g. [21]). Recently,
Fig. 18(a). Solidification modeling of M2 high-speed steel using different
techniques. Experimental values of T solidus  are indicated [38].
the option of assuming that interstitial elements are completely
homogenized in both liquid and solid while substitutional
elements follow the Scheil model (i.e. only complete
homogenization in the liquid) has also been also implemented
as the “partial equilibrium” model [38]. These three models can
be implemented in computational thermodynamics software
without explicitly considering time as a variable. These models
are useful in several cases, depending on what information is
necessary. Non-equilibrium phases and the effective solidus
temperature in the industrial solidification of high-alloy steels,
for instance, can be estimated with reasonable precision using
these simplifications [38].
Fig. 18(a) presents the results of the calculations performed
by Chen and Sundman [38] for M2 tool steel using these
three models. It is evident that the partial equilibrium model
predicts correctly the phase sequence as well as the solidus
temperature. These models, however, are not always accurate
enough when dealing with structural steels solidified under
continuous casting conditions or in the predicition of the actual
profiles of chemical composition in the segregated solid. In this
case, it is essential to consider mass transfer by diffusion, in
both the solid and the liquid phase during solidification. The
results of this type of calculation using software that couples
computational thermodynamics with the solution of diffusion
equations (DICTRA) [21] are presented in Fig. 18(b). The
agreement with the experimental data of Ueshima et al. [39]
is evident.
2.2.2. DICTRA simulation of carburizing of stainless steel
(a) Definition of the problem. Carbon is usually considered as
a harmful impurity in austenitic stainless steels because it may
react with chromium to form Cr-rich carbides and eventually
cause a loss in corrosion resistance. It is thus necessary to keep
the carbon level very low by metallurgical processing in the
steel plant or by adding strong carbide formers like Ti and Nb
 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74 65

Fig. 19. Carbon content profiles at the times indicated during carburizing of
Fig. 18(b). Calculated Mn distribution in cast steel containing %C = 0.13, pure iron at 800 ◦ C.
%Si = 0.35, %Mn = 1.52, considering diffusion in both liquid and solid
phases (DICTRA) [6]. Experimental data from [39].

Table 3
Composition of stainless steel (mass%)

Cr Ni Ti Fe
18 10 1 bal

to the steel. These will react with C to form very stable MC

carbides, and the residual carbon content in solution will be so
low that no Cr-carbides form.
If stainless steel is welded to low-alloy steel, it may be
carburized by the low-alloy steel and gain much increased
carbon content and, as a result, there will be unwanted
carbide formation. That problem was considered by Helander
and Ågren [40]. Exposure of stainless steel in a carbon-rich
atmosphere, e.g. a gas containing hydrocarbons, may also
lead to carburizing. This situation will be considered in the
present example. We shall consider a stainless-steel plate, with
a thickness of 6 mm, with the initial composition given in
Table 3. The initial carbon content is assumed to be very low. Fig. 20. Carbon content profiles at the times indicated during carburizing of
stainless steel at 800 ◦ C. Single-phase austenite is assumed.
We consider an atmosphere having a carbon activity of
unity relative to graphite, i.e. the gas is on the soot limit. The
temperature is 800 ◦ C (1073 K) and we consider an exposure The assumed maximum distance (3 mm) is treated as the
time of 1000 h, i.e. 6 weeks. The question is: what will happen boundary condition defining a closed system. As can be seen,
to the steel? there is a massive carburization and the carbon content after
(b) Simplifications. We first rephrase the question into a 1000 h has almost leveled out at the level corresponding to
thermodynamic/kinetic question. How will the amount of equilibrium with the atmosphere.
carbon and carbides vary with time and distance from the steel In the next simulation, we shall take into account the
surface? We shall make three different simulations with the alloying, but still assume that we have a single-phase austenitic
DICTRA code [41]. structure. We then use mixed boundary conditions on the left-
(c) Thermodynamic formulation of the problem. In the first hand side with the carbon activity unity relative to graphite and
simulation, we consider carburizing of pure Fe in the austenitic zero flux for the other elements. The result is shown in Fig. 20.
state. A fixed carbon activity of unity relative graphite is taken The carbon content at the surface is now much higher due
as the boundary condition, and the size of the system is taken to the presence of the alloy elements Cr and Ti, which lower
as 3 mm. The result is shown in Fig. 19. the carbon activity for a given carbon content, and the profiles
66 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74

