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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).
1. Introduction each problem are highlighted: (a) the definition of the “real”
problem; (b) when simplifications are needed, and the rationale
The last few years have seen a dramatic advance in behind the selection of the relevant part of the problem; and (c)
computer technology, yielding a tremendous increase in the thermodynamic formulation of the problem. The results are
the calculation power available to the PC user. Over the then presented and critically evaluated.
same period, CALPHAD (Computer Calculation of Phase It is hoped that this form of presenting problems may help
Diagrams) techniques have evolved from just performing in several different aspects; firstly, to help identify the basic
complex equilibrium calculations relevant to materials science knowledge necessary for the efficient use of these techniques;
to simulating phase transformations involving diffusion. Both secondly, to accelerate changes in curricula that will make it
tasks can now be performed quickly and efficiently and produce easier for the next generation of students to use these tools;
very good results. This has a large effect on the ability to solve and thirdly to appreciably reduce the time and effort presently
complex problems in several key areas: materials processing, used on teaching how such problems are solved by less efficient
the prediction of material behavior under industrial conditions, methods.
and supporting the design of new materials.
Since 1997, the series of Ringberg Workshops on 2. Selected application examples
Computational Thermodynamics have produced two reports
on the status and evolution of “Applications of Computational One of the important aspects when applying computational
Thermodynamics” [2,3]. The first report focused on reviewing thermodynamics to the solution of a real problem concerns
applications and highlighting the development needs in each the effect of time. As thermodynamics is concerned with
area of application, whereas the second report, while also equilibrium, one must decide how the information on
reviewing applications, attempted to formulate the review in equilibrium will be used. If one expects the system to come
the form of questions and answers in an attempt to improve sufficiently close to equilibrium in the time-frame relevant
the interface between the final user and the providers of to the problem, or if the interest is in evaluating what can
thermodynamic and allied property information. happen in a given system, then time-independent calculations
This reflects the observation that properly translating the are sufficient. If, however, the time available for the processes
conditions of a “practical” problem into a well-formulated to occur is not long enough for equilibrium to prevail, either a
thermodynamic or diffusion problem (within the limitations of time-dependent solution is used or the equilibrium information
the CALPHAD technique) is not a trivial question. One source has to be considered with additional care. For this reason, the
of difficulties in communication between users and providers examples are grouped, taking into consideration the effect of
has traditionally been ascribed to the user–software interface, time on their solution.
but it is the opinion of the authors that more fundamental
questions are probably just as relevant as, or more important 2.1. Time-independent problems
than, problems related to the user–software interface. This
has been confirmed in recent years, as much more user- 2.1.1. Aluminum deoxidation of steel [6]
friendly graphic interface versions of calculating software has Practical and experimental results indicate that the
become available. This has made it more evident that the real deoxidation of liquid steel using aluminum is a fast process,
difficulties experienced by end-users lie in formulating the where equilibrium is reached in a very short time. Thus,
correct questions, as well as interpreting the results of the time-independent equilibrium calculations are sufficient in this
calculations. case. Without taking into consideration aluminum losses, the
It is apparent that part of the problem is related to difficulties amount of aluminum required for steel deoxidation is defined
in understanding the thermodynamic concepts involved in the by the initial oxygen content of the steel to be deoxidized and
problems of interest. If that is true, the best route to achieving the acceptable oxygen content at the end of the deoxidation
more efficient utilization of the current generation of novel process. The classical solution to this problem is a two-
techniques lies in paying more attention to the education and step calculation: first, the aluminum dissolved in the steel
training of the potential users in the relevant areas. at the end of the deoxidation process is calculated, using
Computational thermodynamics has already been success- the oxide solubility product at the deoxidation temperature
fully introduced as an educational tool in several programs and (here, knowledge of the oxide to be formed is necessary);
schools [4,5]. In addition, user courses are offered by virtu- then the aluminum consumed in forming oxide is calculated
ally all the commercial software suppliers. However the avail- based on the oxide stoichiometry, as indicated in Fig. 1. The
ability of these advanced software tools has not yet produced strategy of breaking down the aluminum addition into two
much change in the way the thermodynamics, physical chem- parts is only necessary because of the information used for the
istry and diffusion courses are taught. Although the impact of calculation.
