Journal of Crystal Growth 108 (1991) 637—646 637

North-Holland

New periodic morphologies observed during dendritic growth

of ammonium chloride crystals in thin layers
Eli Raz, S.G. Lipson
Physics Department, Technion, Haifa 32000, Israel

and

Eshel Ben-Jacob
School of Physics and Astronomy, Raymond and Beverly Sackler Faculty of Exact Sciences, Tel-A viv University,
Ramat Aviv 69978, Israel

Received 8 September 1990

We report novel morphologies observed during the growth of dendritic crystals from supersaturated solutions of NH
4CI and
NH4CI(CuSO4). These develop when the anisotropic crystal grows in a thin layer. The crystal shapes are distinctly periodic and
exhibit long-range order; their growth front appears to be marginally stable. Crystals of these forms grow as three-dimensional
structures in quasi-two-dimensional cells, and their dominant periodicity is determined quantitatively by the smallest dimension of
the cell. We argue that the observed phenomena result from an interplay between the geometrical constraint of the cell and the
kinetics of the phase transition at the interface. The observations are consistent with a model in which dendritic growth occurs at
temperatures below the equilibrium roughening temperature of the dominant crystal facet, although kinetic roughening of the facet
occurs.

1. Introduction pattern observed results from the interplay be-

Dendritic growth of crystals is one of the most
intensively studied systems which show sponta-
neous pattern formation during their evolution
[1—5],and an excellent experimental system for
this purpose is the crystallization of a salt from its
supersaturated solution [6—9].The cornerstone of
the emerging picture is the recognition that growth
patterns can be determined by the combination of
external macroscopic thermodynamic forces and
microscopic interfacial dynamics. Diffusion kinet-
ics determine the macroscopic approach towards
equilibrium, and tend to drive the system towards
“decorated” or irregular shapes via the Mullins—
Sekerka instability [10], whereas microscopic inter-
face dynamics introduce both characteristic length
scales and preferred growth directions. The final
tween these two factors. Introduction of a third
length scale, the thickness of the growth cell, re-
suits in further pattern formation on an ap-
propriate scale, which is the subject of this paper.
The results emphasise that the three-dimensional
reality of crystal growth must be recognized even
in a quasi-two-dimensional environment [8,9].
Most recent studies focused on the role of
anisotropy in surface tension [1—4,11]and linear
growth resistance [12,13] as controlling factors.
More recently, Raz et al. [9] measured directly the
surface kinetics in NH4C1 using an optical tech-
nique. Their results indicated that the boundary
conditions at the interface are due to growth
kinetics and the relationship between interface
velocity and supersaturation is very non-linear.
This suggests that growth below the thermody-

0022-0248/91/$03.50 © 1991 — Elsevier Science Publishers B.V. (North-Holland)

638 E. Raz et al. / New morphologies observed during dendritic growth of ammonium chloride

namic roughening temperature is involved. Under

such conditions it is also expected that there will
be a very strong anisotropy in the angular depen-
dence of the growth velocity; in fact this velocity
~ will be essentially zero except for growth in cer-
tain preferred directions. There has not yet been
any theoretical study predicting shapes of crystals
growing under the proposed dynamics; however it
is realistic to expect a sharp selection of growth
velocities and of directions and locations of side-
branches. The experimental results presented in
ref. [9] provide strong indication that this is in-
deed the case.
During the experiments described in ref. [91we
were frequently surprised to observe unusually
periodic dendritic shapes which we have not seen
described in the literature. These shapes include
dendrites with zig-zag stems and side-branches,
hexagonal cellular structures (according to the
origin of the term “dendrite”, these could hardly
~ be called dendritic!), and asymmetrical dendrites
with all the branches on one side. Most of these
structures show much more definite periodicity
,~ i~ than do conventional dendrites. Photographs of
some examples are shown in figs. 1—3. The
~4 surprising feature of these observations is the dy-
Fig. 1. A growing Stem gnes rise to alternating straight namical and structural stability which is evident.
sidebranches spaced at regular intervals on its two sides,. The It clearly originates in the geometrical constraint
stem has a zigzag structure. The side-branches do not branch .
of the cell together with the highly amsotropic
further. (Type Bi, d = 28 ~&m,with 0.05% impunty. The scale
bar is 200 jsm long.) growth velocity, and gives further credence to the
picture of growth at a temperature below an equi-
librium roughening transition.
A different class of periodic structures, which
- develop on an interface in a three-dimensional
system during its growth, has been investigated
- . quite intensively [15,16], but these are unrelated to
the ones which we describe here, which appear
• sequentially in time.

