THIRTY-NINTH CONFERENCE

NUCLEATION STUDIES
By R. BROADFOOT and P. G. WRIGHT
Sugar Research Institute, Mackay
Introduction
Closer control of batch pans and the investigation of continuous
boiling procedures demand a greater understanding of the phenomena of
nucleation. Comparatively little is known of the kinetics of the formation
of nuclei in sugar solutions. Empirical studies have therefore been made
into specifying pan conditions for which nuclei enter the mother liquor
and into their subsequent rate of formation.
Mechanisms of Nucleation
From a simplified viewpoint, crystallizable solute molecules are
considered to be in an ordered low energy state once bonded in a
crystal lattice, while molecules in solution are in a higher energy state
and the movement is completely random. The driving force in crystal-
lization is the difference between the free energies of the liquid and solid
states. When a sufficient number of these freely-moving molecules form
a stable, low energy configuration and exist as a separate entity, then a
"nucleus" is said to have formed on which further solute molecules may
be deposited.
In one possible mechanism for nucleation it is considered that the
molecules in their random motion through the solution may by chance
encounters create a molecular arrangement corresponding to the
configuration of the crystal lattice. The release of the kinetic energy of
the molecules will only result in a stable nucleus for agglomerates larger
than critical size (Ostwald, 1903), as, due to their larger unit surface
free energy, smaller crystals have a greater relative solubility. The
nucleus will only be stable then if the driving force provided by the
supersaturation is sufficient to overcome this tendency to dissolve.
This suggests there could exist a critical supersaturation above which
nuclei will stabilize and grow. Nuclei formation under such conditions is
termed homogeneous nucleation.
Seed crystals in the solution act to catalyze the nucleation process.
Solute molecules in the solution may adsorb onto the crystal surface
without fitting into the crystal lattice. The clustered arrangement of the
solute molecules on the surface simplifies the orientation process and
reduces the ,activation energy in the formation of the nucleus. As a
result a smaller driving force (supersaturation) would then be required
for nuclei formation in the presence of seed crystal. Clontz and McCabe
(1969) have suggested that the molecular agglomerates are sheared from
the crystal surface by inter-crystal or crystal-wall contacts. This has
been termed "collision breeding". Experiments conducted by Powers
(1963) indicated that the shearing action may also result from fluid
motion through the boundary layer. In addition to these nucleation
mechanisms Strickland-Constable (1968) postulated that microdendritic
354 T H I R T Y - N I N T H CONFERENCE 1972

30 60 90
Temperature. OC
Fig. I-Approximate supersolubility pattern for sucrose (after Miers and lsaac (1906))

growths from crystal edges which continually break off to become new
crystals are another source of nuclei for crystal growth. He termed this
"needle breeding".
These suggested mechanisms comply with empirical super-
solubility curves first postulated by Miers and Isaac (1906). An idealized
supersolubility diagram applicable to sucrose is given in Figure 1. In
the simpler cases, a single supersolubility curve was drawn above the
saturation curve. All concentrations in excess of this would be sufficient
to cause spontaneous (homogeneous) nucleation from solution. This
area is known as the labile zone. The region between the saturation
curve and the supersolubility curve is known as the metastable zone.
In this region nucleation does not normally occur. In the case of many
materials, including sucrose in water, the metastable zone is further
subdivided by another supersolubility curve to form an intermediate
zone. In this zone nucleation will occur in the presence of seed crystals
of the solute, i.e., by a secondary mechanism. The position of the super-
solubility curves is highly dependent on the many external factors
influencing the system.
In light of these mechanisms an expression for nucleation in the
presence of seed crystals which has been proposed by Bransom, Brown
and Heeley (1969) as a result of their experiments on magnesium
sulphate heptahydrate-water system appears logical. This is given as
dN
B, = - = k,A ( S S - S S 3 for SS > SSn
dt
= 0 for SS < SS, .. . (1)
1972 T H I R T Y - N I N T H CONFERENCE 355

where B, is the rate of nucleation

SS is the operating level of supersaturation
SS, is the threshold level of supersaturation
A is the total surface area of the crystals
k, is an empirical constant.
This relationship suggests a linear dependence of nucleation rate on
crystal surface area and the mother liquor supersaturation.
Application to Sugar
In practice, supersaturation values drop sharply a little time after
nucleation, due to the rapid growth of the new crystals. The phenomena
tends to occur, therefore, in discrete bursts. Work by Penklis and
Wright (1963) on the sucrose-water system has indicated that a threshold
supersaturation limit exists. They operated a laboratory vacuum crystal-

