Journal of Crystal Growth 20 (1973) 183191 North-Holland Publishing Co.

CRYSTALLIZATION KINETICS OF AMMONIUM SULPHATE

MAURICE A. LARSON* and JOHN W. MULLIN
Department of Chemical Engineering, University College London, Torrington Place, London WCI, England
Received 28 February 1973; revised manuscript received 10 May 1973
Nucleation and growth rates of ammonium sulphate
aqueousboth
solution
are measured
by several
different
3 +insuppress
nucleation
and growth
and modify
the
techniques
and comparisons are made. Traces of Cr
crystal
habit.

1. Introduction

the maximum allowable supersaturation, b the batch

cooling rate, and dc*/dO the slope of the saturation
curve (cf. section 6, Notation). Recognizing that

The crystallization of ammonium sulphate has received considerable attention in recent work and some
ACmax = (dc*/dO) AOmax,
progress has been made in determining the applicable
kinetic relationships for nucleation and growth. The substitution into eqs. (1) and (2) gives
purpose of this paper is to compare some of the data k (dc*/dO)b = k~[(dc*/dO) AO ~m
(3)
maxi
previously available in the literature, which have been
obtained in various ways, and to present new data on or
nucleation and growth measured in pure aqueous solulog b = K + m log AOmax.
(4)
tion. In addition, preliminary results are given showing
the effect of Cr3 + (added as CrCl
3) on the nucleation The slope of a plot of log b versus log AOmax is the
and growth processes.
order of nucleation, m, in eq. (1). They found that
seeded systems, containing one or two individual crys2. Crystallization from pure solution
exhibited orders of 2.62 0.92, i.e., in terms of
1) presented data on tals,
eq. (1),
In
a
recent
paper,
Mullin
et
al.
2.62 0.92
the nucleation of ammonium sulphate obtained by a B = k
11 ACmax
(la)
batch 2).This
coolingtechnique
technique
by Mullin et al.1) also presented data for the growth rates
waspreviously
developed described
from an analN~vlt
ysis of the nucleation process using the assumption of various faces of the ammonium sulphate crystal.
that the nucleation rate is proportional to: (a) the They found that the (100) faces grew at a first order
maximum allowable supersaturation to mth power,
rate with respect to Ac over an undercooling range of
2.1 C,whereas the (001) face growth rate was shown
B = k n Ac~~z
(1) to be approximately second order. These results sugmax,
and (b) the cooling rate
gest that the habit (and thus the crystal shape factor) is
B = k (dc*/dO) b,
(2) very dependent on the level of supersaturation in the
liquor in which the crystal is growing.
where Bis the birth rate of zero-sized crystals, Acmax
Because of the very low levels of supersaturation
supported by ammonium sulphate, stirred tank growth
* Present address: Department of Chemical Engineering and
rate measurements have generally proved unsuccessful.
,

Engineering Research Institute, Iowa State University, Ames,

Iowa, U.S.A.

Growth is extremely slow in the supersaturation range

183

184

MAURICE

A. LARSON

where nucleation does not occur. N~vlt3),however,

has suggested that growth under these conditions appears to be first order.
In a more direct approach toward measuring nude4) measured the relative order
ation
kinetics,
Chambliss
of nucleation and growth. His approach used the data
analysis method proposed by Timm and Larson5) for
a mixed suspension mixed product removal (MSMPR)
crystallizer. For such a crystallizer, a population balance shows that the size distribution, in terms of the
crystal number density a, is given by
n

n0 exp (L/Gi),

B = Gn.

kg(Ac)~

kNMjG(m/9)~,

nt
(No/pm)
M

2.55
3.16
3.36

7.01
3.89
2.63

3.92
4.01

6.97
3.86

5.78
6.58
7.40

L
0
(pm)

2.42x l0~
1.53 x l0~
1.52x iO~

3(6
350
355

M = 4
3.32x l0~

314

2.20x l0~

348

7.34

5.05 ~ l0~

330

6.93
3.94

6.38 t< l0~

3.86 ~ lO~

312
354

7.46

2.61

3.92x i0~

352

7.42

2.56

4.25 x l0~

346

4.33

2.68

l.89x l0~
M
75

362

f n corrected to the value of the suspension density M (g/l00 ml)

shown above each set of runs and based on total crystallizer
volume.