2. Experimental technique
The experiments were carried out in a system
similar to that described in ref. [91. The dendrites
grew in thin parallel-sided cells and were observed
• by reflection in a microscope. In order to ensure
l-ig. 2. A growing stem gives rise apenodically to zigzag side-
branches. Each side-branch is like fig. 1. (Type B3, d = 28 gm, uniform temperature in the x, y plane, the base of
with 0.025% impurity. The scale bar is 200 urn long.) the cell was made from copper, covered by a thin
 E• Raz et al. / New morphologies observed during dendritic growth of ammonium chloride 639

(0.1 mm) aluminium-coated glass mirror. By means and 170 ±2 tim. The top boundary of the cell was
of two wire spacers separated by about 25 mm, we a 1 mm thick microscope slide. We used flowing
could define cells with thicknesses d between 28 water to cool the cell base, and its temperature, in

~t

~ ~ ~
)•~••~
.~
~

~ ~_-c~p~-~

I ‘~‘~‘~/ I
ç~’ t’~~L
~ .•-c- - -
~ C

~ ~
Fig. 3. A hexagonal network of dendrites is set up (Type C). The scale bars are 200 pm long. (a) The hexagons may be regular (Cl,
d = 56 pm), but (b) are not necessarily so (Cl, d = 28 pm). (c) An overview shows the structure to have long range order, and to grow
with a well-defined growth front (C2, d = 28 pm). (d) In detail, a hexagonal unit may have subsidiary short and irregular
side-branches on its arms (CI, d = 120 pm). (e) Addition of 0.02% CuSO
4 produces the same structure, but the random
side-branching is supressed (Cl, d =120 pm).
640 E. Raz et al. / New morphologies
8~ --~~io
6 ~_______
0 \\\‘siwiw~s O.~ 7
L
_____I
— _________________
____________________
1 the initial nucleus, one of a variety of dendritic
Fig. 4. Schematic diagram of the growth cell used in the
present experiments; (1) microscope Stage; (2) tilting table; (3)
water-cooled chamber; (4), copper cell base; (5) thermocouple;
(6) thin mirror
•
(7) spacer; (8) sample;
.
(9) cover•glass (10) dry
nitrogen flow; (11) microscope objective.
the range 1 ±0.2 to 15 ±0.2°C was measured
with a copper—constantan thermocouple. This
method of cooling from the base introduced a
vertical temperature difference of less than 0.1°C,
because of the insulation afforded by the upper
boundary slide. A schematic diagram of the cell is
shown in fig. 4.
We prepared solutions containing 27—29%
NH4C1 by weight in distilled water from analyti-
cal grade material and mixed them well at temper-
atures above their saturation. We also prepared
solutions in which 0.02—0.1% CuSO4 was added;
the effect of this impurity will be discussed below.
For each experiment we placed a drop of the
thoroughly mixed solution on the base of the cell
and covered it while maintaining the temperature
above saturation. The drop would spread to a
diameter of about 12 mm. We then cooled the cell
to its working temperature, in order to obtain
supercooling in the range 10—25°C. These figures
are equivalent to dimensionless supercoolings of
0.08—0.22 [17]. Higher degrees of supersaturation
generally resulted in spontaneous nucleation. We
initiated nucleation by gently tapping the cell, and
recorded the growing crystals on video tape; the
record included the temperature (mY output from
the thermocouple) and the time. We also built a
transparent cell with a sapphire base, whose pur-
pose was to allow direct photography of some
examples of the results on 35 mm film to illustrate
this paper. This cell was cooled by a thermoelec-
tric (Peltier) device. There were no observable
observed during dendritic growth of ammonium chloride
differences between the results obtained in the two
systems.
3. Experimental results
Depending on the thickness of the cell, the
degree of supersaturation and the orientation of
structures was observed. Under many conditions
we observed dendrites similar to those investigated
by Dougherty et al. [7] and Chan et al. [6]. These
dendrites grow mainly parallel to the cell
boundaries (the base and the glass cover slide) and
branch in the [100], [110] or [111] directions, de-
pending on the degree of supercooling. The pre-
sent investigations concentrated on the region of
high supercooling, at growth temperatures be-
tween I and 8°C.Then growth occurs only in the
[111] directions, as was confirmed by measuring
the angles between the various branches, which
are 70.530 and 109.470. Several new dendritic
structures were observed which we attribute to
boundary effects and the strong anisotropy of the
growth. These were as follows:
(A) Dendrites which grew with aperiodic
branches on one side only. (By the word
“aperiodic”, we mean that no clearly defined pen-
