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Acta Materialia 57 (2009) 5862–5875

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Phase-field modelling of as-cast microstructure evolution

in nickel-based superalloys
N. Warnken a,*, D. Ma b, A. Drevermann c, R.C. Reed a, S.G. Fries d,e, I. Steinbach e
a
University of Birmingham, Department of Metallurgy and Materials, Edgbaston, Birmingham B15 2TT, UK
b
Foundry Institute of the RWTH-Aachen, Intzestr. 5, 52072 Aachen, Germany
c
ACCESS e.V., Intzestr. 5, 52072 Aachen, Germany
d
SGF Consultancy, 52064 Aachen, Germany
e
ICAMS, Ruhr University Bochum, Stiepeler Strasse 129, D-44780 Bochum, Germany

Received 4 April 2009; received in revised form 4 August 2009; accepted 4 August 2009
Available online 10 September 2009

Abstract

A modelling approach is presented for the prediction of microstructure evolution during directional solidification of nickel-based
superalloys. A phase-field model is coupled to CALPHAD thermodynamic and kinetic (diffusion) databases, so that a multicomponent
alloy representative of those used in industrial practice can be handled. Dendritic growth and the formation of interdendritic phases in an
isothermal (2-D) cross-section are simulated for a range of solidification parameters. The sensitivity of the model to changes in the solid-
ification input parameters is investigated. It is demonstrated that the predicted patterns of microsegregation obtained from the simula-
tions compare well to the experimental ones; moreover, an experimentally observed change in the solidification sequence is correctly
predicted. The extension of the model to 3-D simulations is demonstrated. Simulations of the homogenization of the as-cast structure
during heat treatment are presented.
Ó 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Multicomponent-solidification; Directional solidification; Homogenisation/solutionisation; Phase field models; Nickel alloys

1. Introduction the differential equations which need to be solved are

Prediction of phase transformations in metals and alloys
requires models for the underlying thermodynamics and
kinetics, and good estimates of critical parameters such
as driving forces, diffusion coefficients and surface tensions
[1,2]. Traditionally, a lack of accurate materials data has
hampered this effort. The calculation of microstructure
evolution in technical alloys—which usually possess more
than three or four alloying additions—have been possible
only with limited accuracy due to the practical necessity
to reduce the problem to a binary or ternary system, con-
sidering only those elements that are assumed to be of
importance [3,4]. An additional difficulty has been that
*
Corresponding author. Tel.: +44 121 414 3527.
E-mail address: n.warnken@bham.ac.uk (N. Warnken).
strongly coupled, so that their non-linearity places signifi-
cant demands on computing resources. Theory for trans-
formations in multiphase, multicomponent systems has
also been lacking.
But this situation is altering. The theory of transforma-
tions in metals and alloys has advanced at pace in recent
years, and methods are available which are capable of
treating multicomponent, multiphase reactions in a realis-
tic way, with the underlying theory rigorously accounted
for [5–12]. Secondly, concerted effort over many years—
for example by the CALPHAD (Calculation of Phase Dia-
gram) community—means that for most systems reason-
ably accurate thermodynamic data are now available and
coded into thermodynamic databases [13,14]. Related
efforts have built databases of diffusion coefficients and
mobilities for the relevant phases [15–17]. Furthermore,

1359-6454/$36.00 Ó 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2009.08.013
 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875 5863
Z
there is now widespread availability of computer hardware,
F ¼ ½f intf þ f chem  dx3 ð1Þ
storage and memory at low cost, so that the possibility of
!
building models is no longer prevented by any lack of X 4rab g2ab
resources. These factors suggest that the time is ripe for sys- f intf ¼  r/a  r/b þ /a /b ð2Þ
gab p2
tematic attempts to model the kinetics of phase transfor- a;b¼1;...;N ;ab
!
mations in complex, metallic systems with all the relevant X X
compositional complexity accounted for. f chem ¼ /a f a f~
ca g þ l i
~ ~ c i
/a ca ð3Þ
a¼1;...;N a¼1;...;N
The research presented in this paper was carried out
with this goal in mind. Nickel-based superalloys—which where rab is the interface energy between phase a and b.
find widespread application in high-temperature applica- Different grains of the same phase, but differing in orienta-
tions such as the turbines used for jet propulsion and elec- tion so that a grain boundary is formed between them, are
tricity generation—are considered [18–20]. Attention is associated with separate phase fields. The interface energy
focused on the liquid to solid transformation; this is of will be anisotropic with respect to the relative orientation
practical importance since many critical components, e.g. between the phases. The term gab is the interface width that
turbine blades and guide vanes, are manufactured to near will be treated equal for all interfaces. The chemical free en-
net shape using casting methods [21–25]. Solidification ergy is built from the bulk free energies of the individual
can then be the cause of melt-related defects in these com- phases fa fc i
@g
 a g, dependent on the phase concentrations
ponents, which predictive methods would help to avoid. At i i
~ ¼ @ci is termed the diffusion potential of component
ca ; l
present, no model exists which addresses the full complex- i [9] to distinguish it from the chemical potential (g is the
ity of alloying in these alloys, the associated morphological chemical free energy density), introduced as a Lagrange
evolution of the dendritic structure and the subsequent multiplier to conserve the mass balance between the phases.
solid-state decomposition upon cooling. An attempt to The local number of phases is N ¼ N fxg, which is subject
do this is now described. to the constraints:
X
2. Multicomponent multi-phase-field model /a ¼ 1 ð4Þ
a¼1;...;N
X
The approach employed is based upon the multicompo- /a cia ¼ ci ð5Þ
nent multi-phase-field model reported in Refs. [9,26], with a¼1;...;N

