Journal of Crystal Growth 76 (1986) 31—49 31

North-Holland, Amsterdam

THE MULLINS-SEKERKA INSTABILITY IN DIRECTIONAL SOLIDIFICATION

OF THIN SAMPLES

B. CAROLI “, C. CAROLI and B. ROULET

Groupe de Physique des So/ides de /‘Ecole Normale Supérieure, associé au Centre National de Ia Recherche Sciennj:que,
Université Paris VII, 2 Place Jussieu, F-75251 Paris Cedex 05, France

Received 10 March 1986

When a solid—liquid front is in contact with a confining wall, the condition of mechanical equilibrium imposes the value of the
contact angle 9, which induces a meniscus-shaped deformation of the front. We studied the influence of this capillary effect on the
Mullins—Sekerka instability observed in directional solidification of thin transparent samples, in the limit of a very weakly curved
meniscus (9 = ,r/2). For this purpose, we first calculated the shape of the meniscus in the symmetric model, with the help of an
expansion (up to third order) of the front equation in powers of the deformation amplitudes. We studied its dependence on thickness
in the vicinity of the Mullins—Sekerka bifurcation. We then performed the analysis of linear stability of this memscus-shaped front,
and showed that both the position of the cellular velocity threshold and the period of the cells are thickness-dependent.

I. Introduction

The Mullins—Sekerka [1] (MS) instability was first observed, and subsequently studied, in the direc-
tional solidification of large samples of metallic alloys: when such rods or plates are pulled in the
externally imposed temperature gradient, the (previously planar) solid—liquid front develops when the
pulling velocity V exceeds a threshold value J’~,a quasi-periodic cellular deformation.
With such experimental conditions, one cannot observe the solid—liquid interface during growth;
moreover, the analysis of the quenched samples cannot provide very precise determinations of the front
shapes. So, in particular, such a method is not appropriate to study in detail the vicinity of the bifurcation
— the region where comparison with theoretical predictions should, in principle, be easiest and most
meaningful.
For these reasons, in the past years, several groups [2] have developed directional solidification
experiments on thin samples of transparent organic materials, which have opened the possibility of direct
continuous observation of growth fronts Sample thicknesses usually lie in the 10—200 ~tm range.
*•

Up to now, it has been tacitly admitted that the values of the critical MS velocity V~and wavelength X~
measured in such experiments are the same as those (VMS and X MS) for infinite samples, and, therefore,
thickness-independent.
Such an assumption would be justified if the cellular deformation were one-dimensional, with its
wavevector in the y-direction parallel to the holding plates, the solid—liquid front remaining everywhere
perpendicular to them. However, it is clear that this cannot, in general, be exactly true: indeed, on the line
of contact between the liquid, the solid and the wall, mechanical equilibrium imposes the value of the
contact angle 0. That is, capillary effects induce a meniscus-like deformation of the front in the transverse
* Also: Département de Physique, UER de Sciences Exactes et Naturelles, Univesité de Picardie, 33 Rue Sant-Leu, F-80000 Amiens,
France
* Such setups are also convection-free (at least for thicknesses smaller than, typically, 200 ~sm) which greatly simplifies the
interpretation of front structures.

0022-0248/86/$03.50 © Elsevier Science Publishers B.V.

(North-Holland Physics Publishing Division)
32 B. Caroli etal. / Mullins — Sekerka instability in directional solidification

L~_________
Fig. 1. Directional solidification setup for a thin film.

x-direction (see fig. 1). The cellular bifurcation observed in the experiments occurs when this non-planar
front becomes unstable against deformations with a non-zero wavevector in the y-direction. This means
that, at least for thin enough films, both the MS velocity threshold and the critical wavelength should be
shifted from their values for the infinite medium and vary with sample thickness. This is indeed
substantiated by the experimental results of de Cheveigné et al. [3] who observe, on a series of CBr4 films
with thicknesses ranging from 10 to 200 ~sm,important variations of V~and X~.
In order to try to analyze quantitatively the thickness dependence of the cellular bifurcation, one must
proceed in two steps:
(i) Calculate the shape of the meniscus, i.e. look for a stationary solution of the growth equations with a
front of the form: z~0~1~(x), which generalizes to a thin sample the planar front solution of the infinite
medium.
(ii) Study the linear stability of this solution against infinitesimal deformations satisfying the boundary
conditions imposed by the plates.
Clearly, the shape ~(x) of the meniscus is velocity-dependent. Indeed, fronts ajust themselves to satisfy
a condition of local thermodynamic equilibrium (the Gibbs—Thomson condition) involving the local
*

temperature, concentration and curvature; and, in the dynamic regime, the concentration distribution
along a curved interface is V-dependent, since it results from the balance between production of solute
excess (or defect) at the growing interface and solute diffusion. An experimental confirmation of this
velocity dependence is provided by the observation of front shapes close to a grain boundary (a closely
related situation, where mechanical equilibrium imposes a non-zero value of dr/dy on the grain
boundary): for values of V slightly smaller than the critical MS value (at which cells appear all along the
front), the amplitude and range of the front deformation are observed to increase, while its shape becomes
cell-like in the vicinity of the grain boundary [4].
Up to now, an analytic approach of the problem of cellular front shapes has only been possible in the
frame of perturbation theory [5,6], which is valid only for small deviations from the planar front situation.
This means that we will only be able, here, to calculate the meniscus shape in the case where the contact
angle 0 is very close to i~-,/2(I d~/dx = I I = tan(ir/2 0) ~ 1 at the contact with the plates). This
—

situation —where the liquid—wall and solid—wall surface tensions would be almost equal is rather —

academic. However, an analytic analysis in this limit should enable us to identify the important effects and
relevant physical parameters and to classify the interesting regimes, thus clearing the way for the future
numerical work which will be necessary for a quantitative interpretation of experiments.
Since we assume that deformations from the planar front are small, it is natural to try to calculate the
meniscus shape in the linearized approximation (i.e. by expanding the growth equations to first order in
the deviations from the planar front solution). We will see that this legitimate for very thin films with