Fig. 21. Carbon content profiles at the times indicated during carburizing of Fig. 22. Weight fraction of carbides at the same time as in Fig. 21 during
stainless steel at 800 ◦ C. Carbide formation is taken into account. carburizing of stainless steel at 800 ◦ C.

have a different shape due to the alloying effect on carbon

diffusion. Finally, in the third simulation, we allow the MC
carbide, M23 C6 and M7 C3 to form. We have used the disperse
model in DICTRA and enter these phases as spheroidal phases.
We have used a so-called labyrinth factor that is f 2 , where f is
the volume fraction of austenite. As can be seen in Fig. 21, the
carbon profile again looks quite different. The corresponding
profiles showing the fraction of phases are shown in Fig. 22.
Close to the surface, the carbon content is highest, we have
M7 C3 and then, at lower C content, we have M23 C6 . The
MC carbide is formed in addition to the other two carbides,
but not in very high amounts. It may also be interesting to
investigate the residual Cr content in austenite in order to see
if the corrosion resistance is sufficient. As a rule of thumb,
one requires 11–12 mass% Cr dissolved in austenite to have
satisfactory corrosion resistance. These series of curves are
shown in Fig. 23.
The disperse model in DICTRA is based on the assumption
that the disperse phases, i.e. the carbides, occur with a
composition and amount that are given by equilibrium for
the local composition. The model does not take into account
Fig. 23. Cr content in austenite at the times indicated. Cr content lower than
any microstructural features, but only thermodynamics and dashed line corresponds to insufficient corrosion resistant.
diffusional mobilities. In the present simulation, the Thermo-
Calc databases TCFE3 and MOB2 were used [21]. It should
be emphasized that, in reality, it would take some time sizes range between 5 nm and 50 nm embedded in an amor-
for the carbides to form and, moreover, one often observes phous matrix with nanocrystal volume fractions of 30–80%
that they appear preferentially at grain boundaries. A more (particle densities of 1022–1028 m−3 ). The precipitation of the
detailed simulation, e.g. by phase-field techniques, would
primary phase occurs in a supersaturated/undercooled liquid
require much additional input information and need much
solution, where growth is usually limited by the diffusion of so-
longer computation times.
lute atoms. The driving force is the determining factor needed
2.2.3. Describing crystallization kinetics — the influence of to evaluate the rate of the transformation and can be calcu-
interfacial energy and diffusion data lated by CALPHAD methods. To model the time evolution of
Very interesting properties can be obtained with the the structure, other quantities such as diffusion coefficients and
nanocrystallization of metallic glasses obtained by controlled interfacial energies are necessary. In the present example, these
heat treatment. Typically, in these nanostructures, precipitate are estimated indirectly from experimental kinetic data.
 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74 67

At the onset of primary crystal precipitation, the nucleation

frequency, I (T ) (assumed homogeneous), is given by [42]:
 
16πσ 3
I (T ) = Io (T ) · exp − (1)
3RT (G T )2
8Nv D(T )  σ 1/2
Io (T ) = (2)
(a)2 RT
where D is the diffusion coefficient, σ is the molar
crystal–liquid interfacial energy, Nv is the number of nucleation
sites per unit volume in the liquid, a is the mean atomic radius,
 is the mean interfacial thickness in units of the mean atomic
radius [43], and G T , for primary precipitation, is calculated
by [44–46]:
Fig. 24. Establishment of local equilibrium at the interface of the primary
liq
G T = Σ x ixt (μixt − μi ) (3) grains.

φ
where x i (i = 1, 2, . . . , c) denote the atomic fractions of each
component i in phase φ (φ = xt → crystal; liq → liquid)
φ
and μi denote their chemical potential at temperature T . Nuclei
form with a critical radius r ∗ given by
2σ a
r∗ = . (4)
G T
Interface controlled growth will lead to a growth rate u(T )
given by
  