some adaptations as follows. The governing equations for The multi-phase-field equations are given by (for details see
the phase-field /a ; 0 < /a < 1 and concentration ci of com- Ref. [27]):
ponent i of a multicomponent material are derived from
X  
the principle of Gibbs energy minimization, where the p2 dF dF
global free energy F is defined from the interfacial energy /_ a ¼  l  ð6Þ
b¼1;...;N
8gN ab d/a d/b
density f intf and the chemical energy density f chem . Both
are expanded in the phase-field variables, their gradients
which is a superposition of dual phase changes between
and the concentrations in the individual phases cia , accord-
pairs of phases. The interface mobility lab is defined
ing to:
separately for each pair of phases. The antisymmetric
approximation for the phase-field Eq. (6) [10] is used with

@fa @f
1374
the chemical driving force defined by: Dgab ¼ @/a
 @/bb
X  
p2
Dendrite Tip Temperature [°C]

/_ a ¼ lab rab /b r2 /a  /a r2 /b þ 2 ð/a  /b Þ

1372 b¼1;...;N
2g

p qffiffiffiffiffiffiffiffiffiffiffi
þ /a /b Dgab ð7Þ
g
1370
where r is the interface stiffness, which considers the inter-
face anisotropy via the Herring torque terms [28]. For a
1368 multicomponent system, a set of k diffusion equations for
every solute component is required; these are in general
not independent but linked by cross-terms. These equa-
0 2 4 6 8 tions are derived by considering the superposition of the
Velocity [mm/min]
fluxes in the individual phases:
Fig. 1. Calculated decrease in the dendrite tip temperature with the ! !
dendrite tip velocity, due to variation in the pile-up of alloying elements X N
dF X N

ahead of the tip. Estimates made using the modified marginal stability
c_i ¼ r ij
/a M a r j ¼ r ij j
/a Da rca ð8Þ
a¼1 dca a¼1
theory of the Appendix.
5864 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875
where the chemical mobilities are denoted M ija and the dif-
2
fusion coefficients by Dija ¼ /a M ika @c@k @c
F
j . The Gibbs energy
a a
data fa and chemical mobilities M ik are estimated from
the CALPHAD databases published by NIST [29,16]. An
extrapolation scheme for the thermodynamic calculations
needed at the interfaces is used to speed up the calculations
[9]. The phase-field model is implemented in the MICRESS
software [30] which was coupled with the ThermoCalc
package [31].
3. Details of calculations for constrained dendritic growth
Nickel-based superalloys which are undergoing direc-
tional solidification show mushy zone lengths on the milli-
meter scale and dendrite tip radii of the order of
micrometers. A simulation which resolves both length
scales properly is currently still not feasible, in particular
not for alloys which are multicomponent in nature.
Approximations are therefore necessary.
In order to overcome this limitation in this work, an
approach based on a simple analysis of directionally grow-
ing dendritic arrays is used, which is based on work pub-
lished by Ma [32]. In the following it is assumed that the
directionally growing dendrites are perfectly aligned with
the thermal gradient. The primary dendrite arm spacing
(PDAS), k1 , defines the characteristic length scale of direc-
tionally growing dendritic arrays. The PDAS is related to
the thermal gradient G and solidification rate v according
to:
k1 ¼ c G1=2 v1=4
This correlation has been confirmed by several researchers
[33–35]. The coefficient c is alloy dependent. In a recent
study it was also shown that it depends on the anisotropy
of the interfacial energy [36]. However, in this work it
has been measured experimentally for the alloy analyzed,
see Section 4. It should be pointed out that the PDAS is
the only characteristic length of the dendrites that does
not change during the processing of the material, i.e. the
PDAS is the same at the dendrite tip during freezing and
in the solidified microstructure. Thus, in order to achieve
a fully homogeneous microstructure, microsegregation
whose maximum wavelength is at the length scale of the
PDAS has to be removed during the solution heat treat-
ment, see Section 7.
Given the above it is apparent that the PDAS is the most
important characteristic length of the dendritic array. A
representative volume element (or unit cell, UC) is there-
fore defined on a transverse section with the size given by
2
ð0:5 k1 Þ . The factor 0.5 appears because—due to symme-
try—only one-quarter of the dendrite has to be taken into
account. The UC is isothermal, but the cooling rate T_
depends on the solidification parameters consistent with
T_ ¼ Gv. The initial temperature is given by the correspond-
ing dendrite tip temperature, which is calculated using the
marginal stability approach, extended to multicomponent
alloys [37,38]. It should be noted that is has been demon-
strated that the marginal stability theory does not capture
the full physics of the dendritic growth problem, unlike the
more up-to-date microscopic solvability theory [39,40].
However, the final equations are very similar in appear-
ance. Details on this are given in the Appendix. The micro-
structure evolution within the UC is then simulated using
the multicomponent multi-phase-field approach.
The UC definition allows the smallest possible UC to
analyzed, thus reducing computational cost. One advan-
tage of using the phase-field method to describe the micro-
structure evolution is that it is straightforward to enhance
the UC to simulate more complex situations. Possible
enhancement in two dimensions can be achieved by using
non-square-shaped UCs and larger UCs with more than
one dendrite. These are compatible with the description
given above if the following condition is fulfilled:
rffiffiffi
A
k1 ¼ ð10Þ
n
which represents a correlation between the area A of the UC
and the number of dendrites n within it. The same relation is
also commonly used to determine the PDAS of dendritic
arrays. Furthermore the UC can be enhanced by extending
it to three dimensions, with the size in the third dimension
chosen to reflect the secondary dendrite arm spacing (SDAS)
at the end of the solidification, see Section 5.5.
4. Experiments
ð9Þ A number of experiments were carried out with a super-
alloy designed specifically for the purposes of validating the
model; the alloy composition is given in Table 1. The
results provide reference data for validating the model
and testing its accuracy.
Cylindrical samples 8 mm in diameter were directionally
solidified. In order to achieve different thermal gradients,
Bridgman furnaces with three different experimental
arrangements were used. This allowed processing at ther-
mal gradients of 4, 10 and 20 Kmm1 with solidification
rates between 0.08 and 5:0 mmmin1 . A typical microstruc-
ture of samples solidified under industrially relevant casting
conditions consists of c dendrites and interdendritic c0 ; for
very low solidification rates only the c phase is observed. In
the high gradient arrangements (10 and 20 Kmm1 ) sam-
ples were quenched to freeze in the mushy zone morphol-
ogy. From these samples the planar–cellular transition
was found to lie at G=v ¼ 224:4 K min1 mm1 and the cel-
lular–dendritic transition at G=v ¼ 126:3 K min1 mm1 .
Mushy zone characteristics were determined from longitu-
Table 1
Composition of the alloy used for the validation studies.
Element Al Cr Ta W Ni
at.% 13.06 10.49 2.67 2.92 Bal.
wt.% 5.80 8.98 7.94 8.84 Bal.
 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875 5865