odicity was present. No detailed analysis is im-
plied.)
(B) Dendrites in which the stem zigzags in a
periodic manner:
(B1) Side-branches are produced every time the
stem changes direction. The branches then grow
long and straight, with no further branching (fig.
1). This type of growth was observed in layers
thinner than about 50 ~.tm.
(B2) The pattern of BI grows, but the straight
side-branches grow secondary branches which
zigzag like the original stem, usually in antiphase
with it.
(B3) A straight stem, which aperiodically pro-
duces side-branches which zig-zag. This is really
like B2, starting at the second stage (fig. 2).
(C) Growth in a hexagonal honeycomb pattern
(fig. 3).
(Cl) The honeycomb is created in thick cells by
the interlacing of several zigzags which grow
 E. Raz et a!. / New morphologies
parallel to one another with equal spacings. The
zigzags are synchronized in time, and clearly all
the stems originated from the same seed. The
aspect ratio of the hexagon changes from experi-
ment to experiment. The arms of the hexagons are
often decorated with small aperiodic sidebranches
which rarely develop (figs. 3a and 3b).
(C2) The honeycomb grows out from a single
nucleus which branches and rebranches in a highly
periodic and synchronized manner, giving a two-
dimensional lattice with surprisingly long-range
order. Occasional defects occur, but the lattice
heals around them. The growth front observed as
the crystal spreads out is smooth and does not
develop instabilities. This form of growth occurs
in thin cells (d < 50 ~tm) and requires very uni-
form temperature. The hexagons are regular and
their edges do not develop subsidiary side-branches
(fig. 3c).
(D) An aperiodic version of C2 appears at low
supercooling, when the solution is not uniform,
This gives rise to a form of densely branched
“spherulite” and is similar to structures which
have been observed in the Ge—Si system [18] (fig.
5).
The addition of small amounts of CuSO4 as an
impurity had great effect on the way in which the
crystals grow. The minimum amount to have an
effect was about 0.02%, while above 0.2% the
growth mode changed completely. We shall dis-
cuss the effect of impurities in more detail in a
~ ~ ~ ~
~ course the usual requirements of conservation of
~ ~
~ equations. Once growth has been initiated, we
~ 4f ~
I~
.~
~ /
Fig. 5. Growth of densely branched crystals from a non-uni-
form fluid. (Type D. The scale bar is 200 pm long.)
observed during dendritic growth of ammonium chloride 641
later publication. However, the morphologies A, B
and Cl were observed both with the pure and
impure media; one of the striking effects of the
impurity, which served to emphasize the periodic
behaviour, was to reduce or even remove com-
pletely the aperiodic aspects of the growth. Mor-
phology C2 was observed only in pure NH4CI.
The figure legends indicate the addition of impuri-
ties. Compare in particular figs. 3d and 3e.
4. Discussion
Our explanation for the observed structures is
based mainly on two ideas. The first is a hypothe-
sis, which was presented in detail in ref. [9], that a
nucleation process is involved in the creation of
side-branches. At temperatures below the equi-
librium roughening transition temperature of a
given crystal surface, growth nuclei on that surface
have to be created statistically. It follows that
growth of the crystal is very slow until a certain
(barrier) supersaturation is reached. Above this
level, growth in that direction of the anisotropic
crystal becomes very fast (its rate might approach
asymptotically a maximum value which is inde-
pendent of the exact degree of supersaturation).
The concentration gradient at the interface does
not, according to this picture, affect the growth
rate alone; it does so consistently with the rate at
which supersaturation is achieved and the degree
at which it should be maintained for a given
velocity [11]. Thus the ingredients of an instability
~‘1 of the Mullins—Sekerka type are present, since of
matter must still be incorporated into the rate
suggested that the surface becomes dynamically
rough,
growth inresemble
that interface
those fluctuations
of a rough created
surfacebyeven
the
the supersaturanon fails below the barrier
level, and only ceases at a lower critical value.
Then the relaxation oscillations induced by this
diode-like behaviour provide a selection mecha-
nism which is responsible for the quasi-periodic
structure of the dendrites.
642 E. Raz et a!. / New morphologies observed during dendritic growth of ammonium
The second constraint is that the boundary
conditions in the fluid have to be satisfied at the