(7)

litre draft tube type crystallizer. The suspension density

was varied by changing the concentration of the feed
stream.
Assuming an order of growth g = I, the order of
nucleation, rn, becomes 1 .5 0.2, which is on the low
side compared with that obtained by Mullin et al.).
However, if a more realistic order of growth is used,

(8)

are assumed, eqs. (6) to (8) may be combined to relate

the nuclei population density with the kinetics. Thus
a0

M
G
(g/lOOml)(pm/min)

vary from 0.3 to 0.7 giving a relative order of nucleation and growth, rn/g, equal to 1.5 0.2. These experiments were carried out at 22 Cin a highly agitated 11

and a power law growth model,

=

~~lPh~t~

(6)

If a power law secondary nucleation kinetic model,

TABLE I
Experimental operating conditions and results for ammonium

(5)

if growth is not a function of size. G is the growth rate

(dL/dt) of a characteristic crystal dimension, i is the
crystal mean retention time, L is the crystal size, and
n0 is the number density of zero-size crystals (nuclei).
The nuclei population density, n0, is related to the
nucleation rate, B,by

B = k~M~(Ac)6,

AND JOHN W. MULLIN

(9)

1.5 (estimated from Mullins data forfacial growth),

then the nucleation order obtained is 2.3 0.3, which
say

where M is the suspension density and M~empirically

represents the nucleation rate dependence on the quantity of crystals in suspension.
Experimental size distributions obtained from continuous MSMPR experiments yield, through eq. (5),

____________________________

106

values
of n
and obtained
corresponding
valuesthe
of size
G. distriThese
values are
usually
by plotting
bution on semi-log paper. The intercept is nand the
slope ( 1 /Gr) contains the crystal growth rate.
Plots of log nversus G give lines of slope (ni/g) 1,
from which the order of nucleation, rn, can be obtained
if the order of growth, g, is known.
In experiments at various suspension densities and
residence times, Chambliss4) obtained the results shown
in table I. In fig. I, log n0 is plotted versus log G for
various suspension densities. The slopes of these plots

z0
~

l0~i

II
22C
7-5g/IOOmI

M-

A
U

M 4Og/IOOm~
M- 3Og/IOOn~I

8 10

20

G, ~m/min

Fig. I.
phate4).

Nucleation and growth kinetics of ammonium sul-

185

CRYSTALLIZATION KINETICS OF AMMONIUM SULPHATE

__
,,,,,,.4//

VA~OTTLE

SATURATOR

~j

L
0

l0~I

WTER

G 2 6~im/min

2468

10

20

CRYSTALLIZER

M, g/IOOml

ROTAMETER

Fig. 2. Nucleation
4).rate of ammonium sulphate as a function of
suspension density

Fig. 3.

Experimental MSMPR crystallizer.

order, j, with respect to suspension density of 0.98.

These results are in quite close agreement with the above.

is in close agreement with Mullins value of 2.62 0.92.

To determine the order of nucleation,], related to the
suspension density, Chambliss plotted the nucleation
rate versus suspension density at constant growth rate
(fig. 2). Clearly the nucleation is secondary and is approximately first order in relation to suspension density.
Youngquist and Randolph6) studied the secondary
nucleation rate of ammonium sulphate by determining
the size analysis of crystals generated in a continuous
crystallizer using in :situ measurements with a Coulter
counter. Their analysis gave a relative nucleation order
with respect to growth, m/g, of 1 .22 and a nucleation

3. Experimental
The data of Chambliss4) were extended using a I
litre beaker (working volume 800 ml) as a crystallizer
and a stainless steel cooling coil as a draft tube. A
marine propeller was used as an agitator with stirring
sufficient only to ensure a well-mixed suspension. The
apparatus is shown in fig. 3. The vessel was fed continuously by gravity from a heated reservoir through a
Rotameter. Feed solution was saturated at 40 C.Heating was provided by circulating water from a tempera-

TABLE

Nucleation and growth data for ammonium sulphate: 800 ml MSMPR crystallizer operated
at 18 C;feed saturated at 40C
Run No.
8
4
9
10
II
12
2
3j~

Cr3~
(ppm)

(mm)

M
(g/l00 ml)

0
0
0
5
5
10
10
20

8.5
11.1
19.6
8.5
8.5
8.5
11.4
10.9

3.8
3.8
3.8
3.8
3.8
3.4
4.1
2.5

The crystals from run 3 were impossible to size.