2λD(T ) G T
u(T ) = 1 − exp − . (5)
2 a RT
Here, λ is the product of the fraction of surface sites where
atoms are preferentially added and the length of the interface
in units of the mean atomic radius.
The kinetics of the process can be viewed in the following
manner. At any time, t, the transformation proceeded up
to a fraction, ξ · f 1 , of the total volume, V , where f 1 is
the total volume fraction available for primary crystallisation
and ξ is the actual degree of advancement of the process.
The Kolmogorov–Johnson–Mehl–Avrami formalism [47–50]
allows the evaluation of the rate of the transformation, since
it has been shown [43] that the Avrami equation
ξ = 1 − exp(−ξex ) (6)
where ξex is the extended degree of advancement of the
transformation, remains valid for a primary crystallisation
process, provided that the temperature dependence of f 1 may be
neglected in the transformation temperature interval. The mean
concentration of the matrix is then given by
cio − cixt
cit = cixt + (7)
1 − ξ f1
where cio is the initial composition of the parent phase.
That is, the nucleation frequency depends on the degree
of advancement of the process. In a first-order approach [43],
the expected decrease in the actual nucleation frequency
is evaluated by multiplying the homogeneous nucleation
frequency I (T ) from Eq. (3) by the factor ϕ[x(t)] given by
1 − x(t)
ϕ(x) = . (8)
1 − ξ x(t)
From the point of view of growth, a still supersaturated matrix
surrounds the nuclei just formed. That is, there is an initial
growth transient, for each individual grain, in which the local
equilibrium between the emerging crystal and the liquid ahead
of the crystal–liquid interface is established (with composition
c∗ ), as shown schematically in Fig. 24. Afterwards, diffusion
becomes the controlling mechanism. During the growth
transient, the interplay between interface- and diffusion-limited
growth acts in a way to increase the importance of the
latter mechanism until it becomes preponderant. The simplest
approach is to assume that the transient is interface-controlled,
whereas the second stage of individual grain growth, in the
extended view, i.e. neglecting spatial impingement between
grains, is diffusion-controlled [51].
Since both D and G T in Eq. (5) change in the course of the
transformation, the interface-controlled growth rate is evaluated
by multiplying the growth rate obtained from Eq. (5) by the
factor ϕ[x(t)] from Eq. (8).
When solute fluxes through the interface are driven by
steady-state diffusion, the growth rate of an isolated growing
grain with radius R under spherical symmetry in this steady-
state regime is given, for a binary system, by [43],
dR Ds f 1
= {ϕ[x(t)]}2 (9)
dt R
where ϕ 2 accounts for soft impingement (overlapping of
diffusion fields).
In a multicomponent system, each of the elements has
its own diffusion coefficient, and consequently the different
elements will generate different concentration gradients. The
general solution in this case has been reported [3]. In the
following, Ds will be considered as an effective diffusion
coefficient to deal with multicomponent systems.
As an example the primary nanocrystallization of a
FINEMET alloy glass with composition Fe73.5 Cu1 Nb3 Si17.5 B5
is discussed in terms of these considerations. The goal is to
establish the limits inherent to the approach to get estimated
values of both the interfacial energy and the apparent diffusion
coefficients, D and Ds , from experimental kinetic data.
The details of alloy preparation and characterization of the
nucleation and growth processes are given elsewhere [43].
68 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
Fig. 25. Selected values of the nucleation frequency (I ), interface controlled
growth rate (u), and effective diffusion coefficient (Ds ) that fit experimental
DSC data.
To describe the kinetics of the overall nanocrystallization
process, the temperature dependence of D(T ) or, equivalently,
Ds (T ), is given by an Vogel–Fulcher relationship [52,53],
namely
D(T ) = Do · T · exp{−B/(T − To )}.
Here, Do , B and To are empirical fitting parameters used to
describe the sharp increase of diffusivity above glass transition.
The ratio B/To is often used to differentiate between strong
(B/To ∼ 100) and fragile (B/To ∼ 5) glasses.
The adjustment of the general trend in the calorimetric
curves depends mostly on the mechanisms involved in the
transformation. The problem is that neither the values of
σ nor those of B and To (or, equivalently, the apparent
activation energy of D) are well known, and the temperatures
at which transformation occurs, and their shift with changing
heating rate, are very dependent on the precise values of these
quantities.
The modelling and calculation of the transformation rate
as a function of temperature at various heating rates has
been performed to determine the optimum range of values for
interfacial energy, D, and Ds , to get reasonable agreement with
the experimental continuous heating DSC curves. All other
values used in the calculation have been maintained constant
at the values already published [43].
Fig. 25 shows the calculated nucleation frequency, interface
controlled growth rate and effective diffusion coefficient as a
function of temperature for the two limiting values considered
for the interfacial energy. Agreement with experimental points,
also shown in this figure, may lead to a quite substantial wider
range of values than those quoted, because of the uncertainty
Fig. 26. Comparison of the calculated and experimental temperature
dependence of the transformation rate, assuming that σs = 0.131 J m−2 and
adjusting D and Ds values accordingly.
(10)
Fig. 27. Comparison of the calculated and experimental temperature
dependence of the transformation rate, assuming that σs = 0.136 J m−2 and
adjusting D and Ds values accordingly.
inherent in the measurements of I and u at a given temperature
by transmission electron microscopy (TEM). In that respect,
continuous heating DSC curves constitute a unique set of
kinetic data exploring a wide temperature range that, even with
some uncertainty, are accurate enough to fix the respective
values of σ , B and To required to get agreement of the modelled
kinetic process.
Figs. 26 and 27 show the calculated transformation rate for
the two limiting values of σs = σ · [Vm2 · N A ]−1/3 , where Vm is
the molar volume and N A is Avogadro’s number. In each figure,