* This holds for materials with atomically rough solid—liquid interfaces (such as, in particular, succinonitrile and carbon
tetrabromide which have been used in this film experiments). Our calculations will be performed for such materials with
quasi-instantaneous interface kinetics.
 B. Caroli et al. / Mullins — Sekerka instability in directional solidification 33

thickness e <XMS and for V < VMS, where XMS is the critical MS wavelength for the infinite sample.
However, this approximation is not legitimate for all values of the thickness. Indeed, in the presence of the
plates, the front deformation ~(x) is a superposition of harmonics of the fundamental deformation mode
(of the infintie medium) with wavevector K0 = 2ir/e along the x-direction (where e is the film thickness).
When either K0 or any of its harmonics becomes neutral, the contribution of this mode to the linearized
meniscus deformation diverges, and a non-linear calculation becomes necessary. In other words, for small
~, such “resonances” occur when the film can accommodate an integer number of the possible cells of the
infinite medium within its transverse dimension.
For e = en = nXMs, resonance is reached for V = VMS. But, the more e/XMS2~T/XMS,
differs from
i.e. an
theinteger,
larger the
the
more theat Wavevector
velocity of the
which this mode “most neutral.
becomes dangerous” modesince
However, differs fromwith
we deal KMSsmall
= deformations, the position
of the bifurcation towards a front deformed along the y-direction is only slightly shifted from VMS, and we
will thus not be interested in meniscus shapes at velocities much larger than VMS.
So, when looking for the cellular bifurcation in thin samples with a contact angle very close to ¶/2, one
may in practice define “resonant” (e~ n X Ms) and non-resonant film thicknesses.
This leads us to distinguish between various regimes:
(1) e << XMS (K
0>> KMS): The meniscus can be calculated in the linear approximation. The cellular
bifurcation occurs at a velocity smaller than VMS, the front profile in the x-direction remaining unchanged
at the bifurcation.
(2) e XMS (K0 KMS): For V VMS, the memscus must be obtained from a calculation to third
— — —

order in the amplitude of the K0 mode. Such a situation has already been studied by Ungar and Brown [7]
on the (completely equivalent) problem of a periodic array of grain boundaries with spacing close to AMS.
Their calculation predicts that the memscus shape should undergo an “imperfect bifurcation” (where the
amplitude of the K0 mode should change by a finite amount, without any front deformation along y) at a
velocity Vmen, with, for small I I = tan(ir/2 0)1, I Vmen VMS I ~
— —

We calculate explicitly the meniscus shape, up to third order in the “dangerous” amplitude and show
that:
— The perturbation approximation is valid, when V VMS, only for:

I ‘~< (2~/l)~”~, (1)

where ~ is the capillary length of our problem, and / = 2 D/ V is the solute diffusion length. ~ usually lies
in the 10 A range at most, while, under the usual experimental conditions, 1> 100 ~tm. So, condition (1) is
in practice extremely stringent.
— In the range of ~ were (1) is satisfied, I Vmen VMS in fact crosses over from a (~)2~/3 behavior (for
—

I ~ (2~/l)~”~) to a ~ behavior (for I~I >> (2~/l)2./’3).

The meniscus we thus calculate exhibits a cellular bifurcation in the y-direction at a velocity V~smaller
than both Vmen and VMS. The resonance in the meniscus amplitude for e XMS, V VMS, results in a — —

corresponding resonant enhancement in the shift VMS V~of the cellular bifurcation. Moreover, while, for
—

> 0 (convex solid meniscus), the wavelength of the cellular instability along the plates X, is of the order
of A Ms’ for ~ <0, A,, 2 A MS/ ~ and the cellular deformation is accompanied by a deformation of the
meniscus, i.e. of the front profile along x.
(3) e> A M5: For values of e/AMS larger than 1, but still of the order of a few units, the meniscus can
be calculated as in cases (1) or (2). Namely, outside the resonant regions (e nAMS), a linear approxima-
tion is valid; close to resonance, the amplitude of the resonant mode is obtained from the corresponding
first order equation.
In this region, several modes of cellular deformation (with different values of the x-component of their
wavevector, quantified by the boundary conditions), become neutral in the vicinity of V = VMS, and one
34 B. Caroli et al. / Mullins — Sekerka instability in directional solidification

must study in detail their relative stability. This simple but heavy algebra gives rise to various ways of
behavior, depending on the value of e/AMS and on the sign of and the only qualitatively simple
~,

features of the results are:

(a) l~z VMS;
(b) VMS V~shows a resonant enhancement for e/AMS n.
—

For “thick” samples (e/AMS>> 1) the above analysis looses its validity: several meniscus modes become
quasi-neutral at the same time, i.e. several amplitudes becomes resonant and a one-mode third order
amplitudes equation becomes illegitimate. In this regime, the problem of calculating the meniscus in the
region of the cellular bifurcation presents difficulties essentially equivalent to those of the unsolved
problem of cellular shapes in an infinite medium. That is, although we know that, for e no, J’~ VMS —* —4

and A AMS, we have not been able to calculate the asymptotic approach to this limit.
—*

In section 2, we calculate the meniscus shape for thin films with small meniscus slopes (small ~) and, in
section 3, we study its stability against cellular deformations. All the calculations are performed in the
symmetric model introduced by Langer [6], which has been shown to present the same physical features as
the more realistic one-sided one, while leading to a much lighter algebra. The qualitative implications of
our results for actual experimental situations are briefly discussed in section 4.

2. The meniscus-shaped front

2.1. The equation for the stationary meniscus

We consider a solidifying binary mixture pulled at velocity V in the temperature gradient G, with a
fixed concentration at infinity in the liquid phase C,~.We assume that this two-phase system can be
described by Langer’s symmetric model [6] (equal thermal conductivities and equal solute diffusion
coefficients D5 = DL = D in the two phases, liquidus and solidus lines on the equilibrium phase diagram
locally parallel with a miscibility gap AC). Of course, these assumptions are unrealistic for a solid—liquid
transition (since D5 ~szDL); however, Langer’s analysis has shown that, while this model gives rise to a
much simpler mathematical formulation, it nevertheless exhibits a cellular bifurcation with the same
structure as non-symmetric ones.
When, taking into account the fact that heat diffuses much faster than concentration, one neglects the
production of latent heat on the front [5], the equation determining the shape of the front ~(x, y, t) (in
the laboratory frame) for a sample infinite along x and y reduces to [6]:

~(x,y, t) +1

_Jdtifdxi dyi( V+ ~ ‘~ fro(x~ y, ~(x, y, t), tIx1, Yi’ ~(x1,Y1’ ti), t~)=0,

(2)

where ~( (~)is the curvature of the interface (assumed to be positive for a convex solid) and ~ is the
capillary length characteristic of the solid—liquid interface.
The thermal length ‘T is given by:

1~’=G/ImLL~CI, (3)

where G is the thermal gradient, z.IC the miscibility gap and mL the slope of the liquidus line.
 B. Caroli et at / Mullins — Sekerka instability in directional solidification 35

~ is the retarded diffusion Green function for an infinite medium in a frame moving at velocity V:
~0(x, y, z, lIxi, Yi’ z3, t1)
2 + (y —y 2 + [z z 2~ —

=
1
[4~rD(t_ti)]3/2P\
(x x1) f
1)
4D(t—t
3 + V(t t1)]
— —

1) (t>t~),

0 (t<t1).