dinal sections of quenched samples; the distance between
the dendrite tip and the bottom of the mushy zone (mushy
zone length) xsl , see Fig. 2, as well as the first occurrence of
interdendritic c0 were measured. The dimension of the
mushy zone, but not the point of c0 formation, was found
to be solidification rate dependent. Furthermore, the frac-
tion of solid evolution along the mushy zone length was
measured from sections taken on quenched samples at
intervals of 0.9 mm. Finally the PDAS was determined
from transverse sections and this allowed the coefficient c
in Eq. (9) to be determined as 1915 m3=4 K1=2 s1=4 (Fig. 3).
To characterize the microsegregation patterns inherited
from processing, wavelength dispersive X-ray spectroscopy
(WDX) was used. For this alloy, it was found that the ele-
ments Al, Cr and Ta segregate to the melt and W to the
dendrites during the primary solidification, although the
partitioning of Cr was weak, implying a partitioning coef-
ficient k Cr close to unity. The solubility of Al and Ta in c0
was very high, while that of Cr and W very low. This leads
to the interesting observation that the highest Cr concen-
tration is observed in the interdendritic region, next to
the lowest Cr concentration, which is observed in the inter-
dendritic c0 . The same behaviour was recently also
observed for CMSX-10 alloy [41]. The volume fraction of
the interdendritic c0 was found to be around 1 vol.%, signif-
icantly lower than for other single-crystal superalloys (e.g.
CMSX-4  10 vol.%).
The liquidus temperature was estimated from differen-
tial thermal analysis measurements as 1386 °C, which com-
pares well with the results obtained from thermodynamic
calculations with the NIST database, which predict a liqui-
dus temperature of 1375 °C, a solidus temperature of
1340 °C and c0 solvus at 1263 °C.

5. Simulations

5.1. Simulation conditions

The UC was discretized using 100  100 square cells and

grid spacings of the order 1 lm. This corresponds to a
PDAS of 200 lm. In order to adjust the size of the UC size
to the required PDAS, the grid spacing was chosen appro-
priately, i.e. a grid spacing of Dx ¼ 0:9 lm, for example,
would be chosen for a PDAS of 180 lm. For the 3-D sim-
ulation it was assumed that the SDAS is one-third of the
PDAS and therefore a grid of the dimensions of
100  100  31 cells was used. The interfacial width gab in
Eq. (2) was chosen as 4 Dx for all interfaces.
Fig. 2. Micrograph of the experimental alloy indicating the distance xsl Consistent with the experimental work, simulations
between the dendrite tip and the base of the mushy zone. were performed for the three different thermal gradients
of 4, 10 and 20 K mm1 and a number of different solidifi-
500
cation rates, ranging from 0.08 to 8 mm min1 .
Treatment of the nucleation of interdendritic c0 at the c/
400 liquid interface was carried out as reported in Ref. [42]. The
critical undercooling for nucleation was assumed to be 7 K.
300
The thermodynamic and kinetic databases from NIST were
used [29,16].
λ1 [μm]