TABLE !-Critical supersaturation values for some cane syrups

(Crystal content 10 t o 30% w/w)

Temperature
Factory 7 l. l
material
80" Pty 70' Pty 60' Pty 80° Pty 70' Pty 60' Pty

Racecoun e
Kalamia
Millaquin
Desludged Millaquin

lizer at a controlled rate of rise of supersaturation until fine grain

nucleation was observed. Threshold supersaturation values were
estimated, after partial correction for growth of the nuclei was consider-
ed. This work has been further extended by Hesp and Dunton (1963).
Table I summarizes key values of the data from these two sources.
From the work of Penklis and Wright (1963), values of the threshold
supersaturation limit, SSn, were found to be significantly influenced by
impurity level and temperature. The regression line of the multilinear
regression fit to their data gave an expression of the form
SS, = 1.12889- 0.2841 ( I / ( S+ I ) ) + (2.333 -0.0709 (T - 60)) ( I / S + I)'. . (2)
where I is the per cent impurity in the mother liquor
S is the per cent sucrose in the mother liquor
T is the temperature ("C)
In the literature, the effect of temperature on the supersolubility curves
for the sucrose-water system has not been given much attention. Contrary
to the above, Davies and Yearwood (1944) claim that its effect on the
limiting supersaturation values for nucleation is slight. These authors
give the metastable zone limit of 1.20 for pure sucrose solutions and
1.30 for 70 per cent purity cane syrups.
Even if we can define the metastable zone limits, there remains the
estimation of nucleation rates in the labile and intermediate zones.
There exists very little data in this area which could be applied to
industrial sugar pan-crystallizer conditions.
356 THIRTY-NINTH CONFERENCE 1972

Van Hook (1971) considers the nucleation of sucrose to be a

diffusion controlled reaction at normal temperatures. He states that its
activation energy is comparable with that of diffusion and viscosity.
He also notes that viscosity has a large influence on nucleation behaviour
even to the point of complete inhibition in very high sucrose concentra-
tions, and points out (Van Hook and Bruno (1949)) that invert sugar
retards nucleation by increasing viscosity in syrups. This work suggests
that there should be some viscosity term in the nucleation expression for
sucrose although, possibly, the influence of viscosity is a dependent effect
of the level of supersaturation.

Experimental Studies
Experiments were designed to investigate the rate of formation of
nuclei and factors influencing the threshold supersaturation limit for the
sucrose-water system.
Experiments to determine the "critical" value of supersaturation
were carried out in the laboratory vacuum pan. In a factorial experi-
mental design the supersaturation at which nuclei were first observed
for different conditions of seed crystal content, temperature, syrup
purity, and for different rates of syrup concentration, was determmed.
In these experiments, the concentration of the mother liquor was
correlated to the boiling point elevation of. the liquor above that of
saturated vapour. The time which elapsed from when the nuclei first
formed to when they could be observed was estimated from knowledge
of the nuclei size for observation and the growth rate. Equations of
growth developed by Wright (1971) were used for this estimation. The
concentration which took place during this time could then be inter-
polated from the correlation and the actual supersaturation at which
nuclei were first formed could be determined.
After the nuclei growth correction, regression of the results and
analysis of variance showed that temperature and rate,of concentration
were not significant variables in their effect on the nucleation point. The
regression curve found to be the best fit to the data had the form

where CC is the crystal weight per cent on massecuite.

The multiple correlation coefficient was .845 and the value of the
standard error of the estimations was 0.036"SS. This relatively large
value reflects the difficulty encountered in being able to reproduce the
critical value for nucleation. This expression gives results close to those of
equation (2) for 60" C . These experiments indicate that the purity of the
mother liquor is the major variable of those considered in influencing
the critical supersaturation and that the quantity of seed crystal present
is also of some importance.
The influence of these two variables is in accordance with Ostwald's
mechanism of nucleation. At higher purity the probability of forming a
molecular agglomerate of suitable configuration is greater since inter-
ference from impurity molecules is then less. The threshold supersatura-
tion would thus be expected to be less at higher purity. In accordance
with this mechanism also the results show nuclei tend to enter the
mother liquor at a lower supersaturation for a greater quantity of seed
crystal present.
 T H I R T Y - N I N T H CONFERENCE 3 57

60
Mother Liquor Purity ,per cent
Fig. 2-Threshold
80
- 100

supersaturation limits for cane syrups.