surfaces of the cell. During crystal growth from
solution both latent heat and excess solvent are
ejected by the advancing interface. These must
diffuse away through the fluid. There is a small
component of convection involved too since the
densities of the solid and fluid are unequal [191
but this will be ignored since it does not affect the
explanation significantly. Thermal convection does
not occur because the cell is cooled from below,
The heat and solvent diffusion obey Fick’s laws,
subject to approriate boundary conditions at the
cell edges. These conditions are: (a) the upper and
lower surfaces of the cell are isotherms and (b)
there is no solvent flow across the boundaries,
Mathematically, on the boundaries T TB = =
constant and v7,,C = 0. Using the principle of
images as in electrostatics [20], it immediately
follows that a dendrite growing near a planar cell
boundary sees, concentration-wise, an identical
mirror-image dendrite growing the other side of
the boundary. Temperature-wise, it sees a negative
image dendrite (i.e. for a point on the dendrite
whose temperature is T, that of the equivalent
point on the image is TB T). If we ignore cou-
— fined mechanism (i.e. not noise-generated) must
pling between the temperature and concentration
fields, two general possibilities exist. If the tern-
perature field is dominant in determining the
growth, then the dendrite and its image “attract”,
because the temperature gradient between them
increases as they get closer, and the growth is
diverted towards the boundary [21]. If, on the
other hand, the concentration field dominates the
growth, the dendrite and its image “repel” and the
dendrite avoids growth too close to the boundary.
The latter represents the case of NH4C1 in which
the temperature field is very weak. In the normal
case of growth in an infinite medium, side-
branches on two parallel-growing dendrites avoid
one another for the same reason.
Now, if the crystal growth were isotropic, or
approximately so, and if gravity is ignored, it
would follow that the dendrite would choose to
grow in the central plane of the cell so as to
remain as far from its images as possible. How-
ever, if the crystal growth is very anisotropic and
the diffusion length is less than the cell thickness
chloride
(fast enough growth), curious growth patterns can
emerge. Suppose that a dendrite stem grows to-
wards the cell boundary at an oblique angle. The
concentration field ahead of the tip is locally
diluted by solvent which is rejected by the growing
crystal. When the tip gets close enough to the
boundary, the dilution will also be affected by the
field around the image and the growth eventually
stops for lack of solute. It should be noticed that
the crystal does not have to touch the boundary
for this to happen, but only to approach it closely
enough for the image field to have a decisive
effect. But if once started, the growth can continue
in only a small degree of supersaturation, the
distance from the boundary at which it eventually
ceases may be quite small compared with the
diffusion length.
Meanwhile, the solvent diffuses away and the
solute concentration at the interface increases,
fastest where the concentration gradient is highest.
Let us assume that the preferred growth directions
are the [Ill] group. A new side-branch will emerge
at a location which has a [111] surface orientation
and where the supersaturation first reaches the
critical level. It seems that a specific and well-dc-
be involved at this stage in order to generate the
long-range order observed. It is clear that this will
be on the side remote from the boundary, and
growth will restart on that side. Since initiation of
growth is competitive, and occurs in the first
equivalent direction for which the supersaturation
exceeds the barrier, it follows that sidebranches
will never start in a backward direction when an
equivalent forward direction exists, or between
two close sterns. Smoothness of the boundaries is
also relevant since the local orientation of the
surface may be a deciding factor in the nucleation
competition. Honjo et al. [22] have shown that
irregularities of a boundary result in disordered
dendrites.
This process leads to several possible mor-
phologies, depending on the direction of growth
and the orientations with lowest nucleation barrier
at the temperature in question. We recall that
growth in the [111] directions is preferred at the
supersaturations used in our experiments. It is
easy to see by calculating angles that the formal
 E. Raz et a!. / New morphologies observed during dendritic growth of ammonium chloride 643