such tools on the relevant curricula was foreseen many years Unfortunately, this strategy does not help the understanding
ago [1], change in these curricula has been extremely slow. of the equilibrium issue. This is a consequence of the classical
The present account is aimed at providing examples from approach to the problem. A different approach can be proposed
the background experience of the participants of this group that if a tool that calculates equilibrium is available. In this case,
may help to rectify this situation. The critical steps in solving 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 55
Table 1
Calculation procedure to define the aluminum addition required for steel deoxidation [6]
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 Calculation result
(a) First step: steel without silicon. Conditions to be fixed (F = 4 = C + 2): (a) Phases present: 1000 kg of liquid steel with enthalpy
= 1.34 × 109 J
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): (b) Phases present: Solid Si (DIA) and FeSi enthalpy
= −1.46 × 106 J
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): (c) Phases present: 1.0043 × 106 g of liquid steel
containing %Si = 0, 3T = 1870.31 K (1597.16 ◦ C)
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. 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 pressure of water in the atmosphere, one could get just the same
diagram. The calculations have been done using the SGTE pure set of lines as in Fig. 3(a), giving a false impression that CH4 is
substance database (SSUB) [15], at a temperature of 1100 ◦ C, not affecting the oxygen potential of the atmosphere.
which is a typical value of sintering temperature. Secondly, a breakdown point can be clearly seen in Fig. 3(b),
The abscissa of Fig. 3(a) (inlet pH2 O ) represents the at a water content that is the same as the CH4 content of
water content of the atmosphere before entering the furnace, the gas. For sintering atmospheres with water content higher
i.e. before it reaches equilibrium with the remaining species. than that value, this hydrocarbon has almost no effect on
However, for these N2 –H2 atmospheres, this value is almost the oxygen potential; hence the reduction capability of these
the same as the actual water partial pressure in the atmosphere atmospheres is controlled by the water content, as if no CH4
at the temperature of the calculation. were present. However, when the water content is lower than
The calculation of these curves has been performed using that of CH4 , the oxygen potential is sharply reduced by several
the following procedure: it is convenient first to redefine the orders of magnitude. For atmospheres with a low H2 content,
components; instead of H, O, N, we use H2 O, N2 , H2 . The saturation is produced due to the carbon activity reaching values
conditions for the calculation are a total pressure of 1 bar, higher than unity (labeled “sooting” in Fig. 3(b)); here, the gas
temperature, a total amount of 1 mole, N2 /H2 ratio (a different composition (the CO/CO2 ratio, and hence the oxygen activity)
constant value for each curve: 99/1, 95/5, 90/10, 60/40, 20/80 is controlled by the Boudouard reaction,
and 1/99), and a certain oxygen activity. The oxygen activity
C + CO2 = 2CO.
is varied and the calculation repeated several times, i.e. the
value is used as the “stepping” condition in the calculation. The lines plotted in Fig. 3(b) have been calculated following the
The abscissa (inlet pH2 O ) is the mole fraction of the component same approach as with Fig. 3(a): the components defined are
H2 O which, as mentioned above, is almost the same value as CH4 , H2 O, N2 and H2 , instead of C, H, O and N. The conditions
the actual mole fraction of the species H2 O in the gas mixture for the calculation are a total pressure of 1 bar, temperature, a
at equilibrium. total amount of 1 mole, N2 /H2 ratio (a different value for each
Additions of hydrocarbons such as CH4 to the sintering curve: 99/1, 95/5, 90/10, and so on), the CH4 quantity (mole
atmospheres are intended to control the carbon content of fraction 0.001), and a certain oxygen activity, whose value is
the sintered parts. However, even small quantities of CH4 used as the “stepping” condition in the calculation.
can change the oxygen potential of the atmosphere. This was In addition, several horizontal lines have been plotted in
illustrated by Ortiz et al. [13,16] and is shown in Fig. 3(b) Fig. 3(a) and (b). They represent the oxygen potential for
for several N2 –H2 sintering atmospheres with a small addition metal/oxide equilibria, of several metals used in sintering (Fe,
of CH4 (0.1%), compared to the same atmospheres without Cr, Mn and the powder Astalloy CrM), at the temperature of
methane (Fig. 3(a), and the dotted lines in Fig. 3(b)), at the the calculation. They give an indication of the atmosphere’s
same temperature of 1100 ◦ C. Several features can be stressed capability for the reduction of the metal oxides.
in this Fig. 3(b): first of all, the abscissa represents the water The carbon activity of these atmospheres is represented in
content of the gases entering the furnace, i.e. before reaching Fig. 4, showing the conditions for methane decomposition with
the equilibrium; if one represents the equilibrium partial carbon formation (sooting).