200
Fit 5.2. Simulation results
G=4 K/mm
100 G=10 K/mm The growth of the dendritic phase within the UC and the
G=20 K/mm
evolution of microsegregation for conditions correspond-
0
ing to a the thermal gradient of G ¼ 20 K mm1 and a
0 0.1 0.2 0.3 0.4 0.5 0.6 solidification rate v ¼ 5:0 mm min1 , is illustrated in
-0.5 -0.25 -0.5 -0.25
G v [K/mm] [mm/min] Fig. 4. The initial circular c dendrite tip quickly becomes
Fig. 3. Variation of the primary dendrite arm spacing as a function of unstable, developing the typical 4-fold symmetry expected.
thermal gradient G and solidification rate v, as obtained from the After the final portion of liquid has solidified (260 s), the
directional solidification experiments. dendritic morphology can still be identified via the segrega-
5866 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875
Fig. 4. Simulated growth of the c dendrites, interdendritic c0 and formation of microsegregation in isothermal sections, for G ¼ 20:0 K mm1 and
v ¼ 5:0 mm min1 .
tion pattern which is inherited from processing. Al segre-
gates to the melt during primary ðcÞ solidification
ðk < 1Þ, and enriches in the c0 phase. Thus the lowest Al
concentration is observed in the dendrite core and the high-
est in the interdendritic c0 . Due to back-diffusion, the den-
drite appears rather diffuse when visualized using the Al
segregation pattern. During the primary solidification, Cr
segregates to the melt, but the partitioning coefficient is
very close to unity. Thus the Cr concentration in the inter-
dendritic region is higher than in the dendrite core. How-
ever, the solubility of Cr in c0 is very low, and thus the
lowest Cr concentration is found in the c0 particles. This
contradicts most solidification and microsegregation theo-
ries which assume constant and steady elemental partition-
ing from the beginning to the end of solidification. Ta
shows a partitioning behaviour very similar to that of Al,
except that the dendritic structure appears sharp and clear
due to its slower diffusion in the solid phase. W partitions
to the c phase during the primary solidification and shows
a very low solubility in the interdendritic c0 . The highest W
concentration is observed in the dendrite core and the low-
est in the interdendritic c0 , which is the reverse for that seen
for Al and Ta. Thus, a steady segregation behaviour is
observed for the elements Al, Ta and W and an unsteady
segregation for Cr. Direct comparison between measured
and calculated microsegregation patterns confirms these
observations (Fig. 5). Good agreement is also found for
the position of the interdendritic c0 particles.
In Fig. 6 the fraction of solid as function of temperature
during directional solidification is shown for the case of lever
rule, Scheil’s model, phase-field simulations and experiments.
Phase-field and experimental results are given for two differ-
ent solidification rates (v ¼ 0:5 and 2:0 mm min1 ) at the
same thermal gradient ðG ¼ 10 K mm1 Þ. Naturally the
lever rule and Scheil’s model results are not sensitive to the
solidification conditions. Due to the initial undercooling
assumed in the phase-field simulations, the fraction solid
close to the liquidus temperature (1375 °C) lies below the pre-
diction of the Scheil’s model. After a steep increase, the
phase-field result stays between the limits given by the lever
 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875 5867

Fig. 5. Comparison of calculated Al, Cr, Ta and W element distribution maps (top) with measured ones (bottom).

100

80
Fractionsolid[%]

60 Lever Rule
Scheil
0.5 mm/min
40 2.0 mm/min
MICRESS 0.5 mm/min
MICRESS 2.0 mm/min
20 G = 10 K/mm

0
1250 1260 1270 1280 1290 1300 1310 1320 1330 1340 1350 1360 1370
Temperature [°C]

Fig. 6. Estimates of fraction solid as a function of temperature, obtained from the Scheil model, lever rule and phase field simulations and comparison
with experimental results.

rule and the Scheil’s model, and good overall agreement
between phase-field simulation and experiments is found.
The results for the higher solidification rate ð2:0 mm min1 Þ
are slightly closer to the Scheil curve and exhibit a longer sol-
idus–liquidus interval. At higher temperatures (>1335 °C)
the measured fraction solid values are higher than the calcu-
lated ones. This could be due to a systematic measurement
error, as at these temperatures the dendrites grow during
the quench.
In practice, the PDAS in dendritic arrays exhibits a dis-
tribution rather than a unique value as indicated by the
error bars in Fig. 3. For this reason the influence of the
variations in the PDAS on the simulated microstructure
was examined. Simulations for two sets of solidification
parameters were performed: (i) G ¼ 4 K mm1 ; v ¼
3 mm min1 and (ii) G ¼ 20 K mm1 ; v ¼ 5 mm min1 .
For these conditions the PDAS k1 and the standard devia-
tion in its value Dk1 were available from the measurements,
and therefore in the simulation the PDAS was varied as
k1  2Dk1 ; this resulted in simulations covering the upper
and lower end of the observed distribution. The cooling
rate and initial temperature is to a first-order approxima-
tion the same for each dendrite in an array. The results
show smaller c0 fractions at the lower, and higher c0 frac-
tions at the upper end of the distribution, when compared
to the fraction at the average PDAS (Fig. 7). The variation
at the lower end is more pronounced than at upper end and
the same trend is also observed for the freezing range.
These results are consistent for the two sets of solidification
parameters and can be explained by back-diffusion in the
5868 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875

1.3 used for the assessment. The diagram for a thermal gradi-
ent of 10 K mm1 is shown in Fig. 8; further assessments
1.2 would be required for an extension to other thermal gradi-
20 K/mm ents. The three major regimes for directional solidification
1.1
γ’ fraction [%]

