International Journal of Thermal Sciences 159 (2021) 106608

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International Journal of Thermal Sciences

journal homepage: http://www.elsevier.com/locate/ijts

Phase change modelling with flexible source-based kinetics for

non-equilibrium transitions
Amin Ramiani Jafari
Department of Materials and Metallurgical Engineering, Amirkabir University of Technology (Tehran Polytechnic), No.424 Hafez St., 15916-34311, Tehran, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, a modeling approach is developed to cope with the phase-change problems having deviations from
Modelling equilibrium conditions. The mathematical model is based on continuity and enthalpy conservation equations.
Heat transfer The core of the model is a source term of continuity which governs the rate of phase change. The formulation of
Phase change
the source term is originally proposed with an infinite series, i.e. an iterative rate-tuner, which accounts for both
Kinetics
Solidification
equilibrium and non-equilibrium phase changes. As the model tracks equilibrium transitions by the stand-alone
Enthalpy method rate-tuner, off-equilibrium paths are described by regulations of the rate-tuner. The model also resolves
undercooling-superheating of phase change materials with a feature tackling nucleation-growth-transition using
an interphase-detector-function. In order to evaluate the model, a computational program was developed from
the equations discretized with finite volume method. The paper presents implementation of the code in three test
problems; Test-case-I employs a typical Stefan problem, i.e. melting of an ice bar in equilibrium condition, which
verifies the model with the exact solution. Test-case-II simulates the ice bar under periodic heating/cooling at its
end, so that non-equilibrium melting/freezing arises at the end of the bar. Depths and fractions of the phase
change are graphed versus the frequency of heating/cooling cycles and the rate-regulator parameter. A spectrum
of kinetic behaviors is presented, depending on the rate-regulator parameter. Three kinetic behaviors are
distinguished, namely; extremely fast (instantaneous equilibrium), intermediate (non-equilibrium) and
extremely slow (bypassed, highly-restricted-rate). Finally, test-case-III deals with a non-equilibrium solidification
in a real case (sodium-acetate-trihydrate) that exhibits undercooling and recalescence due to nucleation-growth
kinetics. The model successfully predicted temperature history curves in comparison with experimental data. The
model is a step toward enhancing our computational tools for non-equilibrium phase changes in advanced
material processing like additive manufacturing, casting, welding, solidification and energy storage systems.

1. Introduction they need more attention.

Advanced materials processing and applications, e.g. additive
manufacturing, laser processing, induction melting and energy storage
systems, deal with a vast range of temperatures and hence involve
multiple phase changes of mixtures of materials. For instance, melting,
evaporation, ionization and solidification take place simultaneously by a
short pulse of laser in additive manufacturing. Such a process exhibits
fast and complex physics which is hard to capture and measure
furthermore. To understand, simulate and predict those processes,
mathematical models are required to be able to manage multiple non-
equilibrium phase-changes of materials. Continuum transport volume
average models with enthalpy method are perhaps the best candidate as
they have been frequently utilized in this concern. However, facing non-
equilibrium phase-changes, those models have shown difficulties and
Mathematical models of volume average partial-differential trans­
port equations for multiphase problems have been evolved for about
four decades [1]. For the meantime, Bennon and Incropera [2–4], Pre­
scott, Incropera and Bennon [5], Wang and Beckermann [6–8] and Ni
and Incropera [9–11] developed continuum models to cope with
phase-change problems in a detailed and physically-realistic manner.
Those models describe multi-scale and multi-phase transports of mass,
momentum, energy and species, with interfacial thermodynamics, ki­
netics and morphology. It has been a thorough application of classical
mechanics, and so much detailed that researchers believed even the
fast-growing computational instruments will not be able to execute
those models in full capacity until many years [12]. In partial capacity
however, several researchers have addressed examples of successful
implementation of phase change models in some specific problems

E-mail address: ajafari@aut.ac.ir.

https://doi.org/10.1016/j.ijthermalsci.2020.106608
Received 14 June 2019; Received in revised form 29 July 2020; Accepted 26 August 2020
Available online 15 September 2020
1290-0729/© 2020 Elsevier Masson SAS. All rights reserved.
A.R. Jafari International Journal of Thermal Sciences 159 (2021) 106608

[13–17]. Ludwig, Kharicha and Wu [18] have reviewed some case 2. Mathematical modelling
studies including continuous casting, two-phase flow patterns, solidifi­
cation dendrite evolutions and macrosegregation. Realistic simulation of 2.1. Conservation equations
dendritic solidification in macro-micro scale has been received a
promising progress [13,19–21] and can be performed as an A representative elementary volume (REV), as shown in Fig. 1, is
interfacial-diffusion-controlled phase change. Multiple phase-changes considered, containing phase k, occupying a volume fraction εk and in
volume average models have been also implemented [20]. An effec­ interactions with another phase l. In order to focus on thermodynamics
tive part of these models is kinetics involved to find the rate of and phase change modelling, it is assumed in this paper that the problem
phase-changes. The amount of each phase is quantified by an equation of is governed by macroscopic heat diffusion and no advection occurs. It is
continuity and its source term accounts for phase-change rate (PCR). also assumed that thermophysical properties, in each phase, are con­
The source terms simulate, for instance, solid nucleation and colum­ stant. For this matter, volume average two-phase heat and mass transfer
nar/equiaxed dendritic growth in conjunction with transports of heat results in equations of continuity and mixture enthalpy as follows [1,4,
and solute elements. Nevertheless, the advanced models still have a 25]:
shortfall of high cost or being cumbersome in practical cases [19].
∂(εk ρk )
Whenever a simulation on a different material is asked, separate = Γ lk (1)
∂t
research and enough proficiency is required to deal with sophisticated
formulations of nucleation, growth, morphology, interphase and other ( )
∂ ρh ( )
issues in the advanced models. Moreover, there is still considerable = ∇ ⋅ k∇T + SΓ (2)
ambiguity in the numerical behavior of the models (i.e. stability, ∂t
convergence, consistency, discretization error and computational cost),
where the over-bars stand for mixture variables which are defined as
since it is strongly depends on those highly-nonlinear source terms.
follows:
Without the kinetics features, on the other hand, the models are defec­
∑
tive. For instance, although apparent heat capacity or basic enthalpy ρ= εk ρk
methods [22,23] are widely applicable, they dictate the amount of each ∑k
/∑
phase at a predefined temperature (or range of temperatures). There­ c= εk ρk ̂c k εk ρk
fore, those are not able to predict metastable phases and kinetics, e.g. ∑k k
(3)
imposing a temperature jump/drop in the model will not lead to a k= εk kk
superheating/undercooling or metastable-phase. In real phase change k
∑ /∑
systems, however, undercooling and metastable phases are frequently h= εk ρk 〈hk 〉k ε k ρk
observed and not ignorable in many cases. It might be the main reason
k k

that engineering software relies too heavily on user-defined modellings The dependent variable of the energy equation (2) is mixture sensible
[24] for phase change problems. Taken together, there seems to be a gap heat, h. The intrinsic volume average sensible heat
in the middle of available solutions, where the models would have both 〈hk 〉k = V1k
∫ ∫T
c dT dV has been considered to be k
c
k k
Vk 0 k 〈h k 〉 ≈ < ̂ k > 〈T k〉 ,
efficiency and kinetic features simultaneously.
where dissipation terms are neglected from the assumption of constant
The aim of the current research is to redesign a phase-change model
specific heat in each phase. Total heat content of each phase involves
with a control on phase-change-rate. The concept and formulations of
reference enthalpy and sensible heat of the phase as 〈Hk 〉k = href k
k + 〈hk 〉 .
the mathematical model have been proposed in section 2 in four sub­
sections; conservation equations, phase-change rate, non-equilibrium The reference enthalpy (i.e. the latent heat), on the other hand, has been
rate and nucleation-growth considerations. In section 3, three bench­ appeared in equation (2) as a phase-change heat source term:
mark problems are drawn to test the performance of proposed model. (
SΓ = Γlk href ref
)
= Γlk Δhref (4)
l − hk
The numerical methodology and discretization, used to solve the prob­
kl

lems, have been explained. Subsequently in section 4, the numerical Other source of heat would be involved if there was any of them in
results have been presented and discussed. Main remarks have been application, e.g. a laser heating power or electromagnetic Joule effect.
concluded finally. However, the only energy source term considered in this paper is the
phase change heat source SΓ and the current study is mainly concerned

Fig. 1. A representative elementary volume (REV) containing phase k, occupying a volume fraction of εk which has gone off-equilibrium and undertaken the phase
change k→l, e.g. melting. The right REV is a volume average representation of the left one.