the experimental transformation rate obtained by DSC is also
included to allow easy comparison with calculated values for
heating rates varying from 1.25 K min−1 to 80 K min−1 .
As can be deduced from inspection of Fig. 26, when the
interfacial energy changes from 0.131 J m−2 to 0.136 J m−2 ,
the homogeneous nucleation rate decreases substantially and,
consequently, the values of u and Ds (or D) have to increase to
compensate such a decrease. At the same time, the apparent
 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
activation energy of the overall primary nanocrystallization
has to be maintained. This is the main reason for the narrow
range of deduced values for σ that are consistent with the
experimental transformation rates. Consequently, the indicated
modelling procedure is quite suitable for obtaining indirect
evaluation of the interfacial energy between the nanocrystals of
α-(Fe,Si) with DO3 structure embedded in a disordered matrix
with global Fe73.5 Cu1 Nb3 Si17.5 B5 composition.
It is worth mentioning that there is a spread in the
experimental values obtained, clearly seen in Figs. 26 and 27
when several curves are shown for the kinetic transformation
at a fixed heating rate. However, it is clear that the modelling
is better at reproducing the earlier part of the transformation
than its end. To obtain better results in the later stages probably
requires a more refined analysis of the impinging stage for
diffusion-controlled growth. To improve the analysis, reliable
values of the supersaturation in the remaining matrix are also
needed. Furthermore, it is important to notice the limitation
in the coupled derivation of parameters from the kinetic data;
clearly, the ability to make predictions would greatly benefit
from an independent determination of values for interfacial
energies as well as diffusion data.
3. Limitations to current applications — evaluating
interfacial energies
The examples above show that progress in computational
thermodynamics is making it possible to solve materials-
related problems with a complexity that could only be tackled
conceptually a decade ago. However, as one proceeds to
formulate and solve these problems, the limited extent of the
data that is available becomes evident. The last few decades
have seen a dramatic evolution in the amount and quality of
assessed thermodynamic data that is included in the available
databases [21,54]. More recently, the same has happened with
diffusion data needed to address transformations in alloys [21,
55]. Bulk thermodynamic and diffusion data are insufficient,
however, to properly predict important microstructure features,
as well as their evolution. In particular, interfacial and
strain energies are important in defining phase nucleation
and morphology. The following section demonstrates how
tools currently available in computational thermodynamics and
related fields can contribute to the quantification of these
important variables.
3.1. Computation of interfacial energies using thermodynamic,
first-principles and semi-empirical atomistic approaches
Nucleation kinetics is one of the key issues in the theory of
phase transformations where a proper quantitative approach is
limited by the lack of data for interfacial energy between the
matrix and precipitating phases. Recent progress in atomistic
approaches shows some feasibility of providing the necessary
information. In the present review, an attempt will be made
to compute the interfacial energy between γ (Ni-rich fcc) and
γ  (L12 Ni3 Al) phases in the Ni–Al binary system using three
different approaches, and then to compare the results. The
methods used in the present work are:
69
(1) a classical thermodynamic approach;
(2) a first-principles calculation; and
(3) a semi-empirical atomistic approach based on the modified
embedded atom method (MEAM) interatomic potential.
3.1.1. Thermodynamic method for the calculation of interfacial
energies for γ /γ  phases in binary and multi-component nickel-
base alloys
The overall value of any interfacial energy contains many
contributory factors, including:
(a) a chemical contribution;
(b) a strain energy contribution;
(c) the presence of dislocation arrays;
(d) the presence of chemical segregation.
The γ /γ  phase transformation in nickel alloys exhibits
a small lattice misfit, which minimises any strain energy
contribution. This, in turn, also minimises the presence of
interface dislocations, which reduces the potential degree of
segregation to the boundary. We can therefore expect that the
interfacial energy for this transformation in such systems will
be dominated by the chemical term.
The simplest thermodynamic approach for the calculation of
interface energies follows the work of [42], who assumed that,
in the case of liquid–solid interfaces, the value of σ for pure
metals scales with the difference in enthalpy:
σ = αHm . (11)
This approach has also been used successfully in studies
related to the relative nucleation of competing phases from the
liquid [56].
A theoretical justification for such an approach has been
given by [57], which relates α to z ∗ (the number of atoms
per unit area of the interface), N ∗ (the number of cross bonds
per atom at the interface), and z (the co-ordination number
of nearest neighbours in the lattice, which equals 12 in FCC
structures). Eq. (11) then becomes:
z∗ N ∗
σ = Hm (12)
z No
where No is Avogadro’s number and Hm is the molar enthalpy
of solution of one mole of γ  in the γ matrix in equilibrium at
the coarsening temperature. A similar approach has been used
more recently by [58].
Eq. (12) should be considered only a first approximation,
with the following limitations. Firstly the derivation uses only
first-nearest-neighbour energies, and secondly it considers that
the particle is only bounded by {111} interfaces. The potential
importance of second-nearest-neighbour interactions has been
stressed by [59], and related studies on anti-phase boundary
energies have shown that third-neighbour energies may also
be needed [60]. However, first-principles calculations indicate
that, for Ni3 Al and Ni3 Ti, the third-nearest-neighbour energy is
about 1/8th of the value of the magnitude of the first-nearest-
neighbour energy. When combined with the relative number
of such neighbours, this much reduces the difference that
might be expected from taking extra neighbours into account.
70 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74