58 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 extrapolation from the binary subsystems [32]. Fig. 8 shows
by addition of whiskers, fibers and platelets of SiC to Si3 N4 . the isothermal section in the Si–C–N system applicable for
Also, the use of precursor polymers has attracted wide attention temperatures 1757 K < T < 2114 K and a total pressure
as an alternative approach to produce Si3 N4 –SiC ceramics and of 1 bar. The composition of a precursor-derived Si–C–N
offers a number of advantages compared to classic powder ceramic (PHMS) is indicated for discussion in the following
technology [29]. With the synthesis of Si–C–N ceramics from sections. The isothermal section shows a silicon nitride–silicon
precursor polymers, one can control the materials composition, carbide–nitrogen gas (Si3 N4 –SiC–N2 ) phase field indicating
structures and properties on an atomic scale. To predict and the stability of Si3 N4 –SiC ceramics. At temperatures lower than
control the sintering conditions for all types of Si3 N4 –SiC 1757 K, SiC and nitrogen react to form Si3 N4 and graphite. At
ceramics, thermochemical calculations can be used. temperatures higher than 2114 K, silicon nitride decomposes
The stability and decomposition of silicon carbide–silicon and forms liquid silicon and nitrogen. A detailed analysis of
nitride (Si3 N4 –SiC) ceramics during the sintering process were the system thermodynamics shows that the nitrogen partial
investigated by thermodynamic calculations. Thermodynamic pressure has to be changed simultaneously with the heating or
descriptions for the Si–C and Si–N systems were accepted cooling of the furnace during the sintering process to stabilize
from the literature [30,31]. The data for C–N gas species were the microstructure of the ceramic materials. The calculated
taken from the database of the Scientific Group Thermodata “ pN2 -temperature” potential diagram in Fig. 9 provides general
Europe (SGTE) [15]. Isothermal sections were calculated by 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. 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.
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).
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.
2.1.10. Interface reaction of yttrium silicates with SiC-coated 2.2. Time-dependent problems
C/C–SiC composites in heat shield applications
Yttrium silicate coatings are potential candidates for When the time available for the processes to occur is not
the oxidation protection of SiC-pre-coated C/C–SiC heat long enough for equilibrium to occur, either a time-dependent
shields for space shuttle systems. Plasma wind tunnel tests solution is used or the equilibrium information has to be
showed that they can withstand temperatures of 1650 ◦ C, considered with additional care. This section discusses some
but at temperatures higher than 1750 ◦ C the coatings fail examples of the application of computational thermodynamics
because of blister formations and subsequent spallation of the 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 Fig. 18(a). Solidification modeling of M2 high-speed steel using different
2000 K. techniques. Experimental values of T solidus are indicated [38].
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
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.
φ
where x i (i = 1, 2, . . . , c) denote the atomic fractions of each From the point of view of growth, a still supersaturated matrix
component i in phase φ (φ = xt → crystal; liq → liquid) surrounds the nuclei just formed. That is, there is an initial
φ
and μi denote their chemical potential at temperature T . Nuclei growth transient, for each individual grain, in which the local
form with a critical radius r ∗ given by equilibrium between the emerging crystal and the liquid ahead
of the crystal–liquid interface is established (with composition
2σ a
r∗ = . (4) c∗ ), as shown schematically in Fig. 24. Afterwards, diffusion
G T becomes the controlling mechanism. During the growth
Interface controlled growth will lead to a growth rate u(T ) transient, the interplay between interface- and diffusion-limited
given by growth acts in a way to increase the importance of the
latter mechanism until it becomes preponderant. The simplest
2λD(T ) G T
u(T ) = 1 − exp − . (5) approach is to assume that the transient is interface-controlled,
2 a RT
whereas the second stage of individual grain growth, in the
Here, λ is the product of the fraction of surface sites where extended view, i.e. neglecting spatial impingement between
atoms are preferentially added and the length of the interface grains, is diffusion-controlled [51].