M(calc.)
B
(g/l00 ml) [No./(100 ml) (min)l
3.9
3.9
3.9
3.9
3.9
3.9
3.9
3.9

2.7 x
2.1 ><
1.8><
1.1 x
1.1 x
8.7 x
7.3><

l0~
i0~
i0~
i0~
10~
l0~
l0~

G
(j.tm/min)

(pm)

13.5
10.5
9.1
18.3
18.3
19.2
14.6

345
350
345
467
467
490
500

186

LARSON AND JOHN W. MULLIN

MAURICE A.

ture-controlled water bath, through a coil in the reservoir. Product slurry was removed intermittently with
a vacuum bottle.
To make a run the crystallizer was operated for 68
retention times. At the end of a run the entire contents
of the crystallizer were filtered, the crystals washed
with methyl alcohol and dried. The size distribution
was determined with 2 in. diameter standard sieves.

The intended suspension density was 4 g/I00 ml and the

temperature of crystallization was maintained at
18 0.5 C.
The results of several runs, along with results when
3
Cr + was present, are shown in table 2. The nucleation
and growth rates for pure solution were obtained from
plots of these data as illustrated in fig. 4 for run 8.
Fig. 5 shows the results of Chambliss4) together with

I0~ _________________________________

those of the present experiments. Here B is plotted

rather than n.The data have been put on the common
basis of number per 100 ml per mm. The agreement is

tO3

quite good considering the different apparatus geometries used, the different temperature of crystallization,
the different raw material, and above all, the probable
difference in stirring intensity. The agitator speed in the
present work was approximately 500 rpm compared

8-5rmo
376g/lOOml
B=2-7IO4No/000mI)lmIn)

I0~
o\

with 1700 rpm used by Chambliss4). This, along with

the lower temperature level in the present experiments,
explains the lower nucleation rates observed.
It should be noted that, within the accuracy of meas-

urement,assuming
the crystal
wasliquor
the expected
yield calculated
the yield
mother
was at saturation
concentration, confirming the existence of an extremely
low supersaturation within the crystallization vessel.
0

400

800

1200

4. Crystallization in the presence of impurities

L, ~um

Fig. 4. Crystal size distribution of ammonium sulphate crystallized from pure solution.
40

______________________________

30

I
a.

JO

/7

20

EXPERIMENTS

The one litre MSMPR crystallizer discussed above

was used to determine the effect of Cr3~ (added as
CrC!
3) on the nucleation rate of ammonium sulphate
at the same conditions used for the pure solution experiments (feed solution saturated at 40 Cand a crysl0~

RUNI2

0 V

/$

4.1. MSMPR

litre

4g/lOOmI

102
.

~)~

~.
~

6-5r,in

5 = 87~lO~
3~
No./tIOOrnll(rnin)

...

T15to45r,,in
5=22C

:
=

lOppm Cr

il55

V = 800 nI
M = 38g/lOOrnl

-*

018C

8-5 to 12-6 mix

20

G, ~Jryt/min
Fig. 5. Nucleation and growth kinetics of ammonium sulphate
(dashed curve taken from ref. 4).

400

800

200

1600

L.,pm

Fig. 6. Crystal size distribution of ammonium sulphate crystallized in the presence of CrCI
3.

CRYSTALLIZATION

KINETICS OF AMMONIUM

tallization temperature of 18 C).Again the supersaturation was not measured because it was too low. In
any case the term supersaturation loses a measure of
its meaning when impurities are present, since it is not
I,
-

viously
(7a)
________

Another

______

~
__________
_____

187

known if the normal equilibrium solubility, c~,applies

under these conditions.
A typical size distribution is shown in fig. 6 and the
results of all runs are given in table 2. Photographs of
the crystalline product obtained from pure
solution
and
of Cr3~
in
presence
10 weight
and 20 of
ppm
Cr3~(parts
perthe
million
partsof by
solution)
are shown in
figs. 7a, 7b and 7c. Fig. 7a is the crystalline product
from pure solution and exhibits the characteristic habit
of ammonium sulphate. Fig. 7b shows the product
from solution containing 10 ppm Cr3~added as CrCl
3,
and
fig.
7c
shows
the
crystals
produced
when
20
ppm
3 + are present. From fig. 7b it appears that the initial
Cr
effect is the development of (110) or (111) faces resulting in a more pyramidal habit. This, along with the
evidence in fig. 7c, shows that the presence of Cr3 + obchanges the relative face growth rates and encourages the appearance of higher index faces, but u!timately there is a breakdown of regular growth leading
to the formation of crystals of grotesque shape.
pronounced effect of Cr3~is the suppression of nucleation. In an MSMPR crystallizer this results in an increase in mean crystal size as shown in
table 2 and fig. 6. These data were obtained from the
size distributions obtained from sieve analyses. In calculating the number distribution a volume shape factor* of unity was used. Clearly, the shape factors of the
crystals in fig. 7 have a variety of values, so the results
can only be interpreted in a qualitative way. It is clear,
however, that the general trend is for nucleation rate to
decrease as Cr3~ concentration increases. This is
shown in fig. 8 for three runs at a residence time of