Table 4 these have been obtained by back-calculation from coarsening

Comparison of calculated and experimental values for the {100} interfacial rate experiments and it is therefore necessary to look in more
energy of binary Al–Ni alloys
detail at the equations used to relate coarsening to the interfacial
Temperature Orientation Surface energy Method Reference energy. A general form of the coarsening equation is given
(K) (hkl) (mJ m−2 ) by [64]:
– 17–20 [70]  1/3
– 42–80 [64] 8Deff Vm σ
k=  (13)
– 16 Nucleation [71] 9G αm (Nβ − Nα )2
– 6–8 Coarsening [66]
900/1000 {100} 14 Coarsening [72] where k is the rate constant, D is the effective diffusion
1073 20–24 Calculated [62]
constant, Vm is the molar volume, Nα,β is the mole fractions

of the relevant phases, and G αm is the second differential of
Table 5 the free energy versus composition curve. For an ideal binary
Coherent interface energy calculations for γ –gamma prime phases in nickel- solution, this can be simplified to:
base superalloys at 1073 K [62]  
8Deff σ Nα (1 − Nα )Vm 1/3
Alloy Temperature (K) Energy (mJ m−2 ) k= . (14)
9(Nβ − Nα )2 RT
Nimonic 105 1073 58
Udimet 700 1073 71 If it is assumed that the solubility limit is very low, the equation
IN 738 1073 76 can be simplified further:
Nimonic PK 33 1073 75
Nimonic 80A 1073 61  
8Deff σ Nα Vm 1/3
Nimonic 90 1073 72 k= . (15)
Nimonic PE 16 1073 91 9RT
Many authors have used Eq. (15) despite the fact that a system
Table 6 such as Ni–Al exhibits appreciable solid solubility and is far
Calculated effect of temperature on the interfacial energy of nickel base from ideal. The use of Eq. (15) has been justified by [64]