We are dealing with a thin sample confined in the x-direction between two identical plates located at
x = 0 and x = e (fig. 1). The presence of these plates imposes two kinds of boundary conditions on the
system:
(i) There is no concentration flow through the plates, that is:
aC(x, y, z, t) — ac’(x, y, ~, t) = 0 5)
x=O aX x=e

This can in principle be taken into account by replacing, in eq. (2), ~o by the Green function ~ for a finite
medium with boundary conditions (5) (and integrating on the 0 <x <C interval only). ~ is simply the sum
of the contributions of the “trajectories” between (x, y, fl and (x1, Yi’ ~) with any number of reflections
on the plates. This is strictly equivalent to considering the front problem in an “extended” medium infinite
along both x and y, where, according to the method of images, the front ~‘(x, y, t) is built by successive
reflections of the actual front ~(x, y, t) (0 <x < e) in the two mirror planes x = 0, x = e.
The extended front ~ is thus constrained to be periodic along x with period 2e and even in x.
(ii) The condition of mechanical equilibrium on the line of contact between the front and the plates
imposes the value of the angle 0 between the wall plane (yOz) and the plane locally tangent to the
interface, i.e.:

2 = — 2 =cos 0. (6)
(1 +~2÷~2)’/ x0~ (i ÷r2+~/2)’/
This condition can be taken into account by adding to eq. (2) the right-hand side term:
2~ 2 3/2 ~ ~(x—ne), (7)
(i+~ )
where we have set:
~=tan(0—s7’/2). (8)
That this is equivalent to (6), can be checked easily by integrating the resulting equation in the region
ne— <x <ne + (c 0), and noticing that, due to the symmetries of the extended front, ~ as well as
—*

all y-derivatives of ~ are continuous across the planes x = ne.

We now want to look for a stationary solution of the meniscus problem, i.e. ~ ~‘(x). Moreover, we
perform the standard non-dimensionalization by using for the length scale the solute diffusion length
1= 2D/V. Setting d0 = ~// and ~ = I/IT = 2DG/VI mL~CI~ and performing the y-integration, one can
then write the equation for the stationary meniscus as:
_, ,-,,(
“0~, ~
3/2 — ~~‘(x) + 1
(i + ~F(x)2)
2 + U’(x) — ~‘(x 2~= 2d
_2fd~rf dx1-~-—expI (x — — x1) 4T 1) + 2’r] ) (i
t~ 0~
.L,-,2\3’~2
50/ “
~
—— ~ — ne)
0 —~ 4irr ~
(9)
36 B. Caroli et al. / Mullins — Sekerka instability in directional solidification

where all lengths are measured in units of I, and the only admissible solutions for ~(x) must be even and
periodic in x with period 2 e

2.2. Amplitude expansion of the meniscus equation

As discussed in section 1, we will now look for the solution of eq. (9) in the limit of small deformations
from the planar front state, i.e. of small ~.

The most general expression of ~(x) satisfying the symmetry conditions in the extended system is:

~(x)= ~~,,cos(nK0x)+ ~~n+1/2 cos[(n+ ~)Kox], (10)

where the reduced “fundamental” wavevector is K0 = 2i~/e.

One may then project eq. (9) onto the various cosine functions appearing in eq. (10). Clearly, the
right-hand side of eq. (9) only has components on terms of integer order cos(nK0x). This immediately
entails that eq. (9) has a solution with ~ = 0 (for all n), i.e. with ~(x) symmetric with respect to the
~ +

plane x = e/2. We will look here for a meniscus with this symmetry: such a choice is the most natural one,
since it corresponds to the highest symmetry compatible with the capillary driving term (right-hand side of
eq. (9)). Moreover, we will show in section 3 that this basic solution which is the analogous for a film of
—

the planar front one in the infimtie medium is locally stable at small velocities.
—

Since we assume that the ~,, are small, we expand eq. (9) up to third order in One thus ~.

straightforwardly obtains the following set of coupled equations for the Fourier components f,,:
30=2do/e(1+~2)3/2. (11)
~ ~ ~ m~n+mnm(n2_m2)
n~0 n,m>_0

For n # 0:
—f(nK
0)~~
+ ~ ~‘m~p[(hl~m+p — 2hm)8m+p_n + (hm_p — 2hm)(6m_p+n + ôm_p_n)I
m,p?~0

+ ~ m[(~m+p+r_3~m+p+3~r_ 3K~d0mpr2)ô+
m, p, r~0

+ 2(~m_p+r — + ~‘~r + 3K~d0mpr2)(ôm_p+r_n + 8m_p+r±n)

3~m+p+ ~ — 3K~d
+ (~r_m_~— 0mpr2)(8r_m_p_n + 6r_m_p+n)}

= 4d0~ (12)

3/2’
where e(1 + r2)

f(q) d 2 + ~ —1
= + (1 + q2)’/’2, (13)
0q
h~mh(nK
0), (14a)

* Note that eq. (9) is also the stationary front equation for an infinite system containing a periodic array of grain boundaries (with a
front planar in the direction parallel to the boundary planes). However, in this problem, there is no a priori restriction on the shape
of ~(x).
 B. Caroli en at / Mullins — Sekerka instability in directional solidification 37

with

h(q)== _(1+q2)’~”
2_(1+q2)l~’2+2, (14b)
and
(iSa)

with

~P(q)= ~ (15b)

This set of coupled non-linear equations for the amplitudes ~,, is the extension, for the film problem, of
Langer’s amplitude expansion for the infinite medium. The finite thickness of the sample appears in two
ways:
— it quantifies wavevectors (along x);
— capillary effects on the walls give rise to the driving terms (proportional to ~).
It may be checked either on eq. (9) or on eq. (12) that the equations for the deformation amplitudes
(n * 0) do not couple to the average meniscus recoil ~ of course ~ is determined by the deformation
terms, according to the Gibbs—Thomson condition.