in units of the mean atomic radius. Since both D and G T in Eq. (5) change in the course of the
The kinetics of the process can be viewed in the following transformation, the interface-controlled growth rate is evaluated
manner. At any time, t, the transformation proceeded up by multiplying the growth rate obtained from Eq. (5) by the
to a fraction, ξ · f 1 , of the total volume, V , where f 1 is factor ϕ[x(t)] from Eq. (8).
the total volume fraction available for primary crystallisation When solute fluxes through the interface are driven by
and ξ is the actual degree of advancement of the process. steady-state diffusion, the growth rate of an isolated growing
The Kolmogorov–Johnson–Mehl–Avrami formalism [47–50] grain with radius R under spherical symmetry in this steady-
allows the evaluation of the rate of the transformation, since state regime is given, for a binary system, by [43],
it has been shown [43] that the Avrami equation
dR Ds f 1
ξ = 1 − exp(−ξex ) (6) = {ϕ[x(t)]}2 (9)
dt R
where ξex is the extended degree of advancement of the where ϕ 2 accounts for soft impingement (overlapping of
transformation, remains valid for a primary crystallisation diffusion fields).
process, provided that the temperature dependence of f 1 may be In a multicomponent system, each of the elements has
neglected in the transformation temperature interval. The mean its own diffusion coefficient, and consequently the different
concentration of the matrix is then given by elements will generate different concentration gradients. The
cio − cixt general solution in this case has been reported [3]. In the
cit = cixt + (7) following, Ds will be considered as an effective diffusion
1 − ξ f1
coefficient to deal with multicomponent systems.
where cio is the initial composition of the parent phase. As an example the primary nanocrystallization of a
That is, the nucleation frequency depends on the degree FINEMET alloy glass with composition Fe73.5 Cu1 Nb3 Si17.5 B5
of advancement of the process. In a first-order approach [43], is discussed in terms of these considerations. The goal is to
the expected decrease in the actual nucleation frequency establish the limits inherent to the approach to get estimated
is evaluated by multiplying the homogeneous nucleation values of both the interfacial energy and the apparent diffusion
frequency I (T ) from Eq. (3) by the factor ϕ[x(t)] given by coefficients, D and Ds , from experimental kinetic data.
1 − x(t) The details of alloy preparation and characterization of the
ϕ(x) = . (8) nucleation and growth processes are given elsewhere [43].
1 − ξ x(t)
68 A. Costa e Silva et al. / Computer Coupling of Phase Diagrams and Thermochemistry 31 (2007) 53–74
activation energy of the overall primary nanocrystallization (1) a classical thermodynamic approach;
has to be maintained. This is the main reason for the narrow (2) a first-principles calculation; and
range of deduced values for σ that are consistent with the (3) a semi-empirical atomistic approach based on the modified
experimental transformation rates. Consequently, the indicated embedded atom method (MEAM) interatomic potential.
modelling procedure is quite suitable for obtaining indirect
evaluation of the interfacial energy between the nanocrystals of 3.1.1. Thermodynamic method for the calculation of interfacial
α-(Fe,Si) with DO3 structure embedded in a disordered matrix energies for γ /γ phases in binary and multi-component nickel-
with global Fe73.5 Cu1 Nb3 Si17.5 B5 composition. base alloys
It is worth mentioning that there is a spread in the The overall value of any interfacial energy contains many
experimental values obtained, clearly seen in Figs. 26 and 27 contributory factors, including:
when several curves are shown for the kinetic transformation
(a) a chemical contribution;
at a fixed heating rate. However, it is clear that the modelling
(b) a strain energy contribution;
is better at reproducing the earlier part of the transformation
(c) the presence of dislocation arrays;
than its end. To obtain better results in the later stages probably
(d) the presence of chemical segregation.
requires a more refined analysis of the impinging stage for
diffusion-controlled growth. To improve the analysis, reliable The γ /γ phase transformation in nickel alloys exhibits
values of the supersaturation in the remaining matrix are also a small lattice misfit, which minimises any strain energy
needed. Furthermore, it is important to notice the limitation contribution. This, in turn, also minimises the presence of
in the coupled derivation of parameters from the kinetic data; interface dislocations, which reduces the potential degree of
clearly, the ability to make predictions would greatly benefit segregation to the boundary. We can therefore expect that the
from an independent determination of values for interfacial interfacial energy for this transformation in such systems will
energies as well as diffusion data. be dominated by the chemical term.