5 mm/min morphologies are indicated: planar front, cellular and den-

1 3 mm/min
0.9
0.8
0.7
-2 -1
λ1 ±Δλ1
Fig. 7. Variation of the calculated c0 fraction with the primary dendrite
spacing for fixed solidification conditions; Dk1 denotes the standard
deviation of the measured primary spacing.
solid phase. Lower spacings reduce the diffusion distance
and therefore increase the effect of solid-state diffusion.
This moves the solidification path away from the Scheil’s
model and closer towards that predicted by the lever rule.
5.3. Kinetic phase diagram
The modelling work has provided new insights into the
solidification sequences occurring in these alloys, and in
particular the construction of a kinetic phase diagram
which correlates the phase transition temperatures with
the solidification conditions (see Fig. 8). Note that the dia-
gram is valid for the dynamic equilibrium of steady-state
directional solidification, as distinct from the static equilib-
rium of a thermodynamic phase diagram. Data obtained
from thermodynamic calculations, analytical models of
solidification, numerical simulations and experiments were
1400
Exp. Solidus
Exp. γ’
Sim. Solidus
Sim. γ’
1350
Temperature [°C]
4 K/mm dritic growth. Each of these regimes are now discussed.
In the planar front regime, solidification proceeds with-
out a mushy zone. In this case, the growing solid phase
consists entirely of microsegregation-free c phase, the com-
position of which corresponds to the mean alloy composi-
tion; the solid phase forms at the solidus temperature of the
alloy [33]. Upon further cooling, the temperature reaches
0 1 2
the c0 solvus temperature and the c0 phase precipitates from
the c matrix via a solid-state transformation. For this case
the transition temperatures, liquidus and c0 solvus, can be
obtained from equilibrium thermodynamic calculations.
Note that the solidification rates in this regime are approx-
imately two orders of magnitude lower that those in indus-
trial-scale Bridgman processes used for turbine blade
manufacturing.
In the cellular front regime, the solidification front
morphology commonly shows cells with a finite depth,
which can be measured from quenched samples. The
growing solid phase consists entirely of c phase, which
exhibits microsegregation due to solutal pile-up ahead
and between the cells. This becomes more pronounced
as the velocity increases. Upon further cooling, c0 forms
via solid-state precipitation, and due to the increasing
degree of microsegregation, the reaction starts at higher
temperatures as the solidification rate increases. Unlike
the case of planar front growth, the solidification front
temperature and c0 formation temperature cannot be
determined from simple analytical models and thermody-
namic calculations. Therefore the lines in the cellular
regime in Fig. 8 are given as dashed lines, being meant
to indicate trends only.
The dendritic growth regime is where the phase-field
model is particularly powerful; here transformation is asso-
liquid ciated with the formation of a substantial mushy region.
The dendrite tip temperature ðT dendrite Tip Þ was obtained
from the multicomponent marginal stability theory, which
liquid + γ gives the highest temperature at the cellular–dendritic tran-

sitions and a monotonic decrease with solidification rate, as

liq. + γ + γ’ the solidification rate increases. This constitutes the liqui-
dus temperature of the dendritic regime. The dendrites con-
γ sist of the c phase and for solidification rates higher than
1300 0:3 mm min1 the formation of interdendritic c0 is
observed. The mushy zone length xsl , as measured from
γ ’+ γ
longitudinal sections of quenched samples, multiplied by
planar cells dendrites G=10 K/mm the thermal gradient yields the non-equilibrium freezing
1250 range DT 0 . Using this in the relationship:
0.01 0.1 1 10
T 0 ¼ T dendrite Tip  xsl G ¼ T dendrite Tip  DT 0 ð11Þ
Fig. 8. The kinetic phase diagram which correlates the phase transition gives experimental estimates of the solidus line of the den-
temperatures—obtained from simulations and experiments—with the
dritic regime of the diagram in Fig. 8 (closed square sym-
solidification rate; the dashed horizontal lines mark (from the top) the
equilibrium liquidus, solidus and the Scheil c0 formation, as well as the bols). The temperature for the formation of the
equilibrium c0 solvus temperatures. interdendritic c0 is determined in a similar way.
 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875
The simulated solidus temperature and the temperature
of interdendritic c0 formation can directly be read from the
simulation results, shown as open symbols in Fig. 8. The
temperature at which interdendritic c0 forms according to
the Scheil model (1293 °C) is also given in Fig. 8 (thin hor-
izontal dashed line) for comparison. An increase in the
solidification rate results in higher solute pile-up at the
solid–liquid interface, which then in turn leads to finer den-