2
A.R. Jafari International Journal of Thermal Sciences 159 (2021) 106608

with Γ lk ; the source term of the continuity equation (1). It should be thermodynamics does not give information about rate and kinetics, it
mentioned that REV internal heat transfer has been excluded from this does give the distance between current state and the equilibrium state.
paper. The interphase temperature has been assumed to be equal to the That distance can be used to derive the corrections. Thus for ΔKkl , it is
average temperature Tkli ≈ T, which has been discussed in section 4. suggested to use increments of mass exchanged in the time-step ac­
The term Γ lk is well known as interfacial mass-transfer-rate (MTR) cording to the distance from equilibrium. The participation of
which will be also referred as phase-change rate (PCR) hereafter. A exchanged mass Δm has been illustrated in Fig. 2. Two unstable situa­
phase change takes place either forward k→lor backward k← l. With the tions have been imagined for an interphase of k-kind at Tkli as shown in
former, L-phase is generated, Γkl takes a positive value and the material the figure. At state (1) an amount of interphase-k, mk , is situated at a
flows outward across the boundaries of k-phase, i.e. (vikl − vk )⋅ nilk > 0. superheated temperature Tkli from a solution of the energy equation. It
MTR is defined as [25]: has been already deviated from the equilibrium state and it tends to get
back to a thermodynamically stable state like (2) with a mass exchange
1[ i ( i ) ] 1 dmk→l
Γ kl = ρ v − vk Aikl ⋅ nilk = = − Γ lk (5) Δmk→l . If that happens, the energy equation should apply the heat of
V kl kl V dt
fusion and decrease Tkli . However, the mass exchange may be over­
The equation just gives a statement of interfacial mass transfer rate. estimated. Then an excess amount of l would be remained with a drop
However, it does not provide any information about the exchanged mass down in the temperature; This is state (3) shown in Fig. 2. It is the next
or the interphase velocity. Another formulation is demanded to find Γkl unstable situation, which tends to get a stable state like (4). That sce­
and to close the mathematical system. Such formulation expresses nario can be continued iteratively toward an equilibrium. To be
thermodynamics and kinetics of the phase change, which is proposed in consistent with the energy equation, the phase change model should
section 2.2. keep the total enthalpy conserved from (1) to (2), i.e. h(2) − h(1) = 0 and
so forth. Thus, a formulation for mass exchange in both unstable situa­
2.2. The rate of phase-change tions can be derived as follows:
( )
For each phase-change couple k→l, there is a phase-change rate h(1) = mk href i
k + ck Tkl (9)
(PCR) denoted by Γ kl which will be required as the source term Γ lk = − ( ) ( ref )
Γ kl in the continuity equation (1). A fundamental formulation to eval­ h(2) = (mk − Δml ) href eq eq
k + ck Tkl + Δml hl + cl Tkl (10)
uate PCR might involve thermodynamics and kinetics of phase change. ( )
eq
A general concept to formulate PCR proposes as: Δmk→l = ±
mk ck Tkli − Tkl
(11)
eq
Δhref
kl + Δckl Tkl
Γ kl = Kk ↔ l (εk − εeq k ) (6)
⏟̅⏞⏞̅⏟ ⏟̅̅̅̅̅̅⏞⏞̅̅̅̅̅̅⏟ Correspondingly, the mass increment Δml→k is obtained for backward
kinetic term thermodynamic
(inverse of driving force direction l→k with the properties of l-phase as
Δml→k = ±ml cl (Tlki − Tlkeq )/(Δhref T eq
It should be mentioned that
resistivity) (deviation from
equilibrium)
lk +Δc lk lk ).
Δm cannot be explicitly used to update mass or volume fractions of phase
The equation describes phase change rate by two factors; a ther­ k, because equation (1) is doing the job. Instead, Δmprovides a formu­
modynamic driving force (deviation of phase fraction from its equilib­ lation for an implicit iterative updating of the kinetic term. The kinetic
rium state εeq
k ) and a kinetic coefficient Kkl (the inverse of resistance to correction can be composed as:
the phase change). Phase changes are controlled thermally (by tem­
perature), and/or chemically (by compositions), and/or mechanically ΔKkl =
Δmk→l − Δml→k 1 (εk ρk ck + εl ρl cl ) ( i eq
)
(12)
= eq Tkl − Tkl
(by pressure/stress). In this paper, phase changes are assumed to be VΔt Δt Δhref
kl + Δc T
kl kl

physical and thermally-controlled. Then, the driving force is conve­ From the combination of equations (6)–(8) the final formulation to
niently computable with an initial guess of εk and a state function calculate the rate of phase change (PCR) is proposed as follows:
defining εeq
k based on local temperature. Taking k as the stable phase at ( n− 1 )
lower temperatures (like solid-liquid for k ↔ l), the equilibrium fractions Γ kl =
Γ kl
+ ΔKkl eikl (13)
of the phases are: i
ekl
{ { ⎧
0 εk + εl Tkli > Tkleq ⎪
εeq = εeq
= (7) ⎨ε i
T kl > Tkleq
(14)
k l
εk + εl 0 Tkli ≤ Tkleq eikl =
k
⎪ i
⎩ εl T kl ≤ Tkleq
where the equilibrium fraction εeq
k depends on the interphase tempera­
eq
i
ture Tkl with respect to the equilibrium temperature Tkl (e.g. melting where Γn−
kl
1
is the rate available from previous iteration. Equation (14)
point). Equation (6) could be already usable just with setting Kkl to be a declares an equilibrium deviation factor, eikl (the driving force) when k is
big number, and it would give a simple model that forces the phase stable at lower temperatures, i.e. Δhref
kl > 0. Otherwise, in the case
fractions to obey equilibrium. Nonetheless, the aim is to illuminate the
Δhref i
kl < 0, the deviation factor ekl is defined with the position of k and l
rate and Equation (6) is to give us a flexibility of non-equilibrium
reversed.
thermodynamics with the kinetic term Kkl . For specific cases, available
kinetic models (as used in Ref. [19]) would help to formulate Kkl .
However, any specific-case-kinetics puts some restrictions to the usage 2.3. Non-equilibrium phase change rate
of the model. In this respect, a simple description is required, which is to
be free from sophisticated geometrical considerations. At the same time, By Equation (13), the phase-change-rate is iteratively calculated and
it needs to be flexible and capable enough. Therefore, the idea is to set updated which manages the phase change to maintain the phase frac­
up an infinite series of iterative corrections to get a finite rate of phase tions at instantaneous equilibrium states. However, the aim has been to
change: develop a phase change model for non-equilibrium transformations. The
idea is to restrict the obtained PCR to simulate deviations from equi­
Kkln = Kkln− 1 + ΔKkl (8)
librium state. Therefore, we are going to calculate the rate using equa­
The previous value of kinetic term is already available as =Kn−
kl
1
tion (13), and to put a constraint on that rate too. To enclose the
eq
kl /(εk − εk ) by definition from Equation (6). For ΔKkl , although
Γn− obtained rate, we introduce a range of [Γ min
kl , Γ kl ] for the rate:
1 max