rule for forward branching is that only one of the

two would indicate backward branching, were it

to occur).
A first example shows how zigzag crystals arise.
We consider a situation in which the (111) direc-
indices
tion is parallel
of the orientation
to the boundary
changes
planes,
sign but
(change
the cell
of
thickness is now several times greater than the
diffusion length (fig. 6). The cell surface is normal
to (112). A growing stem approaches the upper
boundary in the direction (111). When its ap-
proach is close enough, it stops growing, and
renucleation starts in the two equivalent orienta-
tions (111) and (ill). The latter dips down to- Fig. 7. A model showing the honeycomb growth in three
wards the lower boundary and on reaching its dimensions. The model was photographed with the sun over-
vicinity, it once again branches, this time to (111) head; W is the wire model and S is its shadow, representing the
and (111), from which point the process repeats projection on the boundary plane.
itself. Now the two branches (111) and (iii) re-
main in the vicinity of the boundaries, or very
slowly recede from them. They each have only one 3. We can illustrate the geometry of this case by a
possible-direction of branching on a side remote model (fig. 7). The boundaries are planes normal
from the boundary. In the former case, this is to (111), or close to this direction [23]. Growth is
(111), but this branch is a dead end since it preferred along the [111] axes again. Suppose that
quickly reaches the lower boundary, where it could a seed starts to grow close to the upper surface in
only branch back to (111), thus forming a branch the downward direction (ill). When it reaches the
parallel and too close to the original (111) to proximity of the base, it will branch into two
nucleate. Thus the original (111) does not appear equivalent directions which nucleate together,
to branch at all (fig. 1) although short branches of (111) and (111). The first of these, on reaching the
this sort would be obscured from vision, proximity of the upper surface, branches into (111)
A second scenario which has been observed and (ill) and the second into (111) and (111). So
gives rise to the honeycomb structure seen in fig. the process continues. However, it should be not-
iced that two opposite directions have been pro-
duced, (111) and (111), and from fig. 3 it can be