superalloys [62] on the grounds that initial calculations of G αm in the Ni–Al
Alloy Temperature (K) Energy (mJ m−2 ) system (based on the thermodynamic data of [65]) appeared
to indicate a low deviation from ideal behaviour in nickel-rich
Nimonic 115 1073 65
Nimonic 115 1173 63
Ni–Al alloys. It was also considered that error bars in the values
Nimonic 115 1273 61 of the other input parameters did not justify being over-precise
Nimonic 115 1373 58 as far as phase diagram data is concerned. This was possibly
Nimonic 115 1473 55 justified at that time, but more accurate free energies are now
available. It is therefore interesting to note that calculated
Objections can also be raised concerning the approximations values of G αm using current characterizations of this system
involved in calculating the relevant values of H from the indicate appreciable deviations from ideality, so it is preferable
available thermodynamic data, especially in multi-component to use Eq. (13).
systems [61]. The method used to derive the calculated values Values of G αm for binary alloys of Ni–Al and Ni–Ti that have
quoted in this section [62] involves perturbing the temperature been derived [62] using the Thermotech Nickel database are
by T and calculating the driving force that now exists indicated in Fig. 28. It is obvious that values of σ calculated
between the phases of the same composition that were in by Eq. (14) or Eq. (15) will be reduced in proportion to the
equilibrium at temperature T . The relevant H is then obtained value of G αm , which could be one of the reasons for the wide
from (dG/dT ) × T , which can be considered a reasonable spread of values obtained in the literature (especially the very
approximation if T is small and should be at least as valid low values quoted by [66]). For further self-consistency, the
as the methods used by [57] and [58]. calculated values of Nα and Nβ should come from the same
Using Eq. (12) yields values for σ of 20–24 mJ m−2 for data set used for the determination of Hm .
Ni–Al binary alloys and 91 mJ m−2 for the multi-component For multi-component alloys, it is not so easy to calculate
superalloy Nimonic PE16. These are consistent with the general G αm , and so the compromise procedure adopted here is to use
magnitude of the values previous reported in the literature (see an average value of G αm from Fig. 28, assuming that the sum of
Tables 4 and 5). For further details regarding the superalloys (Al + Ti) in the alloy is the most important controlling factor.
listed in Table 5 see [62], and for PE16, in particular, see [63]. Clearly, the accuracy of any calculated value of σ will also
Note that it is one of the advantages of the the thermodynamic depend on using a self-consistent set of diffusion coefficients
method that it can also calculate the expected magnitude of the and molar volumes for the other parameters in Eqs. (13)–(15).
effect of temperature on the interfacial energy in such systems As a further exercise in self-consistency, it is possible to
(Table 6). plot the derived values of σ against the lattice mismatch at
It should be noted that the literature values for σ in binary the appropriate temperature, as programmes such as JMatPro
Ni–Al alloys cover a surprising range (Tables 4–6). Most of can provide integrated access to all the required properties,
 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74

Fig. 28. Ratio of calculated non-ideal value of G αm to ideal value of G αm , for
Ni–Al and Ni–Ti binary alloys.
including their temperature dependence. For a more detailed
analysis, see [62].
The above results should be set in the context of
other interfacial energies, especially for interfaces involving
carbides in steels, which exhibit considerably higher values
(250–550 mJ m−1 ) [67,68]. This is not surprising, as these
71
polarization calculation adopted in the present work means that
the magnetization is considered.
Two types of interfaces were considered: (001) with contains
4 cubic L12 γ  -Ni3 Al unit cells and 4 cubic fcc γ -Ni cell
(Fig. 29), and (011) with 4 L12 γ  -Ni3 Al unit cells and 4 fcc
γ -Ni cell cut in the [011] direction (Fig. 30). The 12 × 12 × 6
and 8 × 12 × 8 Monkhost k points are used for (001) and
(011) interfaces, respectively, to provide a higher accuracy in
the [001] direction.
There are two steps in calculating the interfacial energies as
follows:
(1) Calculate the total energy of the supercell with full atomic
relaxations, E tot(a, b, c), with a, b, and c representing the

relaxed lattice parameters and the interface is coincident
with b and c.
(2) Using a supercell with the same size as step 1, calculate the
total energies for the single γ  or γ phase using the fixed
lattice parameters b and c derived in step 1 but allowing a
to be relaxed. Their total energies are denoted by E γ  (a)
and E γ (a), respectively.
The interface energy then can be calculated as:
values also contain contributions from a higher misfit energy  
as well as grain-boundary dislocations. As a general approach 1