(7b)

$
~

SULPHATE

.
.

~
4

(7c)
Fig. 7. Aiiimonium sulphate crystallized (a) from pure solution,
(b) in the presence of 10 ppm Cr31 (as CrCI
Ic) in the presence of 20 ppm Cr3~(as CrCI 3 iii solution), and
3 in solution),

8.5 mm and two runs at 11 mm.

The results also show that growth rate increases as
Cr3~concentration increases, but this is in direct contradiction to the single crystal growth results to be discussed below. As a consequence, these MSMPR results
can only be explained by recognizing, under the constraints of equal production rate, that if the nucleation
rate decreases, the resulting decrease in crystal surface
area can only result in a higher supersaturation. This
means that a much higher effective supersaturation
existed at high Cr3~concentrations resulting in higher
growth rates.
*

If L is the characteristic screen size of a crystal, its volume is

3,wherek, is the volume shape factor. For cubes k = I, for

k5L
other shapes k. ~ 1.

MAURICE A. LARSON AND JOHN W. MULLIN

188

-\
- \

26
22

slopes of these lines as a measure of the order of

then tothebe order
the presence
of
Cr3~would
nucleation1 2)appear
virtuallyininfinite
suggesting
the occurrence of massive nucleation at the boundary

0 t-~5m,n
r=n mm

I
0
Q

18

4.2. SINGLE CRYSTAL EXPERIMENTS

In order to characterize more fully the phenomena

described above, experiments on growth of single crystals of ammonium sulphate in the presence of Cr3 +
were made. In one set of experiments the facial growth
rate was measured and in the other the growing surface
was observed using reflection microscopy.

of the metastable limit. This is clearly inconsistent with

the observations in the MSMPR experiments where
no massive nucleation occurred.

Cr3~,ppm

(a)

4.3.

20

GROWTH BEHAVIOUR OF SINGLE CRYSTALS

It is clear from the above work that the presence of

16
T=llmin
0 85
n

12

A 4lg/IOOrnl
8 3-4g/IOOmI
B B or, A bas,s

15

a.

8
0

1
0

10

B/

Cr~ppm

Fig. 8. Effect of Cr3~on the crystallization kinetics of ammonium sulphate; (a) nucleation rate. (b) growth rate.

,.~

6-

The results of runs 2 and 12 are plotted in fig. 9 in an

attempt to determine the order ofnucleation in the presence of impurities. The data are limited and the result
is not conclusive, but there is no indication of any pronounced change in order. When both data points are
put on the same suspension density basis, the order is
within the range of that for the pure system. It is interesting to note that Shor and Larson8) found that while
several additives changed the nucleation rate of KNO
3,
they had only
minor
effect
on
the
order.
3 + was used in nucleation experiments simi=
Cr described by Mullin et al.2), the results
larWhen
to those
shown in fig. 10 were obtained. Line a is for a seeded
pure system. The other lines are the results for various
levels of impurity. The main point to note is that the
metastable region is considerably widened in the presence of CrTt This finding is consistent with the
MSMPR experiments. However, if one regards the

10

I~

2b

30

G, ,um/min
Fig. 9. Nucleation and growth kinetics of ammonium sulphate
in the presence of Cr3 ~
100
80
60