3
A.R. Jafari
Fig. 2. Two unstable situations of interphase of k-phase undergoing k→l, assuming k is stable at lower temperatures like solid-liquid. (a) a superheated amount of k
tends to get an equilibrium state (1)→(2). (b) Subsequently an overshot phase change is being receded, (3)→(4) i.e. excess amount of l changes back to k.
Γ min max
kl ≤ Γ kl ≤ Γ kl rate constraint (15)
The constraint will be easily implemented via straightforward nu­
merical modification for boundedness with maximum and minimum
functions. The phase-change-rate constraint (PCRC) Γmin kl and Γ max
kl ac­
count for case-dependent phase change kinetics. Those values express
the inverse of resistivity to the phase change of interest. Test case-II has
been conducted with different PCRCs as a parametric study. However, to
have the kinetic model more descriptive, PCRC should account for two
distinct resistances to the occurrence of phase change; nucleation barrier
and growth mechanism. A phase change often triggers via a heteroge­
neous nucleation phenomenon (thermally-activated statistical mecha­
nism) and go on via a growth kinetics (quasi-steady diffusion-controlled
interface movement) [26]. Therefore the PCRC is proposed to be a linear
combination of nucleation and growth kinetics:
( ) N
Γ max
kl = 1 − fkl
NGT
Γkl + fklNGT ΓGkl (16)
where ΓN G
kl and Γ kl are PCRCs for nucleation and growth kinetics
respectively, and fklNGT is a nucleation-to-growth transition (NGT) factor
being in the range from 0 to 1 (Fig. 3). In the absence of any interphase,
fklNGT = 0, the rate will be restricted to the nucleation kinetics, i.e. Γmax
kl =
ΓN NGT
kl . Next, the NGT factor gets a positive value fkl > 0, as soon as a tiny
amount of k-l interphase is detected around the location (how is dis­
cussed later). Then it partially involves the growth kinetics into the rate
Fig. 3. Representation of Equation (17) for calculation of nucleation-to-growth
transition factor fklNGT as a function of interphase detector variable e. A sharp
transition (nucleation triggering) is obtained by a power of n .
4
International Journal of Thermal Sciences 159 (2021) 106608
by equation (16). Finally, the growth kinetics completely takes the
G
control of phase change rate Γmax kl = Γ kl when an adequate amount of
NGT
interphase is found fkl = 1. The linear merging of nucleation and
growth has been introduced in the model for a couple of reasons; (a)
There might be a quite large difference between the nucleation and
growth rates, so a proper fuzzy logic transition is required to avoid
discontinuity in PCR at the moments of phase-change triggering. (b) The
linear transition can describe simultaneous occurrence of nucleation and
growth in a volume average REV. The NGT factor puts a continuous
transition, but rather a sharp one, between nucleation and growth. The
transition is assumed to have a sigmoid-like trend, in log-scale between
0 and 1, which is proposed as the following relation:
( )
an
(17)
1
fklNGT = 1 −
n
i n
ϕkl + an
where ϕikl is an interphase detector function (IDF) measuring the amount
of area density for the REV. The parameter a accounts for the critical
point of the nucleation-growth transition. It corresponds to total inter­
phase area density at the critical nucleation point. It has been evaluated
in section 2.4, equation (28) according to the nucleation model. The
power n in equation (17) is a positive integer setting a sharpness degree
for the transition. Equation (17) yields a NGT factor fklNGT between 0 and
1. With n = 1 the NGT function is reduced to a log-scale sigmoid form
( )
fklNGT = ϕikl / ϕikl + a as shown in Fig. 3. As the sharpness degree
increased, e.g. n = 2, the transition is pushed ahead on the critical point.
That is to model the nucleation toward a triggering. A sharp nucleation
triggering can be obtained by the power n in the range of 10–20.
In order to formulate Interphase-Detector-Function ϕikl , an evaluation
of interphase area is needed. The IDF is responsible to return zero for no
interphase and a positive value when it detects any portion of an inter­
phase between k and l. Variations of interphase area density with respect
to phase fractions would be a help, if there was any knowledge of those
variations. Evolutions of morphology of interphase strongly depend on
material and conditions. However, complexities of morphological evo­
lutions may be ignored at this moment just to track the existence of
interphase. A very basic form of variations of interphase area may be
used, considering a square function of volume fraction (shown in Fig. 4):
AiV iV
kl = 4Amax (εk εl ) (18)
where AiV
max is the maximum interphase area density which is assumed to
occur at εk = εl = 0.5. Ignoring the complexities in morphology, the
maximum total interphase area per volume might be the product of
averaged maximum area of single particles multiplied by the number
density of particles, i.e. AiV V N
max ≈ nN Amax . The maximum area of a single
A.R. Jafari International Journal of Thermal Sciences 159 (2021) 106608

Fig. 4. Variations of interphase area density within the REV with respect to
phase fraction; a very basic form.

2 − 2/3 1/3
particle is AN N V
max = π dmax = π (nN ) , then AiV V
max ≈ π (nN ) and AiV
kl =
1/3
4π(nVN ) (εk εl ). The simplified formulation determines the amount of
interphase area within the REV (Fig. 5a). However, it cannot be used as
ϕikl , because equation (18) yields null Ai = 0 for an interphase located at
the faces of adjacent REVs (Fig. 5b). We need to set a function ϕikl that is
able to track the occurrence of interphase around the REV as well as in
the REV. Taylor’s theorem [27] describes how to approximate a function
around a point. For this matter, a quadratic Taylor approximation
around node P matches the concept:
( ) ( ) 1 ( )
ϕikl = AiV P + ∇ AiV P .Δx + ∇2 AiV P : Δx2 (19)
2
Terms with a higher order, than the quadratic, are truncated ac­
cording to the point that IDF explores the location up to the first adjacent
volumes. It should be noted that some terms of equation (19) may be
negative as they point to the either sides of an interphase with respect to
viewpoint P. To avoid unwelcome results, all terms are considered with
their absolute values. Also we may use phase fractions from previous
time step to have an explicit function. Finally by implementing the Fig. 5. An interphase of kl is found when both k and l exist either in the control
Taylor approximation on equation, the IDF is proposed as follows: volume or in the neighbor volumes. The control volume P in these three cases
[
( )1/3 o o ⃒ ( o o ) ⃒ 1 ⃒ 2 ( o o ) ⃒
] does not need nucleation to run the phase change, since an interphase is
ϕikl = 4π nVN εk εl + ⃒∇ εk εl Δx⃒ + ⃒∇ εk εl : Δx2 ⃒ (20) available within or on the faces of the control volume P. (a) The value, or (b)
2 the slope, or (c) the curvature of the volume fractions can be an indication of
Fig. 5 explains the concept laid behind equations (19) and (20). An occurrence of an interphase.
interphase of kl is found when both k and l exist within the control
volume or in the neighbor volumes. The figure illustrates three situa­ second phase nuclei form per unit volume of material:
tions of the occurrence of interphase for the control volume P. As shown,
Γ Nkl = ρl VlN I (22)
the value (Fig. 5a), or the slope (Fig. 5b) or the curvature (Fig. 5c) of
phase fractions is an indication to the existence of interphase.
where I is nucleation rate (in 1/m3s) and VlN is average volume of
equilibrium clusters (embryos). The nucleation rate also depends on
2.4. Nucleation and growth kinetics undercooling [29–31]. It has been basically described according to the
rate at which equilibrium clusters form and turn to stable nuclei [32];
The nucleation and growth PCRCs Γ N G
kl and Γ kl in equation (16) are
I = βN Z CN where CN is equilibrium concentration of clusters of atoms
terms to regulate the phase change model for arbitrary non-equilibrium (or monomers), Z is Zeldovich factor for the decay of clusters being
kinetics. By definition, the growth rate is interfacial mass transfer rate about Z ≈ 0.5 and βN is the rate at which atoms jump to a cluster to
within material: convert it to a nuclei. The equilibrium concentration of clusters is
CN = CN N
A exp( − ΔGkl /kB T) with CA as total concentration of surface
Γ Gkl = ρl AiV iG
kl vkl (21)
atomic sites (or monomers) for heterogeneous nucleation;
3 2 V
CN 2 2
A (site/m ) = Ap /aA = π dp np /aA where aA is atom (monomer)
where viklG is area-averaged interface growth velocity and AiV
kl is volume
average interfacial area density. Interface velocity may be evaluated spacing in the liquid phase and nVp and dp are particle density and
from an experimental measurement or a theoretical relation which is particle size respectively. The activation energy ΔGNkl for heterogeneous
basically a function of undercooling and composition of materials [28, nucleation has been given as ΔGNkl = 16 2 2
3 π kGT γ kl f(θ)/ΔT [31]. Where γ kl
29]. The PCRC of nucleation is defined by the rate at which total mass of

5
A.R. Jafari International Journal of Thermal Sciences 159 (2021) 106608

eq
is surface energy of kl-interphase, kGT = γkl Tkl /ρl Δhkl is Gibbs- ( ) ( )
eq ∂ ρh
Thomson coefficient, ΔTkl = Tk − Tkl is undercooling, f(θ) = =
∂
k
∂T
+ (SΓ ) (30)
∂t ∂x ∂x
(2 +cos θ)(1 − cos θ)2 /4 is the heterogeneous function of wetting angle
θ and cos θ = (γ kp − γpl )/γkl [29,31]. The average volume of primary
SΓ = Γ21 Δhref (31)
nuclei is VlN = 43 πrN3 f(θ) with the critical radius of rN = 2kGT /ΔT. The 12

rate of atom jumps βN = νA NA is obtained by the product of atomic jump ( n− 1 )