σ = E tot (a, b, c) − E γ  (a) + E γ (a) 2S (16)

to calculating the energy of complex interfaces is still in its
infancy, such energies tend to have large error bars and are still
mostly obtained by fitting procedure [69].
3.1.2. First-principles calculations for the interfacial energies
between γ  -Ni3 Al and pure Ni
The interfacial energies between γ  -Ni3 Al and γ -Ni at zero
Kelvin have been calculated recently [73,74]. These authors
used the Vienna ab initio simulation package (VASP) [75]
with ultrasoft pseudopotentials and the generalized gradient
approximation (GGA) [76]. Energy cutoff was determined
by the choice of “high accuracy” in the VASP. The spin
2
where S represents the area of the interface.
The calculated energies are summarized in Table 7. Our
calculated interfacial energies are 39.6 mJ m−2 for the (001)
interface and 63.8 mJ m−2 for the (011) interface. Wolverton
and Zunger [77] calculated the formation energy of Ni7 Al in the
D7 structure that can be viewed as alternating planes of Ni3 Al
and Ni4 in the [111] direction. By this calculation, they gave an
estimated energy of 33 mJ m−2 that is considerably lower than
the value of 63 mJ m−2 for the (100) direction by Price and
Cooper [78] calculated using the LMTO method.

Fig. 29. Supercell used to model the 100 interfacial boundary between γ  -Ni3 Al and γ -Ni.

Fig. 30. Supercell used to model the 110 interfacial boundary between γ  -Ni3 Al and γ -Ni.
72 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74

Table 7 Table 9
The calculated interfacial energy between γ  -Ni3 Al and γ -Ni (mJ m−2 ) Calculated (100) interfacial energy at 0 K between Ni3 Al and γ -Ni with various
Al contents (mJ m−2 )
Source {100} {110}
at.% Al in γ -Ni (100) interfacial energy
This work 39.6 63.8
Price and Cooper [78] 63 0 −43
5 −2
10 34
Table 8 15 57
Calculated enthalpy of formation, H f (J/mol), lattice parameter, a (Å), bulk
modulus, B (GPa) and elastic constants, C11, C12, C44 etc. (GPa) of L12 Ni3 Al
For the calculation of interfacial energy, a supercell
and B2 NiAl compounds using the present MEAM interatomic potential, in
comparison with experimental data composed of equal amounts of γ -Ni and Ni3 Al and involving
an interface between the two phases at a given orientation
Property Ni3 Al NiAl
is prepared, as has been shown in Figs. 29 and 30. When
MEAM Experimental MEAM Experimental
the γ -Ni is not pure Ni, in order to minimize the statistical
H f 42 100 42 100a * 65 300 64 000–66 100a error, a large size of supercell (40 × 20 × 20 unit cells) is
*
a 3.567 3.567b * 2.866 2.886b used. Then, the internal energy of the supercell is calculated
B 181 177c 160 158c allowing atomic relaxation. This energy is compared with the
C11 254 230c 200 199c * average energies of γ -Ni and Ni3 Al samples of the same size,
C12 145 150c 140 137c * calculated by maintaining the same lattice parameters with
C44 136 131c 117 116c
the supercell in the two directions parallel to the interface
The property values that were used for parameter optimization are marked with but allowing relaxation into the direction perpendicular to the
“*”.
a [82]. interface. To remove any surface effects, a three-dimensional
b [83]. periodic boundary condition is applied in all calculations. Due
c [84]. to the periodic boundary condition, it should be regarded that
the supercell shown in Figs. 29 and 30 involves two interfaces.
3.1.3. Calculation of interfacial energies between γ  -Ni3 Al and The interfacial energy can then be obtained by the following
γ -Ni solid solutions equation:
An attempt to compute the interfacial energy between
γ  -Ni3 Al and γ -Ni has now been made using an atomistic
approach (molecular statics) based on a semi-empirical
interatomic potential. The interatomic potential used was
the second-nearest-neighbor modified embedded atom method
(2NN MEAM) potential [79,80]. The MEAM for an alloy
system is based on the MEAM potentials for composing
elements. In the present work, the (2NN) MEAM parameters
for Al and Ni were taken from Lee et al. [81] without any
modification. In the MEAM [81], the values of nine model
parameters should be determined to describe a binary alloy
system. Out of the nine model parameters, the following
three, E c , re , B, are the most decisive. The E c , re and
B parameters give effect to enthalpies of formation, lattice
parameters and bulk modulii of individual phases in the relevant
alloy system, respectively. Ideally, it is expected that this
method should reproduce all the known physical properties
of individual phases using one set of model parameters. In
practice, some phases with relatively simple atomic structures
are selected, and the parameter values are determined by fitting
to the known physical properties of the selected phases. In
the present study, for the Al–Ni alloys system, the B2-ordered
NiAl compound and the L12 -ordered Ni3 Al compound were
selected, and experimental data on the enthalpies of formation,
lattice parameters, and elastic constants for the two phases were
used to determine the model parameter values. In Table 8, the
property values for NiAl and Ni3 Al phases calculated using the
present MEAM potential are compared with experimental data.
The property values that were used for parameter optimization
are marked with a “*”.
 