~Al,,i,il
(1 1 1) (1,1,1) (1,1,1)
c•i,i,i>
B (1,1,1)A (111) seen
coincide
close.
course,
is
gives
cells
that
Annot
fairly
bilities,
larger that
This
rise also
regular
than at
small
towayin
aalthoughadiffusion
interesting
the
closing
growth space,
later
angle
defects
theand stage
aexactly.
featuresolength
honeycomb
between
front,
thewhich
does
size of
not that
on these
result
ofthe the
network
the cells
two
boundary
macroscopic
seem
thehoneycomb
atin
tothe appear
branches
ishoneycomb
set
develop
individual
the tips up.
scale,
growthto
planes
Of
insta-
(fig.
cells is
3c).
is
This feature was also observed in dense branching
Fig. 6. Geometry of growth giving rise to the zigzag crystal
shown in fig. 1. The diagram shows the projection on the plane morphologies [18] and occurred in the present
of the cell: The points marked A are on the base, and B at the experiments when crystals grew in a more or less
top of the layer. radial manner from a fluctuation in a non-uniform
644 E. Raz et a!. / New morphologies observed during dendritic growth of ammonium chloride

initial fluid (fig. 5). A possible explanation for this asymptotically independent of the degree of su-
phenomenon is that the growth velocity of a crystal persaturation, but at present we do not have mdc-
after the nucleation barrier has been reached is pendent experimental evidence to confirm this.
The observation could also follow from the non-
I I I linear relationship between the velocity and the
diffusion field, which might allow only a discrete
150 — - set of stable velocities.

5. Dimensions of the cells

If we assume that the branches emerge at two

parallel planes, and that the growth directions are
known, it is easy to find a connection between the
50 - - dimensions of the periodic structure and the sep-
aration between the planes d. For the case where
+ the growth directions are [1111,we find the follow-
ing relationship between d and the projections l~,
12 and 13 of three sides of a hexagonal cell:
50 100 150
(1)
d(~m) . ~ (c,+c1±1)2=4/3,
Fig. 8. Illustrating the relationship between the dimensions of
the honeycomb units and the thickness of the experimental
cell. The ordinate shows the value of d~aicobtained by invert- where
ing eq. (1), and the abscissa the diameter of the spacers d. The
line has unit slope. The data include zigzag structures, for ~2 = d2,/(d2 + 12) (2)
which one 1 is infinite.

____
B ............~ 250

100- • -100

B ~ -50

A ....