Γ 12
frequency νA ≈ 6DkA /a2o and the number of atoms (monomers) available Γ 12 = + ΔK 12 ei12 , Γ21 = − Γ 12 (32)
ei12
at the boundaries of each cluster NA = AiN XA /a2A [32]. The boundary
{
surface of the cluster is AN = 2πrN2 (1 − cos θ) assuming the clusters have ε1
(
Δhref i eq ) ( ref i eq )
12 ≥ 0 and T12 > T12 or Δh12 < 0 and T12 ≤ T12
a shape of spherical cap) and XA is atom (monomer) fraction in the so­ ei12 = ( ref i eq
) ( ref i eq
)
ε2 Δh12 ≥ 0 and T12 ≤ T12 or Δh12 < 0 and T12 > T12
lute. Therefore collecting all the terms, the nucleation rate and its cor­
responding phase change rate will be derived as: (33)
( )
CI C2I 1 (ε1 ρ1 c1 + ε2 ρ2 c2 ) ( i )
I = 12 exp − (23) ΔK12 = ( eq
eq
) T12 − T12 (34)
ΔT TΔT 2 Δt Δhref
12 + Δc12 T 12

( )
CoΓ C1I C2I h
Γ Nkl = 5
exp − 2
(24) T= , i
T12 ≈T , eq
T12 = Tmelting (35)
ΔT TΔT c
[ ]
where CΓo , CI1 and CI2 are constants as following: Γ12 = min Γ12 , Γmax
[ 12
] (36)
32π 3 Γ12 = max Γ12 , Γmin
12
CoΓ = ρ k f (θ) (25)
3 l GT ( ) N
Γ max NGT
12 = 1 − f12
NGT G
Γ 12 + f12 Γ12 (37)
2
ZDk kGT dp 2 nVp (1 − cos θ)
C1I = 8π 2
(26)
a6A

⎧
⎪
⎪
⎧ 6
( ) ⎪1
⎪
Equilibrium
⎨ > 10 very big
⎪ Equilibrium ⎪
⎪
⎨1 Growth control
ΓG12 = case-dependent Growth control NGT
f12 = ( )1/ (38)
⎪
⎩ ⎪
⎪
case-dependent Nucleation-Growth ⎪
⎪ n n
⎪
⎪ 1 − a /ϕ12 + a
n n Nucleation-Growth
⎩

( )
16π kGT 2 γkl f (θ) CoΓ C1I C2I
C2I = (27) Γ Nkl = exp − (39)
3 kB ΔT 5 TΔT 2
According to the model of nucleation, the critical parameter a in ( ⃒ ( ) ⃒ ⃒ ( ) ⃒)
( )1/3 o o ⃒∂ εo1 εo2 ⃒ 1 ⃒⃒∂2 εo1 εo2 ⃒
equation (17) can be evaluated for the nucleation-to-growth transition. ϕi12 = 4π nVN ε1 ε2 + ⃒⃒ Δx⃒⃒ + ⃒ Δx 2⃒
⃒ (40)
The critical point of NGT factor (see Fig. 3) corresponds to total inter­ ∂x 2 ⃒ ∂x 2 ⃒
phase area density at the critical nucleation point a ≈ nVN AN (nVN is
number density of nuclei and AN = 2π rN2 (1 − cos θ) is the area of a critical 3. Benchmark problems
heterogeneous nucleus. Then the critical parameter for equation (17) is
introduced as a function of undercooling: The proposed phase change model was evaluated in a benchmarking
/ 2 study consisting of a number of test cases. As for the verification, firstly,
2
a = 8πkGT nVN (1 − cos θ) ΔT (28) the model with source-based kinetics of phase change was expected to
Other nucleation models e.g. Gaussian model developed by Rappaz give an accurate and efficient solution to a simple equilibrium problem.
[26] could also be used with different parameters to derive equation Then, the second benchmark was carried out to evaluate the model in
(23). The nucleation model proposed in equation (24) has been used in non-equilibrium situations where the rate of phase change is limited and
test case-III and explained more in section 4.Results and Discussion. meta-stable phases appear. Going further, the third test case was carried
out with a non-equilibrium solidification that exhibits undercooling and
recalescence. All three test cases were solved with a same code devel­
2.5. Summary
oped for the summary model. The following subsections explain the
details of each test case of the benchmarking study.
The mathematical model proposed can be summarized for a simple
case of one-dimensional heat diffusion with a phase-change couple (1:
Solid 2:Liquid) to the following equations: 3.1. Test case I: Equilibreium phase-change
∂(ε2 ρ2 )
= Γ12 , ε1 = 1 − ε2 (29) The first benchmark involves a unidirectional transient heat transfer
∂t
in a bar of ice with solid-liquid phase change, well-known as Stefan

6
A.R. Jafari International Journal of Thermal Sciences 159 (2021) 106608

Table 1
Material properties and parameters adopted for the benchmarking study in
Cases I and II.
Properties/Parameters Symbol/ Value Unit
formula

Density of ice ρS 916.8 (kg/m3)

Density of water ρL 1000.0 (kg/m3)
Specific heat capacity of ice cS 2000.0 (J/kgK)
Specific heat capacity of water cL 4186.8 (J/kgK)
Thermal conductivity of ice kS 0.580 (W/mK)
Thermal conductivity of water kL 0.564 (W/mK)
Latent heat of fusion of ice Lf 333.4 × 103 (J/kg)
Melting temperature of ice Tm 0 (◦ C)
Case I:
Initial condition, t = 0 (s) To − 10 (◦ C)
Boundary condition at x = TW 50 (◦ C)
0 (m)
Boundary condition at x = ∂T/∂x 0
Fig. 6. A schematic of the benchmark problems; A bar, made of phase k, 0.1 (m)
initially at a temperature of To , is suddenly exposed to TW from the left side. In Time step Δt 0.25, 0.5, 1, (s)
case-I the boundary temperatures is static (TW > 0 ◦ C Stefan Problem). In case- 5, 10
II a sinusoidal boundary condition is applied imposing heating-cooling cycles of No. of volume elements N 20, 40, 80,
TW = TA Sin(ω t). Case III deals with solidification and undercooling of the bar. 160, 320
NGT factor NGT
f12 1
PCRC of growth ΓG12 Unlimited, (kg/m3s)
Problem [33]. Fig. 6 illustrates the problem. The ice bar is initially at a
1020
uniform temperature of To (subzero degree Celsius). Then, the left face PCRC of Nucleation ΓN – (kg/m3s)
12
of the horizontal bar is suddenly exposed to TW > 0◦ C. Holding the wall
Case II:
temperature, the ice starts to be melted from the left side and the Initial condition, t = 0 (s) To 0 (◦ C)
interface of water-ice moves right with a decreeing velocity. The prob­ Periodic Boundary condition, TW Sin(ω t) TW = 10 (◦ C)
lem desires the distribution of temperature versus distance and time, and at x = 0 (m) ω = 2πν (rad/s)
the positions of the ice/water interface at every moments of melting. ν = 1/30, (1/s)
1/60,
Table 1 lists the parameters and properties used in the problem. This
1/120
test-case was chosen as the first requirement to be met. The Stefan
Boundary condition at x = ∂T/∂x 0
problem has an analytical (exact) solution [33] (Appendix-I) which al­ 0.02 (m)
lows to precisely verify the accuracy of model calculations. Moreover, it Time step Δt 1 (s)
is required to be assured if the developed non-equilibrium model is No. of volume elements N 160
efficient at equilibrium cases and to evaluate how the proposed model NGT factor NGT 1
f12
performs in comparison with frequently-used phase change models.
PCRC of Growth ΓG12 0.1, 1, 5, 10, (kg/m3s)
50, 100
PCRC of Nucleation ΓN – (kg/m3s)
3.2. Test case II: Non-equilibrium phase change 12