drites but also stronger microsegregation. This causes not
only the mushy zone length to increase but also triggers
the formation of the interdendritic c0 . Moreover microseg-
regation also shifts the solid-state c0 precipitation to higher
temperatures. Detailed information about this has not been
extracted from the results available here, but it is reason-
able to assume that the upper limit for this temperature
shift is the formation temperature of the interdendritic c0 .
This is supported by the observation that the interdendritic
c0 nucleates via a solid-state reaction in the c dendrites as
described in Ref. [42].
The results from simulations and experiments indicate
that the dendritic regime in Fig. 8 consists of two regions,
which are distinguished by a vertical dashed-dotted line at
0:3 mm min1 on the diagram. For lower velocities, only
the c phase grows from the melt, and the phase-transforma-
tion sequence can be summarized as liq ! liq þ c ! c
! c þ c0s , where c0s refers to c0 formed by solid-state pre-
cipitation. Above 0:3 mm min1 the formation of interden-
dritic c0 is observed, and therefore the transformation
sequence changes to liq ! liq þ c ! liq þ c þ c0l ! c
þc0l þ c0s , where c0l refers to c0 formed by solidification, i.e.
interdendritic c0 . Interestingly, the temperature of the inter-
dendritic c0 formation is independent of the solidification
rate and approximately 10 K higher than the temperature
given by the Scheil model. The latter can be explained by
the considerable back-diffusion of the alloying elements.
The fast-diffusing elements Al and Cr [29,16] are most
likely to be responsible for this.
Both simulation and experimental results show a signif-
icant increase in the liquid–solid temperature interval as the
solidification rate increases; this effect is particularly pro-
nounced below 0:3 mm min1 . It is also observed that in
the experiment the solidification finishes above or just
slightly below the equilibrium solidus temperature (thin
dashed line). This can be regarded as unrealistic and
indicates that the dendrite tip temperature given by the
analytical model is too high. Above 0:3 mm min1 good
agreement between simulations and experiments is
observed.
5.4. Sensitivity studies
Given the assumptions in the UC model approach used
here, it is not obvious how the model will react to changes
in the solidification parameters G and v; one could expect
that changes are compensated by the cooling rate and the
primary dendrite spacing. To investigate this, a series of
simulations was carried out for combinations of different
5869
thermal gradients (4, 10 and 20 K mm1 ) and different
solidification rates ð0:5–8:0 mm min1 Þ. The calculated
fraction of interdendritic c0 is plotted as a function of the
primary dendrite spacing in Fig. 9. The solid lines are
intended as visual guides to illustrate the trends observed.
The scatter in the results originates from the nucleation
model used for the interdendritic c0 . The graphs show a
decrease in the interdendritic c0 fraction with increasing
PDAS. The slopes of the lines are proportional to the ther-
mal gradient, with the results for G ¼ 20 K mm1 showing
the steepest and for G ¼ 4 K mm1 the shallowest slopes.
For the same range of solidification rates, a lower thermal
gradient leads to a larger variation in the PDAS than a
higher thermal gradient. At the same time, for the same
range of solidification rates, a lower thermal gradient
results in a smaller variation in the cooling rate than a
higher thermal gradient. A large PDAS and fast cooling
would weaken the effect of back-diffusion. This explains
why the high thermal gradient simulations show a larger
variation of the interdendritic c0 fraction than the low-gra-
dient simulations.
5.5. Extension to 3-D calculations
The diagram in Fig. 10a illustrates the morphology of
the c dendrite in a partially solidified 3-D UC simulation,
together with the arrangement of the UC considered in this
case. The centre of the primary dendrite arm is located in
the upper left corner of the UC, while the bottom and
the top plane run through the secondary dendrite arm
and the middle between two adjacent secondary arms,
respectively. The crystallographic directions and the direc-
tion of the thermal gradient are indicated; solidification
proceeds in the direction of the latter. On top of the sec-
ondary arm the formation of a fin is observed, which would
in a more freely growing dendrite eventually becoming a
tertiary arm.
In the lower portion of Fig. 10b concentration profiles
of W along the h1 0 0i direction, starting from the dendrite
1.2
1.1
G = 4 K/mm
1
γ ’ fraction [%]
0.9
0.8 G = 10 K/mm
0.7 G = 20 K/mm
0.6
0.5
100 200 300 400 500
primary spacing λ1 [μm]
Fig. 9. Variation of the calculated c0 fraction with the primary dendrite
spacing, for different combinations of G and v.
5870 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875