40

y
-

20
.~

10
Pure

35ppm

21 ppm 36ppm

8 10

undcrcooIIn4,

20

30

~eC

Fig. 10. Maximum allowable undercooling as a function of

cooling rate in the presence of Cr3t

CRYSTALLIZATION

KINETICS

certain impurities, such as Cr3~,exert a profound effect

on the crystal growth process. Some growth rate measurements of the (0011) faces of single ammonium sulphate crystals were made by a technique described by
Mullin et al.7). The runs were carried out at 25 C
with a fixed crystal, 2-4 mm in size, located in a solution flowing at 3 cm/s.
In pure solution the growth rate in the (001) direction was found to be similar to that determined previously), ranging from about 2 x 10-8 rn/s at Ac
3 x l0~kg per kg of water to about lx l0~ rn/s at
Ac
5 x l0~ kg per kg of water. The second order
dependence of growth rate on supersaturation was
confirmed.
The presence of I ppm Cr3 + (introduced as CrCI
3) in
the solution had no noticeable effect on the (001)
growth rate. The presence of 2 ppm appeared to have
no effect in the early stages of growth, but after about
an hour irregularities were noted on several of the
crystal faces and the (001) growth rate slowed down
slightly. At 3 ppm there was definite evidence of growth
irregularities on the faces almost as soon
as the
3~ there
wasima
purity was
introduced.
At growth
5 ppm on
Cr all faces. In all
virtual
stoppage
of normal
the runs made in the presence of impurity, the supersaturation, Ac, was maintained at 5x l0~ kg per kg of
water.

189

OF AMMONIUM SULPHATE

_______
--. ,~

-~

______

~-~

(a)

______

________
_____

_______
_____

_______
-,

(b)
4.4.

LAYER GROWTHS ON CRYSTAL FACES

Some observations of surface growth features on

ammonium sulphate crystals growing in aqueous solution at 25 C,using reflection microscopy, indicate that
ionic impurities influence the growth mechanism. The
crystals were nucleated and grown in a small observation cell, and were approximately 0.5 mm in size at the
time of observation. The crystals were stationary and
the solution flowed past them at a slow but unmeasured
rate,
Growth in pure solution was generally characterized
by layers originating at random points on the crystal
surface and apparently moving inwards on themselves,
finally to disappear at some well-defined point near the
centre of the crystal face. Fig. I Ia shows a typical example with the layers moving inwards, away from the
edges of the crystal. The layer patterns were generally
elliptical. When the solution was contaminated with
5 ppm of Cr3 (introduced as CrCI
3) the surface

Fig. 11. Growth layers on the faces of ammonium sulphate

crystals growing in (a) pure solution, and (b) a solution containing 5 ppm Cr3t

growth layers became slow-moving and polygonized,

as shown in fig. 1 lb.
These observations are compatible with the kinematic theories of crystal growth9 10) in which visible layers
result from step bunching due to perturbations within
elementary step trains. The initiations of such step
bunches have been observed at well-defined points on
the faces of sucrose11) and ammonium dihydrogen
phosphate2), corresponding presumably to points of
emergence of groups of screw dislocations or other
defects.
The present observations with ammonium sulphate
suggest that the step bunches are not formed at growth
centres but at random points along the step trains,
giving rise to visible layers. For growth in pure solu-

190

MAURICE A. LARSON

AND JOHN W. MULLIN

tion, the elliptical nature of the layers reflects the anisotropy of the surface structure, which consists of alternate regions of positive and negative ions, and suggests
that surface diffusion is important in the growth mechanism.
The polygonization of the growth layers in the presence of Cr3 + is consistent with adsorption of these
foreign ions at kink sites along the elementary steps,
effectively reducing the number of kink sites, imposing
a crystallographic dependence on the step velocity and
reducing the overall face growth rate,