A non-equilibrium phase-change happens when a phase-change-

material is exposed to a relatively high cooling/heating rate. In this
condition the amount of phases would not further obey equilibrium
values. Then resistances control the progress of phase change. Although
that is quite frequent in materials processing, there is a lack of bench­
mark problem of this kind that allows for model testing. In this study, a
benchmark problem was innovated to specifically highlight and mea­
sure non-equilibrium progress of a phase change. The test case is
considered to be a unidirectional transient heat transfer in a bar of ice,
initially resting at equilibrium state with To = 0 ◦ C. The geometry and
the material is chosen to be the same as Case I. However, from the left
end, the bar is exposed to successive cycles of heating-cooling by
introducing a sinusoidal wall temperature TW = TA Sin(ω t) to the
boundary condition (See Fig. 6). If the frequency of the cycles ν = ω/2π
was zero (static boundary condition), the problem would be reduced to a
Stefan problem (an equilibrium phase change would be expected). As
the boundary temperature starts to cycle, the phase-change material
experiences a dynamic heating-cooling. With a fairly high frequency in
this situation, the material will undergo off-equilibrium transitions so
that a partial phase change or no phase change might be expected
[34–36]. It is assumed that; the thermo-physical properties of the ma­
terial do not change; the material has two possible distinct phases; and
each phase possesses a constant level of reference enthalpy. A solution to
this problem, that shows the effect of the frequency, is beyond the ability
of equilibrium phase change models. Although this can happen in a real
case, the present problem is considered as a hypothetical case to
accentuate verification of the non-equilibrium phase change modelling.
Parameters used in this test case are summarized in Table 1.
3.3. Test case III: Nucleation and undercooling
A non-equilibrium phase change frequently exhibits nucleation and
undercooling/overheating phenomena in real systems, for which the
proposed model is required to be able to give valid predictions as well.
The third benchmark problem was set to test the issue in the present
model. In this case, unidirectional solidification of a phase-change-
material (PCM) was numerically simulated to predict its non-
equilibrium undercooling using the phase-change kinetics model. The
PCM was chosen as recommended by Gunther et al. [37] to be sodium
acetate trihydrate graphite composite (SAT-G). They have indicated that
the material, with high viscosity, prevented the formation of convec­
tions in the liquid and provided a heat transfer regime that could be
reliably assumed to be a pure conduction. In this benchmark the ge­
ometry of the problem is similar to Fig. 6 except that the length of the bar
is 5 cm and the material is at equilibrium superheated liquid state
(k-phase) initially. As the material is exposed to a chilling temperature
from the left side, it starts to be cooled and solidified. The physics of the
problem however involves nucleation, which leads to postpone the

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A.R. Jafari International Journal of Thermal Sciences 159 (2021) 106608

Table 2 3.4. Numerical method

Material properties of SAT-G [37–41] and parameters for Cases III.
Properties/Parameters Symbol/formula Value Unit Discretization. Using finite volume method (FVM) [42,43], the dis­
cretized equation of phase was derived by integrating the continuity
Case III:
Density ρ 1300 (kg/m3) equation (29) over the volume element containing node P:
Specific heat capacity c 3000 (J/kgK) [ ]V
Thermal conductivity k 3 (W/mK)
ε2P ρ2 − εo2P ρo2 = V Γ12 (41)
Δt
− 11 2
Effective mass diffusion DA 0.5 × 10 (m /s)
coefficient aP ε2P = aoP εo2P + bP
Enthalpy of solidification of Δhref − 175 × 10 3
(J/kg) / / (42)
ls aoP = ρo2 V Δt, bP = SC V, aP = ρ2 V Δt + SP V
SAT
Latent heat of SAT-G (~20% Δhref 140 × 103 (J/kg)
graphite)
ls The energy equation (30) has two dependent variable h and T. To be
Melting point Tm 58 (◦ C) able to solve the equation with a standard CFD solver, it is favorable to
Surface energy of S/L γsl 8 × 10− 3
(J/m2) have the accumulation and the diffusion terms with a same dependent
interphase variable; In this regard h was chosen. Therefore the diffusion term ∇⋅
Wetting angle θ π/2 (rad)
(k∇T) was replaced by ∇⋅(k∇T) + ∇⋅(k /c∇h) − ∇⋅(k /c∇h). That is an
Inoculant particle density nVp 103 (1/m3)
always true statement, and accordingly, the energy equation (30) was
Inoculant particle size dp 10− 6 (m)
rearranged as follows:
Nuclei density nVN 103 (1/m3)
( ) ( )
Monomer spacing aA 20 (nm)
∂ ρh ∂ k ∂h
NGT factor f12
NGT Equation = + SD + SΓ (43)
(17) ∂t ∂x c ∂x
PCRC of growth ΓG12 10 (kg/m3s)
PCRC of nucleation ΓN
12
Equation (kg/m3s) where the source term SD = ∇⋅(k∇T) − ∇⋅(k /c∇h) accounts for diffu­
(39)
sion correction due to variations of mixture specific heat. Integral of the
Initial condition, t = 0 (s) To 79 (◦ C)
energy equation (43) over the volume element of node P with neigh­
Boundary condition at x = ∂T hConv TC = 31 (◦ C)
0 (m) ∂x
=
k
(T −
hConv = 800 (W/m2K)
boring nodes W and E gives:
TC ) [ ] ( ) ( )
o V
Boundary condition at x = ∂T/∂x 0 ρhP − ρo hP = De hE − hP − Dw hP − hW + SD V + SΓ V (44)
0.05 (m)
Δt
Time step Δt 1 (s) ∑
aP hP = aNB hNB + bP
No. of volume elements N 95
( ) NB
(45)
k A o ∑
aNB = Dnb = c δx
, bP = aoP hP + SC V, aP = aoP + aNB − SP V
NB
starting of the phase change and to form an undercooling and a reca­
nb

lescence in the temperature history curves. The material properties of
SAT-G [37–41] and parameters used in this case are listed in Table 2.
Experimental time-temperature data obtained by Gunther, Mehling and
Hiebler [37] were adopted to validate the results of the model in this
benchmark.
The phase change material SAT has shown undercooling up to 70 ◦ C
in homogeneous nucleation in the absence of graphite [38]. Experiments
by Gunther et al. [37] on SAT-G have shown undercooling’s of 25 ◦ C and
15 ◦ C with ~1500sec and ~2000sec nucleation time, respectively. Ac­
cording to these data and with some numerical study using the hetero­
geneous nucleation model, S-L surface energy and wetting angle of
SAT-G were roughly estimated. The material properties and parameter
listed in Table 2 were used to evaluate the constants of the nucleation
model according to equations (25)–(27). The values obtained as CΓo =
3
3.44 × 10− 20 (kgK ), CI1 = 8.36 × 1010 (K2 m− 3 s) and CI2 = 6.58×
105 (K3 ) for test-case III. From equation (21), the growth PCRC is
roughly estimated to be ΓGkl ≈ (103 kg/m3 )(10m− 1 )(1 mm/s) ≈
10 kg/m3 s and used as a constant. It is reminded that the growth rate
will not be constant in the simulations; it will be regulated by the growth
PCRC by equation (15). It is noted that Gunther et al. [37] have also
provided a calculation Algorithm to solve the problem (test-case III).
Their algorithm used one-dimensional heat conduction and an apparent
heat capacity for the phase change. They involved nucleation and
growth, respectively with a predefined nucleation temperature from
datasheet of the material, and a temperature dependent growth speed
from quadratic fit to experimental measurements. The approach they
presented is fundamentally different from the current model. Between
their model and the present work, the common parameters are density,
specific heat capacity, conductivity and boundary conditions. Other
parameters of the current model, related to nucleation and growth ki­
netics, are adopted from other references [38,40,41].
The terms SC and SP in the discretized equations (42) and (45) are
obtained from a source term linearization [42] in the form of S = SC +
SP φP . It is noted that εk and h are always-positive variables. Also εk must
lie in the range between 0 and 1. Therefore, the source terms Γ lk and SΓ
can be decomposed to positive and negative parts as S = S+ − S− . That
helps to get proper SC and SP to get always-positive coefficients, i.e. to
eliminate the possibility of getting a negative or an out-of-range value.
The discrete form of the interphase detector function φikl , equation (40),
for k = 1 and l = 2 in one dimensional control volume P on a uniform
grid spacing becomes (sea Fig. 5):
{
( )1 ( o o )
ϕi12 = π nVN 3 4ε1P ε2P
(46)
+|2(εo1P εo2E +εo1E εo2P +εo1P εo2W +εo1W εo2P ) |
|(
+ 2 εo εo +εo εo +εo εo +εo εo − 4εo εo
1P 2E 1P 2W 1E 2P 1W 2P 1P 2P })
(
+ εo εo +εo εo − εo εo − εo εo
1E 2E 1W 2W 1E 2W 1W 2E )|
Numerical Setup. A multiphase numerical setup was developed based
on the mathematical model proposed. The computational domain,
shown in Fig. 6, was divided into a number of volume elements as
indicated in Table 1 and Table 2 for different case studies. The final set of
the discretized mathematical formulation were implemented using an
open-source CFD code, called SENSE, in FORTRAN language. Boundary
conditions were applied according to Table 1 and Table 2 for the case
studies. Fully-implicit and constant time-stepping was used for transient
terms. The convergence criterion was set to be the summation of all
relative variations of all dependent variables becomes less than 10− 6.
After debugging’s, the numerical setup finally shows desired conver­
gence and stable performance for all the case studies. For numerical
processing in case-I and case-II, the computational time was less than a
minute and for case-III it was less than 3 min in average on a Core-i7