The simplest thermodynamic approach for the calculation of
3. Limitations to current applications — evaluating interface energies follows the work of [42], who assumed that,
interfacial energies in the case of liquid–solid interfaces, the value of σ for pure
metals scales with the difference in enthalpy:
The examples above show that progress in computational
thermodynamics is making it possible to solve materials- σ = αHm . (11)
related problems with a complexity that could only be tackled
This approach has also been used successfully in studies
conceptually a decade ago. However, as one proceeds to
related to the relative nucleation of competing phases from the
formulate and solve these problems, the limited extent of the
liquid [56].
data that is available becomes evident. The last few decades
A theoretical justification for such an approach has been
have seen a dramatic evolution in the amount and quality of
given by [57], which relates α to z ∗ (the number of atoms
assessed thermodynamic data that is included in the available
per unit area of the interface), N ∗ (the number of cross bonds
databases [21,54]. More recently, the same has happened with
per atom at the interface), and z (the co-ordination number
diffusion data needed to address transformations in alloys [21,
of nearest neighbours in the lattice, which equals 12 in FCC
55]. Bulk thermodynamic and diffusion data are insufficient,
structures). Eq. (11) then becomes:
however, to properly predict important microstructure features,
as well as their evolution. In particular, interfacial and z∗ N ∗
strain energies are important in defining phase nucleation σ = Hm (12)
z No
and morphology. The following section demonstrates how
where No is Avogadro’s number and Hm is the molar enthalpy
tools currently available in computational thermodynamics and
of solution of one mole of γ in the γ matrix in equilibrium at
related fields can contribute to the quantification of these
the coarsening temperature. A similar approach has been used
important variables.
more recently by [58].
3.1. Computation of interfacial energies using thermodynamic, Eq. (12) should be considered only a first approximation,
first-principles and semi-empirical atomistic approaches with the following limitations. Firstly the derivation uses only
first-nearest-neighbour energies, and secondly it considers that
Nucleation kinetics is one of the key issues in the theory of the particle is only bounded by {111} interfaces. The potential
phase transformations where a proper quantitative approach is importance of second-nearest-neighbour interactions has been
limited by the lack of data for interfacial energy between the stressed by [59], and related studies on anti-phase boundary
matrix and precipitating phases. Recent progress in atomistic energies have shown that third-neighbour energies may also
approaches shows some feasibility of providing the necessary be needed [60]. However, first-principles calculations indicate
information. In the present review, an attempt will be made that, for Ni3 Al and Ni3 Ti, the third-nearest-neighbour energy is
to compute the interfacial energy between γ (Ni-rich fcc) and about 1/8th of the value of the magnitude of the first-nearest-
γ (L12 Ni3 Al) phases in the Ni–Al binary system using three neighbour energy. When combined with the relative number
different approaches, and then to compare the results. The of such neighbours, this much reduces the difference that
methods used in the present work are: 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
(1) Calculate the total energy of the supercell with full atomic
relaxations, E tot(a, b, c), with a, b, and c representing the
Fig. 28. Ratio of calculated non-ideal value of G αm to ideal value of G αm , for
relaxed lattice parameters and the interface is coincident
Ni–Al and Ni–Ti binary alloys. with b and c.
(2) Using a supercell with the same size as step 1, calculate the
including their temperature dependence. For a more detailed total energies for the single γ or γ phase using the fixed
analysis, see [62]. lattice parameters b and c derived in step 1 but allowing a
The above results should be set in the context of to be relaxed. Their total energies are denoted by E γ (a)
other interfacial energies, especially for interfaces involving
and E γ (a), respectively.
carbides in steels, which exhibit considerably higher values
(250–550 mJ m−1 ) [67,68]. This is not surprising, as these 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
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
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