a ic c0 is shown as black spotted regions, whilst the dendrite

morphology is revealed by plotting W-isosurfaces, corre-
sponding to 2.1 and 3.5 at.%. In order to generate the
image shown in Fig. 11, 16 UCs were combined and visu-
alized. It is clear that the interdendritic c0 forms in the plane
between the secondary dendrite arms and that the larger c0
particles are found along the h1 1 0i direction. The overall
secondary c0 fraction (0.37 vol.%) is slightly lower than in
the corresponding 2-D simulation (0.60 vol.%).
Naturally the computational time of these simulations
depends on the complexity of the problem and the size of
the calculation domain. Therefore the enhancement of
the UC to three dimensions has a significant influence on
b 4 the CPU time. A simulation for G ¼ 20 K mm1 and
v ¼ 5:0 mm min1 takes less than 1 day on a current PC
3D bottom
server. In the case of 3-D simulations the simulation time
3 also increases linearly with the number of cells in the third
direction. It is also found that the solidification time has a
W [at%]

3D top 2D
2

0 50 100 150 200

Dendrite core Distance [μm] Interdenditic

Fig. 10. 3-D representation of the unit cell (UC) (a) and comparison of
linescans from the bottom and top of the 3-D UC with the corresponding
2-D result (b).

core and running towards the interdendritic region in the

bottom and top plane of the 3-D UC, are given. The same
scan obtained from a 2-D UC simulation is also shown for
comparison. Both simulations were performed for the same
solidification parameters (G ¼ 10:0 K mm1 and v ¼ 0:5
mm min1 ). The curve taken from the bottom of the 3-D
simulation shows a steady decrease in the W concentration
towards the interdendritic region, although a significant
slope of the curve is observed only in the last 30 lm
towards the interdendritic region. The curve from the top
plane of the UC shows a very different concentration pro-
file. An initially steep drop of the W concentration at the
core of the dendrite is followed by a local maximum and
a steep decrease in the interdendritic region. The shapes
of the two curves reflect the morphology shown in
Fig. 10a. The local maximum of the bottom plane curve
marks the position at which the fin of the secondary arm
inpinges on the top plane of the UC (or more precisely with
the fin of the adjacent secondary arm). The curve from the
2-D simulation by way of comparison shows a steadier
decrease of the W concentration and even indicates the
location of interdendritic c0 in the interdendritic region.
The 2-D curve also stays well between the limits of the
curves from the 3-D UC.
The location of the interdendritic c0 can be clearly iden- Fig. 11. Predicted microstructure from 3D calculations, revealed by
tified from the simulation results (see Fig. 11). Interdendrit- appropriate choice of W isosurfaces (2.1 and 3.5 at.%).
 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875
major influence on the CPU time: the two scale linearly.
Thus, simulations for lower thermal gradients and lower
withdrawal rates take longer.
6. Discussion
Despite the assumptions made, it has been demonstrated
that the model predicts much of the microstructural infor-
mation relevant to the directional solidification of the
superalloys. In particular, the complex interaction between
elemental partitioning, evolution of dendritic morphology,
back-diffusion, thermodynamic interactions and competing
length scales are accounted for. The model can be extended
readily to other grades of superalloy, to include (i) those
commercial superalloys (CMSX-4, Rene N5) which find
commercial application; and (ii) other prototype grades
which are being considered for use in advanced turbine sys-
tems. Therefore, it is tremendously useful both for assess-
ing the microstructure expected during processing and
hence the castability of alloys already in service, but also
for the purposes of anticipating manufacturing issues
which might arise with new grades of alloy, at the alloy
design stage.
An important finding is that the fraction-solid evolution,
the solidification interval and the amount of interdendritic
phase which forms are affected strongly by back-diffusion.
This supports findings reported earlier by other researchers
[43]. It is found that the degree to which back-diffusion
changes the solidification path depends not only on the dif-
fusion kinetics, but also on the diffusion distance. Thus due
to the formation of dendrite arms, the diffusion distance
shortens and back-diffusion becomes more important. This
leads to the observed velocity-dependent solidification
interval and explains why interdendritic c0 forms only
above a given threshold of solidification rate. Classical
1-D microsegregation models often use the secondary den-
drite arm spacing as the characteristic length, but this
approach does not account for the composition difference
between the dendrite core and the interdendritic region
with the associated length, the PDAS. Subsequent simula-
tions of solution heat treatment have to take this into
account. The UC approach demonstrated here allows both
lengths to be captured, as the dendritic morphology allows
for short back-diffusion distance while the PDAS remains
the characteristic length scale. Finally back-diffusion also
raises the temperature of the interdendritic c0 formation
by 10 K when compared to the Scheil model. The experi-
ments and previously reported results [44] support the
phase-field results. The 3-D extention of the UC leads to
greater surface to volume rations and therefore to even
more back-diffusion.
Further points relate to the use of the UC for modelling a
single representative dendrite in the array. Whilst there is
confidence assumptions will be relaxed as greater computa-
tional resources become available, the results show already
a good sensitivity to changes in the solidification parameters.
This is not immediately clear from the governing equations,
5871
as one could also expect that this would be compensated for
by a changes in the PDAS. The results confirm that different
combinations of G and v result in the same PDAS but differ-
ent microstructures. This can be understood by looking at
the different relationship between PDAS and the cooling
rate, with the latter mainly determining the solidification
time. This influences significantly the dendrite morphology
and the amount of back-diffusion. However, the model is less
convincing in the cellular-dendritic regime; there, the
assumption of independently growing dendrites is no longer
valid. Furthermore a significant solutal pile-up will build up
ahead of the solid–liquid interface. This contradicts the
model assumptions and explains the difference between the
simulations and experimental results. However, these condi-
tions are unlikely to occur in technical directional solidifica-
tion processes of turbine blades, since withdrawal rates of
3 mm min1 and thermal gradients of 4 K mm1 are
employed. Therefore, this effect is unlikely to hamper the
application of the model in practice.
7. On the possibility of through-process modelling of
microstructure evolution of turbine blades
The simulation results raise the possibility of taking a
significant step towards the goal of estimating the micro-
structural condition at service entry, and thus the
through-process modelling of microstructure evolution in
these alloys. Clearly, in order to simulate the solution heat
treatment of single-crystal components, an accurate
description of the solidification microstructure is necessary,
as this defines the starting condition for the simulation; the
model presented provides this. As back-diffusion is taken
into account, it is relatively straightforward in principle
to simulate the homogenization of the solidification micro-
structure during subsequent solution heat treatment. In
principle, calculations performed in this way would help
to anticipate the heat treatment required for any new grade
of superalloy. They might also aid in the optimization of
the design of the heat treatment process.
To illustrate that this is indeed possible, calculations
have been performed for the microstructure evolution
expected during a 10 hour isothermal solution heat treat-
ment at 1285 °C (see Fig. 12). It is apparent that after
30 min the fast-diffusing elements Al and Cr already show
very little remaining microsegregation, while the microseg-
regation of the slow-diffusing elements Ta and W is hardly
affected. After 1 h new regions of inhomogeneity appear in
the dendrite side arms (Al), and move to the dendrite core
after 2 h (Al and Cr). This phenomenon is attributed to the
cross-diffusion effects present in the system. The gradient in
the W field drives the diffusion in the Al and Cr field. Thus
the overall homogenization kinetics is controlled by the dif-
fusion of W. After 10 h of solution heat treatment Al, Cr
and Ta are microsegregation free, while W is still not fully
homogenized. The amount of interdendritic c0 is noticeably
reduced.
5872 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875

Fig. 12. Simulated microstructure evolution during solution heat treatment at 1285 °C, illustrating the effect of homogenization of as-cast structure by
diffusion.