2.3. The linearized solution

In the small ~ limit, it is natural to assume that the ~ can be obtained from the linear response to the
drive. In this approximation, eqs. (12) decouple and yield:
~,= —4do~/ef(nK
0) (n*0), (16a)
~o= —2~/e~s. (16b)
This solution obviously looses its validity when any of the ~,, becomes large, i.e. when, for at least one
value of n, f(nK0) 0.
Note that f( q) = 0 is the equation defining the neutraljnodes of deformation of the planar front in the
infinite system. The shape of f(q) is shown in fig. 2. For 2d0 < 1 (i.e. for V < Vmi,,, = D/E), it has one
single minimum. In the2/susual
andvelocity
E — iO~ cm, soofthat
range directional
2d solidification experiments V — 10—100 ~tm/s.
Typically D — 10~cm 0 c< 1, and

f(q) ~fmin —

f(q)

p-~ ~

Fig. 2. The function f(q) defined by eq. (13), for three values of the pulling velocity V.
38 B. Caroli et at / Mullins — Sekerka instability in directional solidification

where *

~(2d0)~”3 + d0 1 ~(2d0)’~3. (17)

4tLMS = 1 —
—

So, for ~ > ILMS (V< VMS for a given G), whatever the value of K
1”3 (e = eN = NAMS), 0, f(nK0) >0. It
expression is only
(16a) for for
~N ~ ~ I-’MS
diverges
that f(nK0) may vanish. If NK0 K~5 (2d0)
when ,t = ILMs and, in this region, the linear truncation of eqs. (12) is no longer valied. If e is not too close
=

to a multiple of AMS, the first zero of f(nK

0) only appears when ~ ILMS reaches a finite negative value.
—

So, whatever e, there always exists a velocity threshold close to which one at least of the meniscus
amplitudes is strongly enhanced and a non-linear calculation becomes necessary.
However, in a film, the front may deform in the y-direction, which gives rise to the experimentally
observed cellular bifurcation. Since we only consider here the case of weakly curved meniscus, clearly, this
bifurcation will occur for p. p.MS, and it is only for “resonant” values of the thickness e nA MS that
non-linear effects may become important before it takes place.
Outside these resonant thickness regimes, ~(x) can be obtained from eq. (16). We have been able to
calculate it explicitly only in the very thin limit K0>> (2d0) 1,13, or, in physical variables:
3, (18)
e ~ (~l2)1/3= (4D2~/V2)’/’
and for p. : P~MS(V~VMS), where the term (1 + n2K~~1”2
can be neglected in the expression of f(nK
0).
In this limit, one finds that the meniscus has the simple cosine shape (for 0 <x <e):
~(x) = 2d0~~i + 1 — 1 ~icos(a(ir—K0x))
— ~, (19)
2 as1n(ai~) j
~ ~t d0K~ a
with
a (1 —

2.4. The “resonant” meniscus

Let us now consider the resonant case where e CN = NAMS N(2d 1~3 for p. p.~
1~
(i.e. close to the
0)
bifurcation region).
As discussed above, in this regime f(NK0) 0. Although non-linear terms in eqs. (12) prevent a true
divergence of ~N’ it is nevertheless likely that, at resonance, ~N>> ~ N~In order to make a more definite
ansatz, one then sorts out, from eq. (12) for n = N, the dominant quadratic and cubic terms. These turn
out to be, respectively, proportiional to ~N’ ~2N and ~,. That is, the amplitude of the resonant mode
couples to that of its second harmonic. In the equation for ~2N’ the dominant non-linear term is the one
proportional to ~. This leads us to formulate the following ansatz, the consistency of which we will check
a posteriori:

~N—(~o)~ ~2N_(~)2/3, (n*N,2N).

~ (20)
For n * 0, N, 2N, the ~,,‘s are therefore still given by eq. (16a). ~N and ~2N are then solutions of the
coupled equations:
4) = 2d
—f(NKo)~N— 2N~N~2N~ ~N(4~N ~2N~ ~K~d0N 0K0~/ir, (21a)
—f(2NKQ)~zN+ 2hN)~= 2d0K0~/1T,
~(1~2N — (21b)
and
3 p.~p.MS~
where K0~N~(2d0)~”
* Similarly, we will perform all subsequent calculations to leading order in d
0 only.
 B. Caroli et al. / Mullins — Sekerka instability in directional solidification 39

(ha)

1N to the meniscus amplitude at e = eN = NXMS as a function of the pulling velocity V. The

Fig. 3. The resonant contribution
meniscus undergoes an imperfect bifurcation for V = V,~.

From eq. (13), to lowest order in ~ = (p. — p.MS)KMS and in (C/eN) — 1 = (e/NAMS) — 1,

f(2NK 3, (22a)
0) — (2d0)V
f(NK
0) (2d0)~”[~(a/N — 1)2 + &,II. (22b)
3~2~I’N.
Since
Eq. NK0—KMS>>1,
(21a) can then behN— —NK0=
rewritten, with—(2do)~”
the help of eq. (21b) (and to dominant order in (2d
0 ) ‘):

4d 3~’/~N, (23)
0 s~N(2do)i~ +~+~(~!~_1)2
2 CN = —(2d0)~

where d0 is understood to be calculated as the MS bifurcation of the infinite medium.

Eq. (23) is the extension, for a system “driven” by the front-wall capillary effect, of the equation
obtained by Langer [6]for the infinite system, from the two-mode approximation valid close to the MS
bifurcation.
In the absence of the capillary drive (~ = 0), eq. (23) exhibits the usual fork bifurcation from the state
= 0 to a deformed state ~N * 0. This occurs for 6p. ~(a/N 1)2, i.e. when the K0 mode becomes
— —

neutral in the infinite system. The right-hand side capillary term transforms this bifurcation into an
imperfect one [7](see fig. 3), occurring at the value of p. for which one switches from a one- to a
three-solution regime for ~ That is, at this “meniscus bifurcation” (where the front profile along the
plates remains unaffected):

3(e~) 2 So — k50)
1~3(2d —
9N2/3 (24)
2 CN ITN(2d0 )1/3 (8,~~2) 0)‘~‘
which, at constant thermal gradient, defines the velocity threshold for the meniscus bifurcation ~ since:

8p.~ (VMS — V$,~)/VMs(2do)1”3. (25)

That is, at resonance (e = eN), the dependence of the shift VMS — ~ on ~ exhibits a cross-over between
two regimes:
(i) For I I ~ (2d 2”3N,
0)
,., 2/3
Vmen — ‘MS .~ So 1 2/9
VMS — (8~2)h/’3~~) 0