8
A.R. Jafari
7500U Intel CPU laptop. The performance of the model for phase-
change rendering was quite fast, stable and convergent for all cases.
Algorithm. The algorithm of the calculations containes an iteration
loop for each fully-implicit time step. The iteration loop was designed to
run in the following order of commands; For all nodes:
1. Calculate temperature T; equation (35).
2. Calculate rate of phase changes Γ 12 ; equation (32) with equilibrium
deviation (33), kinetic correction (34) and rate-constraint (37).
3. Calculate volume fractions ε2 and ε1 ; continuity equation (29).
4. Calculate mixture enthalpy h; energy equation (30) with phase-
change heat source (31).
5. Check variations of temperatures and phase fractions.
6. Iterate until convergence.
4. Results and discussion
The proposed model was firstly used to simulate melting of an ice bar
(Case I. Stefan Problem). Fig. 7 shows where the melting front is located
with time. The continuous curve indicates the exact solution of the
problem. Simulated results has been depicted by squares of various sizes
for different grid densities. The size of grid is started from 5 mm (with
20 volume elements or 22 nodes in 10 cm length).Then it is reduced such
that the number of volumes was doubled in each simulation. The dis­
cretization error measured to be about 10% for 20 volume elements, and
was refined to less than ~1% error when the volume elements increased
to 80. The convergence and accuracy of the numerical model was pre­
cisely assured even more with increasing volume elements to 160 and
320 and reducing time-steps up to 0.25 s. Temperature distribution
along the bar being melted was also evaluated against the analytical
solution. Fig. 8 displays the distribution of temperature at time t = 3000
s along with the distribution of liquid volume fraction within the bar.
The location, at which the slope of the temperature curve has changed, is
the position of the interface of water/ice. With less than ~1% error, finer
grid densities yield a desired agreement with exact solution both in
liquid and solid regions. Finer grids also predict a sharper interface of
melting.
Comparing the present model with the previous enthalpy methods,
here is a point to be highlighted. Although the solution of this test case is the
same from both, there is a difference between the calculation algorithm of
previous enthalpy method and the proposed model. In the enthalpy
methods, the phase fractions are explicitly obtained from enthalpy or
Fig. 7. Progress of the interface position (melting front) with respect to time for
the ice bar in Stefan problem; comparison of numerical results with analytical
solution. Case I.
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International Journal of Thermal Sciences 159 (2021) 106608
Fig. 8. Distribution of temperature in the ice bar (Stefan problem) after 3000 s.
Comparison with analytical solution. Case I.
temperature via a Heaviside jump (for isothermal phase changes) or a path
function such as equilibrium lever-rule or non-equilibrium Scheil-like
equations (for mushy phase changes). It means previous enthalpy methods
assume that a phase change takes place strictly (and algebraically) at a
predefined temperature (or in a predefined range of temperatures). In the
present model however, that assumption has been removed. Here, the
phase fractions are calculated from the continuity differential equation
(29). (neither from a jump function nor a path function). The continuity
equation involves the rate of change of phase fractions by the kinetic source
term provided (infinite series equation (32)). In this model, the relation­
ship between temperature and phase fraction is implicit and non-algebraic
(not strict). That allows a phase change to take place at any temperature,
even below or above the equilibrium point(s). That is how the model does
not dictate the equilibrium thermodynamics. In addition, in the previous
enthalpy methods, the formulation of phase change (the algebraic state
function between enthalpy/temperature and phase fractions) has to be
modified when non-equilibrium effects are to be considered (e.g. Lever-
rule function is replaced by a Scheil-like function). In the present model,
the formulation for PCR is the same for simple equilibrium cases and non-
equilibrium ones. If the calculated PCR is remained unbounded, the solu­
tion will converge to an equilibrium solution as obtained for case-I. When
PCR is bounded by a proper PCRC, the solution will deviate from equilib­
rium route. That will be discussed in the results of test cases II and III.
The rate of melting of the ice bar has been exhibited in Fig. 9 from
both analytical and numerical results. The position of the interface has
been also plotted on the right axis of the diagram. The numerical rate has
been reported from the model and the analytical rate was obtained from
interface velocity as Γ kl V = ρk Aikl vikl ; Where vikl = dxi /dt and xi is
addressed in Appendix-I. While the analytical rate is showing a smooth
and decreasing trend, the numerical rate (circled line in Fig. 9) is
bouncing step-wise on the same trend. This bouncing matches what has
been previously observed in enthalpy method [44]. Time-averaging of
the numerical rate yields a value similar to the exact solution for each
node. The grid density has been chosen as to form 40 volume elements in
total to detect this step-by-step melting of the bar, i.e. each step for one
volume element. The reason for step-wise behavior of the numerical rate
is related to the volume average temperature; According to Equation
(12) the rate is calculated after temperature, and the temperature has an
increasing trend during melting. Therefore the rate would tend to be
increasing for each volume element. At the same time, the model is
managing to render a decelerating movement of a sharp interface at
A.R. Jafari
Fig. 9. Numerical predictions for variation of phase change rate Γkl V during
heating of the ice bar. The numerical (circle) line is volume average rate within
the domain. In comparison to the smooth exact solution, the numerical rate
shows a step-wise variation according to discretized domain and decelerating
movement of sharp interphase. Case I.
Fig. 10. Predicted distribution of PCR at t = 3000 (s) for different grid den­
sities. When the size of volume elements is reduced, PCR is resolved con­
structing a sharp interphase. Instantaneous equilibrium demands extremely big
rate at the interphase. Case I.
equilibrium. That has become possible with the step-wise rate calculated
by the model.
There is an important point in the spatial distribution of PCR. Fig. 10
shows values of the numerical PCR along the bar during its melting at
time t = 3000 s for different grid densities. The temperature line in­
dicates the location of the interphase. The values of PCR shows a peak;
so that the rate is zero along the bar except in the volume element
containing the interface at that moment. As the grid density is increased,
the location of the peak becomes more accurate toward the exact
analytical location. It may be expected to have the height of the peak
also converging to a value. Apparently, the peak tends to rise up in an
accelerating manner as the volume elements become smaller. Despite
what is expected, the model shows that the height of the peak diverges to
infinity. What is correct in fact, is that the rate of a phase change, being
10
International Journal of Thermal Sciences 159 (2021) 106608
at an instantaneous-equilibrium (hypothetical), might be infinite at the
exact location of the interface. The formulation of PCR in Equation (13)
is unbounded, i.e. the numerical rate will be increased or decreased
iteratively and it will go on until an equilibrium is reached. Now, it is
worth noting what could happen if PCR was bounded to a limit. It is
postulated that a phase change deviates from its equilibrium path
because it has too restricted rate to follow and maintain the equilibrium
state. Therefore, a concept of restricted rate was used by Equation (15)
to simulate non-equilibrium phase changes.
Periodic heating-cooling (boundary conditions of Case II in Table 1)
was numerically applied to the ice bar to simulate oscillations of
melting-freezing with a frequency of v = 1/60s = 0.0167 (Hz). This
situation can be addressed in some specific real physical systems, e.g.
LHTES energy storage applications [35]. Investigations [34,36] have
revealed that phase-change materials under cycling heating occasionally
undergo sensible heat transfer (undercooled/superheated) and show
partial phase change. Understanding of behaviors of materials in this
situation is not our current objective and could be more complicated;
may be metastable phases arise, latent heat is deteriorated, and/or
dominating nucleation barriers prevent the phase change. What we
currently need to know is that any phase change with diffusion kinetics
requires time, and thus the material, under rapid-enough successive
cycles of cooling-heating, would not have the time to maintain the
equilibrium conditions. Therefore a partial phase-change could happen
or even no phase change would take place. Both of them are beyond the
capability of equilibrium models which dictate the phase fractions.
Using the proposed model, Fig. 11 shows obtained results for distribu­
tions of temperatures and liquid fractions. The curves have been plotted
for one cycle of oscillation after enough cycles passed to reach a
pseudo-steady depth of melting-freezing. The solid-line patterns show
temperature distributions and the circle-dash-lines indicate liquid frac­
tions along the bar. The four diagrams of Fig. 11 correspond to four
limits (Γ max maximum absolute value in kg/m3s) of PCR; referring
Equation (15). The limits have been chosen to be 50, 10, 5 and 1
(kg/m3s) for Fig. 11 (a), (b), (c) and (d), respectively. Fig. 11a reports a
shallow depth of melting-freezing, but reached 100% of liquid and 100%
of solid in a cycle. That is related to the first limit, which provides a quite
large range of rates, meaning that the phase change has been nearly not
restricted. Thus, it has shown freely maintained equilibrium and get to a
complete melting-freezing. As the PCRC has been decreased, the depths
of phase change have been increased in the rest of the diagrams
(Fig. 11b, (c) and (d)). The liquid fractions therefore show partial
melting in the period of heating-cooling, although the temperatures
indicate that the material has been warmed up to several degrees beyond
the melting point temporarily. The numerical model has successfully
managed to a converged solution for a metastable (non-equilibrium)
phase-change handling. The next point to be mentioned in Fig. 11d is
that the liquid fractions show a flat profile indicating an entirely sup­
pressed melting-freezing. This is the case in which a phase change has a
very slow kinetics to follow the variations. Then, temperature curves are
almost not affected by the latent heat so it can be said the phase change
has been bypassed with rapid variations. Lastly from Fig. 11, it can be
understood that the depth of melting-freezing is related to the kinetics of
the phase change. More specifically, the degree of deviation from
equilibrium determines the depth of phase-changed-layer in an oscilla­
tory heating-cooling practice. The degree of deviation from equilibrium