0— ~ I I I I —0
0 1 2 3
t (sec)
Fig. 9. Positions of the tips of the two branches of zigzag growth as a function of time. Note the hesitation after one branch has
stopped and before the second one starts. One cycle is shown.
 E. Raz et a!. / New morphologies observed during dendritic growth of ammonium
and c4 c1. By way of contrast, for the case where
growth is along [100]
3 clearer pictures of the periodic structures. Indeed,
= 1.
i=1
To a first approximation we can take d as being
the physical distance between the boundary planes,
although we should expect the value of d ap-
propriate to eqs. (1)—(3) to be somewhat less by an
amount of the order of the diffusion length (which
determines the distance over which the dendrite
“feels” the image). These formulae are invariant
with respect to the orientation of the boundary
planes, and can be applied to cells of any aspect
ratio or to zigzag growth, which corresponds to
cellular growth with one infinite dimension (i.e.,
one c, is zero). The results of measurements on
many examples of cellular and zigzag structures
are shown in fig. 8 in which we display the value
of dcaIc, derived from the observed structures by
inverting eq. (1), as a function of d, the distance
between the boundaries (i.e. the thickness of the
spacers). It will be seen that the points are con-
sistent with a line of unit slope for [111] growth
(i.e., calculated and measured values agree).
Looked at in detail, we can follow the growth
of a single branch crossing the medium. Fig. 9
shows the position of the tip of growth as a
function of time for two successive edges in zigzag
growth. First one tip stops growing as it reaches
the boundary. Then after a while, the branch
nucleates, reaches a maximum velocity and then
stops at the far boundary. Of significance is the
hesitation [8,9] (in even greater detail, the branch
thickens in a rather isotropic manner during this
period) before the new branch nucleates.
6. Effect of impurities
Finally we should remark on the significance of
the CuSO4 impurity. Although we have not yet
carried out any systematic experiments on this
system, we surmise that the impurity increases the
nucleation barrier. This has the result of suppress-
ing the creation of sidebranches which only ap-
pear under the more extreme conditions of super-
chloride 645
saturation which occur after the crystal growth has
ceased for a while (see fig. 9). This results in
(3) the unrestricted growth of this mixture often gives
long dendrites with no side-branches and either
cusped or quasi-paraboloidal tips, depending on
the degree of supersaturation [24]. Maurer et al.
[25] have seen similar dendrite tips in pure NH4Br
and also attributed them to dynamic roughening.
7. Conclusions
The experiments described in this paper show
the existence of a new family of well-defined pen-
odic morphological structures for an anisotropic
crystal growing in a thin, quasi-two-dimensional
cell. The morphologies show long range order and
their growth fronts are marginally stable. It would
seem very unlikely that a model for dendritic
growth involving noise could explain the long
range order [71,and we attribute the very de-
terministic character of the growth to a nucleation
model for the development of dendrites which was
recently proposed [9]. This model applies only to
crystals growing when the facet in the preferred
growth direction is below its equilibrium roughen-
ing temperature, which explains the strong ani-
sotropy observed as well as the apparently limited
temperature range in which the structures have
been seen. The addition of CuSO4 impurities ap-
parently inhibits nucleation and therefore empha-
sizes the periodic patterns. Our understanding of
the structural and dynamic stability of this new
meta-ordering is still incomplete.
Acknowledgements
We acknowledge the technical assistance of Y.
Moses and S. Hoida, and stimulating conversa-
tions with J.S. Langer, S. Fishman, E. Polturak
and T. Viscek. We are grateful to the US—Israel
Binational Science Foundation, the German--Israel
Foundation, the Fund for Basic Research admin-
istered by the Israel Academy for the Sciences for
support of this research.
646 E. Raz et a!. / New morpho!ogies observed during dendritic growth
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[14] E. Ben-Jacob, P. Garik, T. Mueller and D. Grier, Phys.
Rev. A38 (1988) 1370.
[15] J. Bechhoefer and A. Libchaber, Phys. Rev. B35 (1987)
1393.
[16] L.R. Morris and W.C. Winegard, J. Crystal Growth 5
(1969) 361.
of aminonium ch!oride
[17] The dimensionless unit of supercooling is I — C~
5/c, where
ceq is the saturated concentration of the solution at the
temperature in question and c is the actual concentration
of the solution.
[181 E. Ben-Jacob, G. Deutscher, P. Garik, ND. Goldenfeld
and Y. Lereah. Phys. Rev. Letters 57 (1986) 1903.
[19] GB. McFadden and SR. Coriell, J. Crystal Growth 74
(1986) 507.
[20] The method of images is usually presented as a method of
solving Laplace’s equation. However, it only requires
uniqueness of the solution and definition of static
boundary conditions 4~= constant or V.’, = 0 (let us say,
on the cell surfaces). The non-linear equations involving
the diffusion of solvent and heat and crystal growth are
deterministic and appear to us to satisfy these criteria.
[21] Although we have done no experiments in this direction,
it is of interest to speculate on the effect that boundaries
would have on growth in a thermally dominated system
(ice, for example, at temperatures below roughening, which
is probably around 0°C). We should expect growth to
occur in the preferred growth direction which remains
closest to the boundary, which would indicate a single
growth direction where this is parallel to the boundary, or
a non-periodic network if two such directions are parallel
to it. But if no growth direction is close to lying in the
boundary plane. a three -dimensional network hugging the
boundary will be Set up. and will presumably have a
periodic nature, although we do not see at present what
determines its periodicity.
[22] H. Honjo, S. Ohta and M. Matsushita, .1. Phys. Soc. Japan
~ (1986) 2487.
[23] In this case, Orientations with zero or one negative index
are upward-going.
[24] E. Raz, S.G. Lipson and F. Ben-Jacob. to be published.
[25] J. Maurer, P. Bouissou, B. Perrin and P. Tabeling.
Europhys. Letters 8 (1989) 67.