This is the result predicted, on the periodic grain boundary problem, by Ungar and Brown’s [7]singular
40 B. Caroli et a!. / Mullins — Sekerka instability in directional solidification

perturbation expansion. Since d0 << 1, it is seen that it corresponds to very small ~. Note that, in this
regime, V~> VMS. 2”3N,
(ii) For I I >> (2d0)
(V~) VMS)/VMS — ~/i~N.
— (27)
In this region, the sign of the shift is that of ~.
In both cases, at the bifurcation, on the branch of solutions (branch (I) of fig. 3) which continues the
subcritical regime:

~ —2(~/srN)1”3(2do)4”9, (28a)
while the bifurcating branches emerge from the new (doubly degenerate) solution:

~1) = (~/.i~-N)~”3(2d = —~‘~/2

4”9 (28b)
0)
Note that this, together with eq. (21b), justifies the coherence of ansatz (20).
From eq. (24), when I (C/CN) ii increases from zero to finite values, the meniscus bifurcation shifts
—

towards larger velocities. In the region of interest V VMS, the meniscus is then subcritical, and I ~N I
(~ I) decreases from the value given by eq. (28a) to its linearized value (eq. (16a)). The characteristic
thickness range on which this decrease takes place defines a resonance peak width ~ around thickness
eN. A simple inspection of eq. (23) shows that:
(i) For I I <<N(2d 2”3,
0)
~ 2(2d 6N2,~’3. (29a)
0 )1~~3}
~“
(ii) For I I
N(2d 2”3,
>>
0)
~e~/AMs ~ — (29b)

2.5. Conditions of validity of the approximations for p. p.MS

In order to establish these conditions, it is useful to distinguish between three ranges for the film
thickness e.
(i) Thick films: it is immediately seen from eqs. (29) that the width of the resonant regions surrounding
each eN = NAMS increases with N, i.e. with film thickness.
Clearly, the two-mode truncation expressed by ansatz (20), which enabled us to calculate the memscus
at resonance (i.e. when the linear approximation is insufficient) becomes inadequate when several modes
become quasi-neutral together (i.e. when K
0 is small enough). This happens when two successive resonant
peaks overlap, i.e. when
L~e~>
AMS.
Using eqs. (29), one finds that the above calculations are therefore only valid for not too thick films, such
that: 1/2,
(1) If I~I.~az(2d0) 1/2 , 1/2
e/AMS<<(2do) /I~’oI . (30a)
(2) If I~I>>(2d 2,
0)’~
e/AMS~<(2d 1”3/I~I. (30b)
0)
 B. Caroli en al. / Mullins — Sekerka instability in directional solidification 41

So, as already mentioned in section 1, we are not able, with the methods used here, to describe the
asymptotic approach of the limit of infinite thickness. This stems from the fact that, when e becomes large,
the spacing K0 between the modes allowed by the boundary conditions becomes so small that there are
many of them in the critical region.
In this case, as is known from the work on Rayleigh—Bénard convection in large cells [8], one should
rather use a description based on the amplitude equation of the infinite system (far from the walls)
supplemented by “reduced” boundary conditions on the slowly-varying amplitude. Due to the fact that,
contrary to the convection case, the true boundary conditions for our problem do not simply reduce to
=0 on the plates, we have not been able to derive reduced boundary conditions. Whether this is feasible
or not remains an open question with bearing, not only on film problems, but, more importantly perhaps,
on the calculation of front cell profiles.
(ii) Intermediate thickness: As we will see, this regime corresponds in practice to values of e/XMS of
order 1 (up to a few units).
In this regime, ~(x) is given by the results of sections 2.3 and 2.4, provided that the terms we have
neglected are effectively small. Outside resonant peaks, estimating quadratic and cubic terms in eqs. (12)
with the help of eq. (16), this gives:
3 (31)
I~I <<(2d0)~”
An analogous estimate performed in the resonant region leads exactly to the same limitation.
Note that, since (2d 1~3= (2~/l)1/3 = AMS/l << 1, condition (31), which limits the validity of perturba-
tive calculations of the0)meniscus shape, is in fact very stringent.
(iii) Very thin films: (e 4Z AMS) For such films, in the interesting region p. I~MS’no resonance occurs
and the linear approximation is valid provided that, again, non-linear terms are small, which yields:
I~I<<min{1; (2d 2)}. (32)
0/e
So, for very thin films such that (in physical variables)
e << XMS(AMS/l)1”2, (33)
the linear approximation for ~(x) is valid as soon as:
I~I<<1. (34)
That is, in the very thin limit, ~(x) can be calculated for realistic values of the contact angle.

3. The cellular bifurcation in thin films

3.1. Formulation of the linear stability problem

We now want to study the local stability of the meniscus-shaped front calculated in section 2, ~(x).
That is, setting:
Z(x, y, t)=~(x)+~(x, y, t), (35)
we must study the time evolution of the infinitesimal front deformation 6~.
The deformed front Z must satisfy the capillary condition (eq. (6)) along the plates. Moreover, as
discussed in section 2, its x-dependence can be Fourier-analyzed according to eq. (10). Taking advantage
of the translational invariance of the system in the y-direction, we can set:

8~’(x, y, t) = ~ t) cos(~Kox). (36)

42 B. Caroli eta!. / Mullins — Sekerka instability in directional solidification

We are interested in the position of the cellular bifurcation in parameter space. For this purpose, we
only need to search for the condition of first occurrence of neutral deformation modes, i.e. modes such
that a = 0. So, we only need to consider time-independent deformations, which must therefore satisfy the
2D version of the stationary front equation of the symmetric model [6](i.e. eq. (2) with ~(x, y, t)
Z(x, y), supplemented with the capillary right-hand side term given by eq. (7)).
In order to be coherent with the third order approximation used to calculate the meniscus, we expand
the front equation up to third order in Z. Since we are studying linear stability only, we only retain, in the
resulting expansion, terms of order 0 and 1 in 6~.Taking into account the fact that ~(x) satisfies eq. (9),
we finally obtain:

—f~/2(k)8~fl/2(k)cos(~Kox)

~ &~~/2(k)
~{Lfl/2P(k) cos[(~ +p)Kox] +Lfl/2~(k) cos{(~_p)Kox})
n,p~0

+ ~ ô~fl/~(k)~ {Sn/2mP(k) cos[(~ + m +p)Kox}

n,m,p~0

+Sn/2_mp(k) cos[(~ — m +p)Kox]

+Sn/2m_p(k) cos{(~+ m _p)KoxJ

+Sn/2,_m,_p(k) cos[(~ _m_p)KoxJ} =0, (37a)

where
Lfl/2~(k) = hfl/2±~(k)— hfl/2(k) — h~(0), (37b)