1
σ = E supercell − E Ni + E Ni3 Al 2A (17)
2
where A represents the area of the interface. It was found
that the interfacial energy of the (100) interface calculated in
this way strongly depends on the composition of γ -Ni (see
Table 9). The individual calculated values in this Table are
average values of ten calculations using differently generated
random solutions of the fcc γ -Ni phase. The negative value
calculated for the interfacial energy between pure nickel and
Ni3 Al is another way of expressing that, in the presence of
pure nickel, Ni3 Al would dissolve to form a solid solution of
lower energy than the two-phase mixture. The Al content of
γ -Ni in equilibrium with Ni3 Al at 1073 K is about 15 at.%.
Therefore, if the temperature dependence of the interfacial
enthalpy can be assumed to be small, then the calculated value
for the Ni–15%Al can be regarded to be close to the interfacial
enthalpy between Ni3 Al and γ -Ni at 1073 K. It should be noted
here that the quantity computed in this study is the interfacial
enthalpy not the free energy. Because the interfacial entropy
would have positive values, the calculated values in Table 9
should be regarded as upper limits of interfacial energies at
individual temperatures where the equilibrium Al contents
in γ -Ni with Ni3 Al correspond to the given Al percentage
values.
3.1.4. Concluding remarks on calculation of interfacial
energies
All three approaches described here yield low interfacial
energy values (<100 mJ m−2 ) for the interfaces between
 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
γ  -Ni3 Al and γ -Ni, in qualitative agreement with experimental
information (6–80 mJ m−2 ). In a situation where accurate
experimental data are not available and current first-principles
calculations can show a scatter of more than 50%, it does
not seem reasonable to compare the accuracy of individual
approaches. However, each method has its own definite
advantages. The thermodynamic approach can provide a
good estimation for wide range of multi-component materials
systems. The semi-empirical approach can consider anisotropy
of interfaces, misfit strain effects, segregation effects, as well
as the chemical effects, and can be used for simulations of the
early stages of nucleation. As the most fundamental approach,
the first-principles calculation [85] should ultimately provide a
reference value for the other approaches.
4. Conclusions
The examples presented in this paper show that computa-
tional thermodynamics has evolved to a point where complex
material thermodynamics problems can be solved with relative
ease. Furthermore, the coupling of diffusion modeling with the
conventional computational thermodynamics is making possi-
ble the solution of many problems that are important to the un-
derstanding of phase evolution in materials. One can foresee the
availability of tools that efficiently predict microstructure with a
minimum of guesswork and fitting constants, but two important
questions must be considered. Firstly, although computational
thermodynamics is now a mature discipline, its dissemination
as an everyday tool to the materials engineer has been slow.
One possible reason is the fact that a significant part of the
syllabusi for thermodynamics courses in engineering education
today still focus on problem-solving techniques that pre-date
computational thermodynamics and are self-limiting in the ap-
plications that can then be handled. One possible way of con-
tributing to the reduction of this gap would be a discussion of
how to change engineering curricula in order to include more
familiarity with the modern calculation methods now available,
without neglecting the essential axioms of thermodynamics.
These clearly remain unchanged, regardless of the calculation
tools available.
A second important observation relates to the need for
data. Thermodynamic methods rely on data. As computational
thermodynamics evolves from “bulk thermodynamics” to the
prediction of microstructure and its evolution, more extensive
data on important properties such as interfacial and strain
energies will be necessary. While proven approaches for
deriving these values from the application of kinetic theories to
experimental data might continue to be used, it will seriously
limit the ability to make predictions and extrapolations, one
of the strengths of computational thermodynamics. More
advanced calculation techniques, as discussed in the last section
of this paper, might be the only solution to derive the necessary
properties and also avoid interference by other unforseen
factors.
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