corresponds the resistance to phase change and can be described by
inverse of maximum rate of phase change, i.e. Γ−max 1
.
To investigate how kinetics would affect the phase-changed-layer in
the ice bar under periodic heating-cooling, Fig. 12 was prepared through
a numerical study with the proposed model. The depth of melting-
freezing, d, was calculated for different PCRCs and for different fre­
quencies of heating-cooling. As Fig. 12 reveals, the rate limit Γ max affects
the depth of the phase change layer in a range of 0.1–100 kg/m3s.
Higher depths have been obtained from decreased Γmax (more restricted
A.R. Jafari
Fig. 11. Numerical results for distribution of temperatures and liquid fractions of the ice bar under periodic heating-cooling with a frequency of ν = 1/ 60 (Hz)
during one cycle of oscillation after reaching a pseudo-steady depth of phase change. The PCR have been restricted to Γmax , which is (a) 50, (b) 10, (c) 5 and (d) 1 in
(kg/m3s). The liquid fractions (circle-dash-lines) show partial melting, especially in (b) and (c) indicating non-equilibrium phase changes. Case II.
Fig. 12. Numerical results for the depth of melting-freezing under periodic
heating-cooling of the ice bar. Case II.
phase changes), showing more deviation from equilibrium states. As the
frequency is increased, the depths have declined and the phase changes
with more restricted rate (slow kinetics) have been more sensitive to
that. However, the frequency have had a little effect on the fast-kinetics
phase changes (as the right half of the diagram shows a little sensitivity
to frequency). Searching for a suitable curve to fit revealed that the
variations of phase-change-depth can be neatly described by the
following trend:
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International Journal of Thermal Sciences 159 (2021) 106608
d1 − d2
d = d2 + (47)
1 + (τ Γ max )n
where d1 is thermal depth of periodic heating-cooling without phase-
change, d2 is thermal depth for equilibrium phase change and τ is a
time factor. Both d1 and d2 inversely depend on frequency so that they
tend to be zero as the frequency becomes huge. For Equation (47) in the
scope of the present paper, it is worth just mentioning that the equation
can be used along with experimental data to have a calibrated limit Γmax
for the mathematical model of phase-change kinetics.
Fig. 12 simply characterizes three regions for kinetics of a phase
change. The first region, denoted at the right side of the diagram, in­
dicates when a phase change has a very fast kinetics which follows
instantaneous equilibrium without any resistance (unbounded rate or
very high Γ max ). The second region at the middle of the diagram, gives a
spectrum of kinetics from fast to moderate to slow phase-change in a
range of Γ max in an order of 10 to 0.1 (kg/m3s) for pure ice/water. The
third region at the left, denotes the condition in which the phase change
is bypassed because of a strong resistance. This situation can be observed
in reality when there exists a significant nucleation barrier, e.g. super-
cooling of pure water in a hydrophobic container. In this situation the
model predicts almost no phase change. From the results shown in
Fig. 12 it can be assured that the model supplies a complete spectrum of
possibilities of phase change kinetics. Numerical performance of the
model in the whole spectrum, from extremely fast rates (equilibrium), to
non-equilibrium to very slow rates was evinced to be verified, efficient
and consistent. The processing time for simulations in the first region
was about triple times more than those in the third region.
In test-case III an amount of molten sodium acetate trihydrate (the
PCM) was considered to be solidified under a unidirectional cooling in a
long cavity with parameters given in Table 2. The model was used to
simulate the solidification process, equipped with the PCRC presented
A.R. Jafari
Fig. 13. Temperature history curves at different positions of solidifying SAT-G
predicted using phase change model (Case III) in comparison with experimental
measurements by Gunther et al. [37].
by equation (16). Fig. 13 shows numerical predictions for some nodal
temperature history curves in comparison with experimental data pre­
sented previously by Gunther et al. [37]. Temperatures of four locations
(1) 0.5 cm (2) 1.5 cm (3) 2.5 cm and (4) 3.5 cm from the cooling end of
the 5 cm bar has been recorded versus time. As the cooling curves show,
the PCM, which was initially molten in 79 ◦ C, has been subcooled up to
~20 ◦ C below its melting point without any phase change at all loca­
tions. At the same time in the model, that undercooling increases the
driving force of the phase change and the rate tends to be high (Equation
(34)). However, since the IDF of the model has not found any interphase
(equation (37) to (40) with fklNGT = 0) the phase change is restricted by
nucleation kinetics (equation (39)). It takes about half an hour in real
time to activate a nucleation mechanism and to trigger the phase change
according to activation energy of nucleation. As soon as the interphase
detector alarms ϕikl > 0 by equation (40), the rate-limiter passes the
kinetic control to the growth mode. At this moment solidification begins
and proceeds immediately at a high maximum rate of ΓGkl which is
warming up the subcooled PCM because of a significant
latent-heat-release. This is when recalescence happens (indicated in
Fig. 13) until the temperatures are increased up to about the melting
point. Then, the driving force of the phase change drops and the rate is
reduced below the growth limit, being adjusted numerically by equa­
tions (32) and (34) with the cooling conditions. Subsequently, the so­
lidification continues almost like an isothermal one and it takes a while
to reach the positions far from the cooling end. The experimental data
depicted by dash-lines validates the numerical predictions. There is less
than ~10% error in temperature predictions, somehow away from so­
lidification region, which is thought to be probably from uncertainty in
reference enthalpy and heat capacities, the assumption of same prop­
erties for solid and liquid, and rough estimations for kinetic parameters
adopted. Nevertheless, the experimental lines show a relative agreement
and validate the kinetics predicted by the model. Gunther et al. [37]
have also presented a numerical solution to this problem. Their simu­
lated temperature history curves showed agreement with the experi­
mental data. However, their model was relied on a predefined
nucleation temperature and an empirical growth velocity. It is reminded
that the presented model in this study does not use a predefined
nucleation temperature or empirical kinetics. In fact the nucleation
temperature was a result of this model, which is a step forward in the
modeling of phase change kinetics.
Given that the focus of the study was on the specific source term,
caution must be paid to some limitations and extensions of the model for
general use. In particular, fluid flow and gradual phase changes, which
are frequent in materials processing applications, are excluded in the
12
International Journal of Thermal Sciences 159 (2021) 106608
current model. For fluid flow cases, the discretized continuity equation
cannot be used in the presented form (i.e. equations (41) and (42)). The
numerical discretization for fluid flow thus needs to be improved
properly. For the cases where gradual phase changes happen, e.g. mushy
solidification within a range of liquidus and solidus temperatures, the
equilibrium temperature needs attention. The equilibrium temperature
eq
Tkl is interpreted as an explicit constant value, e.g. a melting point, for
sharp phase changes. However, for non-isothermal gradual phase
changes, a varying semi-implicit equilibrium temperature is recom­
mended. That has been proposed through a method called SIMTLE by
Jafari, Seyedein and Aboutalebi [45]. Another point to be discussed is
i
the assumption of T kl ≈ T, mentioned in section 2.1, which poses a
question; How the internal temperature gradients between phases could
be ignored, while the problem is considered as a non-equilibrium case. A
realistic REV would probably include internal conduction, convection,
radiation and morphological effects of the interface. Some references
have addressed microscopic heat transfer and details of formulation of
interphase temperature [4,21,46]. However, phase changes are essen­
tially diffusion-controlled at micro-scale, since the diffusivity of mass is
about 1000 times lower than the diffusivity of heat. Here, the phrase
"deviation from equilibrium" points to the occurrence of meta-stable
phases, which can happen even with isothermal phases, e.g. water and
ice (and the interphase as well) at − 10 ◦ C. Even though the
off-equilibrium state exists in this example, there is no temperature
gradients between phases to address the non-equilibrium situation.
i
Therefore, the assumption, Tkl ≈ T, puts no significant limitation in
phase change modelling, and helps to build up the model independently
of microscopic heat transfer. However, interfacial heat transfer effects
would be totally summarized into a solution of an interphase tempera­
ture [47] and the assumption can be removed from the model.
5. Conclusion
A mathematical model was proposed to manage kinetics of phase
change problems. The model was based on enthalpy method and con­
servations of heat and mass which are governed by Equations (1) and (2)
and enclosed by Equation (13). The main contribution of this work is a
source-based formulation to calculate the rate of phase changes. The
model was successfully implemented in a benchmark study consisting
three test cases; two-phase Stefan problem [33] (equilibrium), cyclic
heating-cooling (non-equilibrium), and a real solidification case with
undercooling (non-equilibrium). The model was verified against
analytical solutions and experimental data. It demonstrated a conver­
gent, consistent and efficient numerical performance. The following
conclusions are made:
1. Kinetics of every thermally-controlled phase change can be modelled
by a mathematical framework of an iterative rate-tuner coupled with
energy equation, which is originally proposed with Equation (13).
This model has shown helpful features including convergence, con­
sistency, no-sophistication, flexibility and efficiency.
2. The results of the model was successfully verified and validated for
equilibrium in test case-I against analytical solutions. It predicted a
sharp interphase and consistent rates for isothermal melting as
shown in Fig. 9 and Fig. 10. Very big rates were obtained at sharp
interphases as the grid size was decreased to capture instantaneous
equilibrium phase-change.
3. An innovative benchmark problem for non-equilibrium phase
change was presented and solved. Non-equilibrium melting-freezing
of an ice bar was simulated under periodic heating-cooling with
different frequencies. A rate-regulation was applied by Equation (15)
and the model showed that it has the potential to supply a spectrum
of possibilities for kinetics of a phase change. As demonstrated in
Fig. 12, three regions of kinetic behavior has been predicted;
Extremely fast (equilibrium, unbounded-rate), moderate (non-
A.R. Jafari International Journal of Thermal Sciences 159 (2021) 106608