Sn/2.m,p(k) = ~[~1~n/2+m±p(k) + ‘I’fl/2(k) — ~‘m+p(0) — 2’I’~+fl/2(k)+ 2~I’m(0)]

2K~
—
3d0K~
8 uimp2 d0K~
8 k 2 + 3n mp, (37c)
with ~~/ 2 + n2K~/4)1”2),where di stands for f, h or ‘~Pas defined by eqs. (13), (14b) and
(15b). 2(k) ~((k
Projecting eq. (37a) onto each allowed transverse mode cos(rK
0x/2) (r = 0, 1, ...) results in an infinite
set of linear homogeneous coupled equations for the &~‘n/2(k). It can be checked by simple inspection of
eqs. (37) that this set decouples into two seperate subsets for amplitudes with integer and half-integer
indices respectively. This expresses the fact that these two groups of modes are, respectively, even and odd
with respect to reflection in the mid-plate plane x = e/2.

3.2. Bifurcation equations

The condition for this homogeneous set of equations to have a nontrivial solution gives the condition of
existence of neutral modes as:
(38)
where L1(k) is the determinant of the system. It is a function of the wavevector k of the deformation along
the plates, and depends on the external parameter p. via the f-functions and the meniscus amplitudes c,,.
 B. Caroli et aL / Mullins — Sekerka instability in directional solidification 43

For ~ = 0 (i.e. ~,,= 0), ~ is diagonal, and

~(k)=fl[—ffl/
2(k)]. (39)

As discussed in section 2.3:

(1) Forp.>p.~5(V< VMS), each factorffl/2(k)~f,~fl=p.—p.MS, and eq. (38) has no solution.
(2) For p. = p.~~:f~ nsf(kMS) = 0. That is, there appears as many neutral modes as there are solutions
k~°32of the equation:

~/(k~0)2)2+n2Ko~/4 ‘KMS, (40)

i.e., as there are modes with a total wavevector 2of~ elength KMS,
< (p + but with
l)AMS/2, thereitsarex-component quantified
p + 1 such modes, with
naccording top;
= 0, 1,..., thefor
boundary
n > p, conditions. For may
neutral modes pAMs/
of course appear, but only for finite negative values of
p.~p.MS. In the small ~ limit we consider, the cellular bifurcation occurs at p. p. MS and we will not be
interested in the modes with n > p.
For finite ~, ~ is no longer diagonal, but factors into ~ = ~ ~ HI’ where ~ and ~ HI are associated,
respectively, with integer and half-integer n values. Let us consider, for example, the structure of L~I:

~
02(k)
= z~10(k) —f1(k)+&~(k) z~12(k) ... . (41)

One easily finds, from eqs. (37), that:

(42a)
(42b)
6~(k)=e’((~~))(n*0). (42c)
So, the equation for the neutral modes with integer n/2 values can be developed into:

L~1(k) fl
n=0
[—f~(k)+6~(k)] ~ ~
n, m~0
~nm~mn fl [j~(k)] +~((~,fl)o. (43)
(p~’n,m)

Let us now look for the equation of the neutral mode “of type (the mode which is of pure
~‘

n-character for ~ = 0). By continuity, for this mode f~(k) 0, but the f~ ~(k) remain finite. So, eq. (43)
can be reduced to:

~ +~. (44)

This set of neutral mode equations must be supplemented with those for half-integer modes, which are
obtained from eq. (44) by: n—’n+ ~, m—’m+ ~ (n, m~0).
For each value of n, one must then look for the value p.,, of p. for which one neutral { n } mode first
appears. The position of the cellular bifurcation in parameter space is given by:
p.~=Max(p.~) (i0,~,1, ...). (45)
44 B. Caroli et aL / Mu!lins— Sekerka instability in directional solidification

3.3. Non-resonant thicknesses

In this regime (i.e. for e not too close to nAMS), as discussed in section 3.3, all the meniscus amplitudes
are of order ~ and can be obtained from the linear approximation (eqs. (16)).
We will calculate the shifts p.,, ~ to lowest order in — So, taking into account eqs. (42), we may
~.

rewrite eqs. (44) as:

1~,/2(k,p.)nsffl/2(k)—~ifl/2(k)=0, (46a)
where

‘&10(k, p.) = {~0(k)+ £~ ~0m(~~10~’) }, (46b)

and, for n * 0:
~‘,,/2(k, p.)=8,,/2(k), (46c)
with, from eqs. (37):
3), (47a)
= m~i~{3~0~ - ~m(k) + *m(0)] ~ +fP(~
and, for n * 0:
d~fl/ 2), (47b)
2(k)_—~,,h,,(0)+9(~
(47c)
4moOt~) = ~m[”~mO’) — h
0(k) — hm(0)1. (47d)
The bifurcation of an n/2 mode occurs when:

1~/2(k,p.)=0, -~F,~/2(k,p.)0. (48)

Since
2 we
~ e look
< (pfor the first ofwe
+ l)AMS/2, these
onlybifurcations (the one
need to examine thewith
p + largest
1 modes as discussed
p.)which in section
bifurcate close to3.2,
p. = when
p.Ms,
pAMS/
k k~) 2K~/4)1”2.
2= (K~5
To lowest n ~, one then finds, from eqs. (46) and (13), that the bifurcation of an n/2 mode takes
order in —

place for:

p.fl/
2_p.MS÷~1fl/2(kfl/2,
p.Ms), (49a)

k,,/2 = k~2+ a~Ifl/2/affl/2(k) (49b)

8k ~LMS,kk~2

Using eqs. (46c), (47b), (16a), (14) and (17), we then find, for 0 <n ~
= p.n/2 — = — 1/3 ±LH(nKo/2KMS), (50a)
(2d0) / (2d0) i~(2d0) KMS
where
2/(2u — 1)2(u + 1). (50b)
H(u) = 2u
 B. Caroli et aL / Mullins — Sekerka instability in directional solidification 45

Since H(nKo/2KMS) 0, it is seen that the sign of the shift ~p.,,/2 is that of (— ~ the n/2 bifurcation
>

(n * 0) occurs at V> VMS (respectively V < VMS) for a convex (respectively concave) solid meniscus.
Of course, H diverges in the vicinity of u = 1/2 (e = nXMS), i.e. in the regime of resonant thicknesses
(see section 3.4).
From eqs. (46b), (47a), (47c), (47d), (16a), (14) and (15), one gets for the bifurcation of the n = 0 mode:

3= (~)1/3 = (~2~1/3 )2~ £A(nKO/KMS) + (~)2 2K~~~B(nKo/KMS),

(2d0)~
(51)

where
~i+ 2\1/2 1
A(u)= U — , (52a)
(-~u2+ 1/u — ~)2(~u2 — 1 + (1 + u2) 1/2)

3[(u2 + 1)1/2 — u — 1] +
B(u) = . (52b)
112 1/ 3\2
~U -rI/U—v)

One easily cheks that:

(i) For very thin films, such that KMS/Ko <<(2d
0)2/9 i.e., in physical variables:
2~3, (53)
e/XMS~ (XMS/l)
the A terms in eq. (51) are negligible with respect to the B ones and, keeping only terms up to order
(e/XMS)2, one gets:

(2d 3 ~ — .~~~(e/XMS)2]. (54)

0)~
(ii) For e/XMS>> (XMs/l)2~3 (but out of the resonance peaks), the A term in eq. (51) is dominant. From
eq. (52a), A > 0, so that 8p.
2(2d 0>1”3/~2is
0 (P~< aVMS).
function of e/XMS only. We have calculated it numerically for
The quantity 6p.0ir 0)
e < 2 X MS and outside resonance. It is plotted in fig. 4.
Note that the condition of validity of our calculations (eqs. (31) or (34) entails that, for all n, 8p.,, ~
(2d 1~3.
0) these results, it is now possible to obtain the position of the cellular bifurcation in a thin film of
From
non-resonant thickness:
(i) If the meniscus corresponds to a convex solid front, 6p.
0> 0 (V0 < VMS), while, for all n # 0 modes,
<0 (J’~/2> VMS), and J’~= V0 is given by eq. (51).
The front deformation which sets in at the cellular bifurcation is always of type ~ i.e.:
— its experimentally observable wavelength (wavelength in the y-direction) is, up to corrections of order
~2 the MS one for the corresponding infinite system;
— it is quasi x-independent, i.e., very close to V~,it does
8p.n/not deform the meniscus.
(ii) For ~ <0 (concave solid meniscus), all the 2 (for 0 ~ n ~p) are positive. The discussion
becomes much heavier and each non-resonant range of values of e must be examined separately, the only
general result being that, again, p.> ~ i.e. the cellular velocity threshold is lower than in the infinite
medium.
46 B. Caroli et aL / Mullins — Sekerka instability in directional solidification

~/
Fig. 4. Plot of X = (~
2(2d 1/3/~2versus e/XMS. For resonant thicknesses (shaded intervals) as well as for e/AMS <<
0)~ a universal
(XMS/l)2”3, X is no longer 0) function of e/AMS..

Moreover, one can show that:

(a) For e/AMS < 1/2 (p = 0), = p.~
~ as in case (i) above.
(b) For 1/2 <e/XMS < 1 — L1e~/XMS, 6p.l/
2/4K~~)1~2. 2 = ~9(J~I)> ~ and p.,~ = p.1,,2 k~= k~°,)2= KMS(l —

K3The cellular deformation at the bifurcation is associated with the appearance of an asymmetry of the
meniscus with respect to the mid-plate plane x = e/2.
In fact, a careful analysis of the dependence of ~p.l/
2 on e in the region e/AMS 1”3]1”2.
< 1/2 shows that the

change from
(c) For regime
p/2 <e/XMS(a) to
< (b)
(p +takes
1)/2place
(p> continuously on a width
1), the first unstable of always
mode order [~/(2d0)
has n * 0. It is that with the
largest H(nKO/2KMS) (n <p). From the shape of H(u), it can be found in the following way: define the
integer v by e/XMS — 1 <v < e/AMS; then
— if H(PKo/2KMS) > H((i’ + 1)Ko/2KMs), p.~=
— if the inequality is reversed, p., =
That is, for ~ < 0, as soon as e> A Ms/2, in the non-resonant regions, ôp.,, ~ I I and the wavelength of
the cellular instability along y, given by eq. (40) with the appropriate n, may be much larger than AMS.

3.4. Resonant thicknesses

As discussed in section 2, when e approaches a resonant value eN = NAMS, the meniscus amplitudes ~N
and ~2N are enhanced. While, for n * N, 2N, ~,,Cr ~, close to the corresponding meniscus bifurcation,
defined by eq. (24):

~NC~O”, ~2NC~O”. (55)

If, as we will check a posteriori, the bifurcation of an n/2 mode takes place at a value of p. where eq.
(55) holds, in the functions ‘?1fl/
2(k, p.) defined by eqs. (46), two terms at most are dominant, and one
must recalculate ~p.,,/2 accordingly.
At the Nth resonance, the (2N + 1) modes with n = 0, 1,..., N may give rise to a bifurcation
8p.,,/ in the
region p. — p.~. One must therefore calculate and compare the (2N + 1) corresponding 2~In order to
simplify the discussion as much as possible, we choose only to examine here the case of exactly resonant
thicknesses e = eN.
 B. Caroli et aL / Mullins — Sekerka instability in directional solidification 47

One can then, depending on the form of the dominant terms in ~‘n/2 (k, p.), distinguish three cases:
(a) n/2 = N: The important terms in al/N are proportional, respectively, to ~2N and ~. Then,
proceeding as in section 3.3, one can show, with the help of eqs. (37), that eq. (49a) yields:

= 2~/(2d0), (56)
where ~N is the solution of eq. (23). From this, one immediately finds:
~ (N) ,. — ~.(II)
Ô
p.N~ ~ ~N~N
where ~ and ~j~) are given by eqs. (24) and (28b). 6~N describes a deformation confined to

This can be understood as follows: for e = NA MS’ = 0, i.e.

k~°~
the x-direction. Result (57) simply expresses the fact that the new branch of solutions for ~N appearing
above the meniscus bifurcation (see fig. 3) has an infinite slope at p. =
This analysis can be pushed further into the supercritical region (p. <p.c,~).It shows that branches (I)
and (ha) of solutions for ~N are locally stable, while branch (hlb) is unstable.
(b) n/2 * N, 2N: The dominant term in al/,,,,
2 is proportional to ~. One straightforwardly finds, with
the help of eqs. (37), (44) and (49), that

8p.,,/2= ~[~(n/N) + ~(—n/N)], (58)

where ~N is given by eq. (23) in which &p. = ~ and

1”2]
(2 + u)[2 (2 + u) 2 — (59)
4[(2 + u)1”2 1] [(2 + u)1” + 2]
—

These equations yield finally:

2 ~ 2/3 [~(n/N) + ~(—n/N)]”3 (60)

(2d 3— (2d 3 (2~N)2”~3
0)”~ 0)”
Among these bifurcations, the one which occurs first corresponds to the n (n * N, 0 ~ n 2N 1) ~ —

which maximizes ‘I’(n/N) + ‘I~( n/N). This has to be solved for each N separately. In any case, for these
—

modes:
(i) 6p.,,~
2> 0

2’2d \I,/3 2/3 (61)

(ii) ~ ~ = k 0) 1/3
(2~-N) (2d0)

One then readily checks, using condition (31) for ~, that p.,,,,2 ~np.0> p.~, i.e.:

<VMS, ~/2 < V0 < ~ (62)

2 (with ~N given by eq. (23)). One then finds that:
(c) n = N: The dominant term in QIN/2 is — ~NhN(O)/
— if~>0, p.N/
2<p.o’
— if~’<0, ~N/2>~n/2 (n—0,1,...,2N+1; n*N),

with &p.~/2Cr ~
48 B. Caroli et al. / Mullins — Sekerka instability in directional solidification

So, one can finally conclude that, for all satisfying condition (31):
~‘

— the cellular bifurcation occurs before the memscus one, which, therefore, is not accessible;
— it also occurs for V,~< Vm5, i.e. before that in the infinite medium.
The shift VMS V~is enhanced with respect
— to that
2/3) for in the non-resonant
a concave one VMS J’~ regime.
= ~( I For
I 1/2)a convex
and, atsolid
— the
meniscus at resonance, VMS V f(~
bifurcation, the meniscus undergoes an asymmetric deformation.
=
—

4. Conclusion
We have been able here to calculate analytically the velocity-dependent shape of the meniscus
deformation of the solid—liquid front in thin films, and the position and apparent wavevector (period of
the cells along the direction of the plates) of the cellular bifurcation.
However, we must insist on the fact that the validity of our analysis is severely limited: as discussed in
section 2.5, it cannot describe thick films. For most thin ones (with, typically, e of the order of a few AMS,
i.e., roughly, in the 10—200 p.m range), it is valid only for I in the very small range defined by condition
(31). It is only for very thin films (condition. (33)) that it extends to more realistic values of I I
(I~I <<1).
We should also mention here that the symmetric model we have used gives rise to a normal cellular
bifurcation (corresponding to the normal imperfect one shown in fig. 3), while the more realistic one-sided
model [5] corresponds to an inverted bifurcation except for films contained between plates of high thermal
conductivity and mixtures with a segregation coefficient K> 0.45 [9]. If such is not the case in
experiments, one should in principle extend the analysis to the one-sided case. This, however, will not
modify our qualitative results, except, possibly, for the one concerning the value of p.~and the nature of
the first bifurcating modes in resonant regions.
The question then arises of what qualitative conclusions can be drawn for more realistic situations,
where is not very small.
Clearly, we can firmly state that:
— The position of the velocity threshold for the cellular bifurcation is thickness-dependent.
— Concave and convex memscus do not behave “symmetrically” (V~(~,e) * J’( ~, e)). This asymme- —

try might, perhaps, be a manifestation in our system of the non-llinear mechanism responsible, in infinite
systems, for the asymmetry of cell shapes, which are always peaked towards the cold side, and smooth on
the hot one.
— The cell wavelength at the bifurcation depends on thickness. (This dependence can be termed “robust”,
since, even for very small I I’ for some values of e, k~ KMS should be finite.)
—

Among our results, one feature seems to be particularly stable: in all regimes, we find that the cellular
bifurcation of the film takes place at a velocity lower than that for the infinite system. We believe that this
conclusion should most probably remain valid in a much larger range of ~ than that defined by condition
(31). This is indeed confirmed by the experimental results of the Cheveigné et al. [3].
Another qualitative feature of our results can, on the contrary, certainly not be extended to larger values
of ~, namely the clearcut distinction between resonant and non-resonant thicknesses. Indeed, this
distinction is based on the existence of regimes where non-linearities are completely negligible. Such
regimes disappear when I J > (2d 1”3.
0)
At this stage, one should therefore insist on two qualitative points. When performing directional
solidification experiments on thin samples, one should keep in mind that:
(i) Capillary effects due to the plates are not negligible in very thin films. So, one cannot legitimately
assume that very thin samples simulate the behavior of theoretical two-dimensional systems.
(ii) When studying, for instance, front shapes at various velocities, meaningful comparisons can only be
performed for films of the same thickness.
 B. Caroli et aL / Mullins—Sekerka instability in directional solidification 49

From this discussion it appears that, if the analytic approach developed here leads to some important
qualitative predictions, it is clearly insufficient to provide a quantitative analysis of actual experiments.
This will demand extensive numerical studies, first of velocity-dependent meniscus shapes, a task already
pioneered by Ungar and Brown [7] on the equivalent problem of periodic grain boundaries in a 2D
medium, and then of the linear stability of these fronts with respect to 3D deformations.

References

[1] W.W. Muffins and R.F. Sekerka, J. App!. Phys. 35 (1964) 444.
[2] See, for instance: K.A. Jackson, in: Crystal Growth: A Tutorial Approach, Eds. W. Bardsley, D.T.J. Hurle and J.B. Mullin
(North-Holland, Amsterdam, 1979);
R. Trivedi, Met. Trans. iSA (1984) 977, and references therein;
F. Heslot and A. Liebchaber, in: Proc. 59th Nobel Symp. [Phys. Scripta T9 (1985) 126];
S. de Cheveigné, C. Guthmann and M.M. Lebrun, J. Crystal Growth 73 (1984) 242.
[3] S. de Cheveigné, C. Guthmann and M.M. Lebrun, to be published.
[4] See, for instance:
L.R. Morris and W.C. Winegard, J. Crystal Growth 5 (1969) 361;
R.J. Schaefer and M.E. Glicksman, Met. Trans. 1 (1970) 1973.
[5] DJ. Wolikind and L.A. Segel, Phil. Trans. Roy. Soc. London 268 (1970) 351.
[6] J.S. Langer, Acta Met. 25 (1977) 1121.
[7] L.H. Ungar and R.A. Brown, Phys. Rev. B30 (1984) 3993.
[8] M.C. Cross, Phys. Fluids 25 (1982) 936, and references therein.
[9] B. Caroli, C. Caroli and B. Roulet, J. Physique 43 (1982) 1767.