nucleation kinetics of the pure system near some point

aa on the upper line. Consequently substantially the
same result would be expected and this, in fact, has
been found. In the presence of Cr3 + the metastable
region is widened (see fig. 10), as indicated by lines b,
c and d in fig. 12, but in a back-mixed system underdoing secondary nucleation some nucleation undoubtedly takes place in the metastable region, as indicated
by the lines of low slope.
The method of Timm and Larson would very likely
measure nucleation rates within the metastabie zone at
points near bb or dd, giving a very low order nucleat5. Discussion
ion. This is entirely consistent with the MSMPR exThe two different methods of determining nucleation perimental results reported above. On the other hand
rate described in this paper appear to give similar re- the method of N)2vlt, carried out under conditions of
suits for the pure system, but partially contradictory mild agitation and in the presence of only one or two
results in the cases where impurities are present.
crystal seeds, would not show nucleation until the
It is clear, however, that the two analyses are to limit of the metastable zone was reached. Hence the
some degree different in concept. The method of N~vlt near-vertical lines in fig. 10, which correspond to the
essentially determines the slope of the nucleation curve lines of high slope in fig. 12, indicating a very high or[the order of nucleation, m, in eq. (1)] for the point der nucleation, in an MSMPR crystallizer operating
at which massive nucleation occurs, that is, at the with a reasonable suspension density, it is extremely
boundary of the metastable zone. On the other hand, unlikely that the region of massive nucleation is ever
the method of Timm and Larson determines the slope reached,
of the nucleation curve in systems where only moderate
The single crystal studies confirm a pronounced
nucleation is occurring,
effect on the growth of ammonium sulphate crystals by
A loglog plot of the nucleation kinetics of the pure traces of the ionic impurity Cr3t The relative growth
ammonium sulphate system may diagrammatically be rates of the various faces are drastically altered and the
represented by line a in fig. 12. The system has a nar- character itself is changed, as seen in fig. 11. It appears
row metastable region and relatively low order kinetics that these changes in growth mechanism in some way
when substantial nucleation occurs, It is reasonable to affect the secondary nucleation kinetics, although it
assume, therefore, that both methods would determine would seem that the nature of this growth would be
favourable to higher nucleation rates.
____________________

b-d increasing Cr3

6. Notation
b
Cooling rate (C/min)
B Nucleation rate (number per mm per 100 ml)
c
Solution concentration (g/lOO ml)
c*
Equilibrium solubility (g/lOO ml)
Ac
Supersaturation, c_c* (g/l00 ml)
~
Maximum allowable supersaturation (g/l00 ml)
g

:::: i---

Log Ac
-.
Fig. 12. Nucleation kinetics of ammonium sulphate shossing
effect of Cr3 ~.

G
]
k
kg

Order of crystal growth [eq. (8)]

Crystal growth rate, dL/dt (j.tm/min)

Order of nucleation with respect to suspension

density, M [eq. (9)]
Constant in eq. (2)
Growth rate constant [eq. (8)]

CRYSTALLIZATION

k,,

k0
kN
K
L
LD
rn
M
n

KINETICS OF AMMONIUM

SULPHATE

191

Nucleation rate constant [eq. (1)]

the manuscript. The authors are also indebted to the

Nucleation rate constant [eq. (7)]

Nucleation rate constant [eq. (9)]
Constant in eq. (4)
Crystal size (j.tm)
Dominant crystal size (i.tm)
Order of nucleation
Suspension density (g/lOO ml)

Iowa State University Faculty Leave Program for

making this collaboration possible.
References
I) J. W. Mullin, M. Chakraborty and K. Mehta, J. AppI. Chem.
20 (1970) 367.
2) J. N~vlt,J. Crystal Growth 3/4 (1968) 377.

Crystal number density (number per mm per Rm)

Number density of nuclei (number per mm

Time (mm)

-r

Crystal mean retention time

per

lim)

(mm)

Temperature (C)
0*
Equilibrium saturation temperature (C)
A0 Supercooling, O~O(C)
AOi,,ax Maximum allowable supercooling (C)
O

Acknowledgement
The authors are indebted to Roger J. Davey of University College Londcn for the photographs in fig. II
and for useful discussions during the preparation of

3) J. N~vIt,private communication,
4) C. W. Chambliss, Nucleation and Growth Kinetics in a
Cooling Crystallizer, Unpublished Ph. D. Thesis, Iowa State
University, 1966.
5) D. C. Timm and M. A. Larson, AIChE J. 14 (1968) 452.
6) G. R. Youngquist and A. D. Randolph, AIChE J. 18(1972)

421.
7) J. W. Mullin et al., J. AppI. Chem, 17 (1967) 151; Trans.
Inst. Chem. Engrs. London 45 (1967) 285; Can. J. Chem,
Engng. 47 (1969) 483.

8) S. M. Shor and M. A. Larson, Chem. Eng. Progr. Sympos.

Series No. 11067(1971) 32.
9) F. C. Frank, in: Growth and Perfection of Crystals, Eds.
R. H. Doremus et al. (Wiley, New York, 1958) p. 411.

10) N. Cabrera and D. A. Vermilya, in: Growth and Perfection of

Crystals, Eds. R. H. Doremus et al. (Wiley, New York,
1958) ri. 393.
II) N. Albon and W. J. Dunning, Acta Cryst. 12(1959) 219.
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