The efficiency of solution heat treatments is often evalu-
ated from the fraction of residual interdendritic c0 present
at the end of the heat treatment, and this can also be pre-
dicted. Fig. 13 shows the predicted evolution of the fraction
of the interdendritic c0 as a function of time for different
solution heat treatment temperatures, ranging from 1275
to 1305 °C, as obtained from simulations. It is seen that
interdendritic c0 dissolves significantly faster at higher tem-
peratures. To test these calculations, experimental heat
treatments were carried out and these show the similar
overall dissolution kinetics as the simulations—see
Fig. 13 symbols. Note that the error bars on the experimen-
tal values—which correspond to the standard deviation of
the measured c0 fractions—appear rather large since the
overall c0 fraction is not very high. However, the absolute
variation of the measured c0 fraction is within reasonable
limits. This provides confidence in the model as a useful
predictive tool.
Interestingly, the simulations predict an increase of the
c0 fraction during the early stages of the heat treatment at
lower temperatures (1275 and 1285 °C)—see Fig. 13. The
dissolution of the interdendritic c0 is predicted to occur
only after an incubation period. This is due to the pres-
ence of microsegregation, which has a stabilizing effect on
 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875 5873

2
1285 °C
1.75 1295 °C

1.5

Fraction γ’ [%]
1.25 1275 °C

0.75
1285 °C
0.5
1295 °C
0.25
1305 °C
0
0 1 2 3 4 5 6 7 8 9 10 11
time [h]

Fig. 13. Simulated fraction of interdendritic c0 phase during solution heat treatment at various temperatures, and comparison with experimental results.

the interdendritic c0 ; the dissolution is found to start only Application of the model has provided new insight into
after the microsegregation has been sufficiently homoge- the phase transformations occurring during solidifica-
nized. This effect is not observed in the experiments; here tion; back-diffusion is important and a threshold for
the interdendritic c0 is surrounded instead by a c=c0 two- the c0 formation temperature has been predicted.
phase mixture, which formed during cooling of the solid- Extension of the methods to include homogenization of
ified material. More work is needed to account for these the as-cast microsegregation is demonstrated. This offers
effects. the hope that the service-entry microstructure can be
estimated as a function of all relevant processing steps
(casting, heat treatment); this represents a through-pro-
8. Summary and conclusions cess modelling capability.
A model, based upon on the phase-field method, was
presented for the prediction of microstructural evolution Appendix A. Dendrite tip growth parameters
during solidification of nickel-based superalloys. The fol-
lowing conclusions have been drawn: The dendrite tip radius for a given tip velocity vtip and
composition of the melt at the tip ci is given by:
It is demonstrated that the model can account for the sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
full compositional complexity of technically relevant 2C 1
Rtip ¼ 2p P mi ð1kÞc  ð12Þ
alloys which contain substantial quantities of Al, Ta, i vtip
Di
W and Cr among other elements.
The microsegregation, phase fractions in the as-cast where Di are the individual liquid diffusion coefficients of
microstructures, the solidification-rate-dependent dimen- the alloying elements and C ¼ r=DS f the Gibbs–Thomson
sions of the mushy zone and the sequence of phase forma- coefficient, r is the interfacial energy and DS f the entropy
tion are correctly predicted. The model also shows good of fusion per volume. The dendrite tip radius Rtip and the
response to changes in the casting conditions. The tip undercooling are correlated by the Ivantsov solution I v :
enhancement of the simulation approach to the 3-D UC  
c  c0i Rvtip
is demonstrated. X¼ i ¼ I v ð13Þ
ð1  kÞci 2Di
Since the model is connected to established thermody-
namic and kinetic databases of parameters, it has the with ci the interface liquid concentration of element i and
advantage of using well-assessed information; moreover c0i the corresponding far field (alloy) concentration. Eq.
its fidelity will improve as the accuracy of the underlying (13) is evaluated for each element separately. For a given
databases is improved. tip radius, the tip concentration is given by:
The model represents a valuable tool for the prediction c0i
of microstructure in commercially relevant superalloys ci ¼ ð14Þ
Xð1  kÞ  1
but also those which are under development. Therefore,
it is useful both for process modelling/simulation for The actual dendrite tip temperature is obtained when the
assessing manufacturability but also for the purposes temperature equivalent of the solutal pile-up is summed
of the design of new alloys. up over all alloying elements:
5874 N. Warnken et al. / Acta Materialia 57 (2009) 5862–5875
X
T tip ¼ mli ðci  c0i Þ ð15Þ culate the dendrite tip temperature. Starting from an
initial estimate of the tip radius and the alloy composi-
The dimensionless undercooling X is calculated with the tion, the dimensionless undercooling X and a new tip
Ivantsov solution [45], which is different for 2-D and 3-D concentration ci is calculated with Eqs. (13) and (14).
problems: This new concentration is inserted into Eq. (12) and the
pffiffiffiffiffiffi pffiffiffi
2-D : X ¼ pP exp P erfc P ð16Þ result is compared to the previous estimate of the tip
radius. If the agreement is poor, the result is used as
3-D : X ¼ P exp P E1 P ð17Þ
the new guess for the next iteration. Usually convergence
where P ¼ Rv=2D is the solutal Pclet number, erfc denotes is reached after two or three iterations. It is found that
the error-function-complement and E1 the exponential the dendrite tip temperature (Fig. 1) and tip radius
integral. (Fig. 14) decrease with the solidification rate. The den-
The Ivantsov solution was derived for an isolated den- drite tip temperature defines the starting condition for
drite tip. Thus for a dendrite array with overlapping solutal the UC simulations.
fields, deviations in the tip radius and temperature are
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