equilibrium, limited-rate) and extremely slow (bypassed phase
change, highly-restricted-rate).
4. The proposed phase-change model includes a dual mechanism rate-
controller, equation (16), for problems consisting nucleation-
growth phenomena. The rate-controller uses an interphase detector
function to decide which mechanism is dominant and to adjust the
rate accordingly. The model successfully predicted a real solidifica­
tion of sodium-acetate-trihydrate with undercooling and reca­
lescence. The predicted cooling curves appear to be well supported
by experimental data [37] as shown in Fig. 13. The operation of the
model in controlling kinetics of phase change was discussed and
compared with previous techniques.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Aknowledgement
The author would like to thank Dr. Davoud Haghshenas Fatmehsari,
Dr. Hossein Mirbagheri and Dr. Sadegh Firoozi who gave kind advices
for writing the manuscript. The author also gratefully acknowledge the
constructive comments of the anonymous referees. The Department of
Materials and Metallurgical Engineering at Amirkabir university of
Technology is acknowledged.

Appendix-I. Analytical solution of stefan problem

The exact solution of two phase Stefan problem was used for verification of the presented model. The problem was identified in section 3.1 and
illustrated in Fig. 6. The solution determines the transient location of the interface and transient distribution of temperature within liquid and solid
phases as [33]:
√̅̅̅̅̅̅̅
xi (t) = 2λ αL t , t > 0 (48)
{ /
TW − (TW − Tm )erf(ξL )/ erf(λ) x ≤ xi
T(x, t) = (49)
To + (Tm − To )erfc(ξS ) erfc(βλ) x > xi

√̅̅̅̅̅̅̅̅̅̅̅̅
Where α = k/ρ c is thermal diffusivity, β = αL /αS is ratio of diffusivities and the term λ is obtained from calculation of the root of the transcendental
function [33]:
StL StS √̅̅̅
− =λ π (50)
exp(λ2 )erf(λ) β exp(β2 λ2 )erfc(βλ)
Stefan numbers for liquid and solid are defined separately as StL = cL (TW − Tm )/Lf and StS = cS (Tm − To )/Lf . The solution to the transcendental
function was attained via an iterative bisection method.

Nomenclature

Letters/Abbreviations
A surface area
AiV interphase area per volume
a parameter
aA atom (or monomer) spacing (m)
C constant, coefficient, concentration (1/m3)
c specific heat capacity (J/kgK)
D thermal diffusivity coefficient
Dk mass diffusivity in phase k (m2/s)
d diameter, depth of phase-changed layer (m)
E Activation energy (J)
e equilibrium deviation factor
f mass fraction
f function
fi conversion ratio of phase change
ΔG Gibbs free energy of phenomenon
H total enthalpy (Sensible and latent heat)
ΔH relative enthalpy
h enthalpy (sensible heat) (J/kg)
hConv heat transfer coefficient (W/m2K)
I nucleation rate (1/m3s)
k thermal conductivity (W/mK)
kB Boltzmann constant, 1.38064852×10− 23 (J/K)
kGT Gibbs-Thomson coefficient (Km)
K kinetic term (kg/m3s)
Lf latent heat of fusion
m exchanged mass (kg)
n integer parameter, sharpness degree

13
A.R. Jafari International Journal of Thermal Sciences 159 (2021) 106608

nV number density (1/m3)

n normal vector of the interface
r radius (m)
S heat source term
St Stefan number = c ΔT/Lf
T temperature
ΔT Undercooling/Superheating = T − Teq
t time
V volume (of the element of interest)
v velocity vector
v velocity
x position
Z Zeldovich factor of nucleation

functions
erf ( ) error function
erfc ( ) complementary error function

Greek Letters
α thermal diffusivity = k/ρ c
β rate of atom jumps in nucleation (1/s)
ε volume fraction
φ general dependent variable
ϕi interphase detector function
Γ interfacial mass transfer rate (kg/m3s)
γ surface energy (J/m2)
ν frequency (1/s)
ρ density (kg/m3)
θ wetting angle (rad)
ω angular velocity (rad/s)
√̅̅̅̅̅
ξ similarity independent variable = x/2 αt

Superscripts
mixture (overbar)
eq equilibrium
G growth
i interfacial
N nucleation
n iteration
Ref reference value
V volumetric

Subscripts
A atom
k phase index
l phase index
kl interphase index, k-l direction, k-side
lk interphase index, l-k direction, l-side
L liquid
m melting
N nucleus
o initial value
p particle
S solid

Abbreviations
MTR interfacial mass transfer rate
PC phase change
PCM phase change material
PCR phase change rate
PCRC phase change rate constraint
REV representative elementary volume
VAM volume average model

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A.R. Jafari International Journal of Thermal Sciences 159 (2021) 106608

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