Figure 2 shows the threshold supersaturation limits obtained for
cane syrups in the purity range 65 to 100 per cent and temperature of
50 to 70' C, as applied to a crystal content of 20 per cent. The values
obtained by Penklis and Wright (1963) and Hesp and Dunton (1963), as
given in Table I, lie close to these critical limits.
Temperature and rate of concentration had more effect on the
observed supersaturation values at nucleation as they did affect the
extent of correction required, through their influence on the nuclei
growth rate and the amount of concentration taking place in the growth
time. However, this influence was again not significant on a statistical
basis. The uncorrected supersaturation values are naturally somewhat
higher than the threshold limits proposed in Figure 2. The extent of
correction for nuclei growth is greater for lower purity mother liquor.
Nucleation rates for high purity syrups in the presence of seed
crystals were determined using an unsteady state method. Both the
Coulter Counter and microscopic methods were used to measure nuclei
counts. The conditions used approximated to those in factory units,
except that the crystal content level was lower. Five litres of syrup were
concentrated rapidly in the laboratory pilot pan to a predetermined
concentration and temperature. The concentration could be estimated
during this step by correlation with the electrical conductivity measure-
ment taken from the pan. At the desired concentration a quantity of
prewashed crystals of about 800 microns in mean size was introduced
into the pan. After injection of the seed crystals, conditions were kept
steady by complete or partial reflux of all condensate for a short period,
usually five minutes. After this period, the concentration was reduced
to achieve a relatively low value of oversaturation so that growth of the
crystals and nuclei would take place without further nucleation. The
nuclei induced at the high concentration were allowed to grow in this
way for 0.5 to 1.0 hours so that they would more readily be counted.
In the first series, the Coulter Counter system of detection and counting
of nuclei was used. This procedure is described in Appendix 1. The
results are given in Table 11.
358 THIRTY-NINTH CONFERENCE

A low count, indicating a lack of nucleation was obtained for

supersaturation values at the seeding point of less than about 1.18. At
values in excess of 1.20, however, very high counts were noted, with
quite a deal of variation in counts. The variations did not enable the
proposition of the Bransom, Brown and Heeley model (that nucleation
rates increase linearly with oversaturation above the critical value) to be
supported. This is shown by Figure 3, where the logarithm of the nuclea-
tion rate is plotted against the oversaturation. The nucleation count
above a supersaturation of 1.18 varied from 2.5 X 105 to 2.5 X 106
crystals per m1 for the five minute holding period. The equation

B, = 1.8 x log A for SS > 1.18

= 0 for SS < 1.18

roughly represents the results obtained, where B, is in no./(ml min) and

A is the area of seed crystals in square metres/ml of massecuite.

TABLE Il-Nucleation data for pure syrup (first test)

Crystal Over-
Temp. Time content saturation Count Log
"C min % ("1 count
0.40 1 575000 5.7586
0.151 1250 3.0963
0.3 12 897000 5.95 17
0.247 1 187500 6.0735
0.184 I 0.0000
0.292 194740 5.2885
0.296 1 5 1 5000 6.1792
0.38 1 1875000 6.27 18
0.428 605000 5.7807
0.364 1385000 6.1403
0.739 1395000 6.1434
0.488 12 1 5000 6.0834
0.237 575000 5.7586
0.358 806400 5.9054
0.344 332500 5.5207
0.650 277500 5.4422
0.270 1 35800 5.1319
0.262 3 15000 5.4973
0.197 696000 5.84 15
0.209 250000 5.3969
0.493 122500 5.0872
0.218 1043750 6.0 175
0.218 550000 5.7393
0.138 l 0.0000
0.45 1 13 15950 6.1 181
0.499 768000 5.8843
0.337 I 100000 6.0403
0.212 575250 5.7588
0.069 I 0.0000
0.358 3 18750 5.5024
0.350 53 1250 5.7242
0.258 1653600 6.2 173
0.28 1 1375000 6.1371
0.306 1950000 6.2889
0.289 2 150000 6.33 12
0.163 26 14375 6.4 l62
i972 THIRTY-NINTH CONFERENCE

Fig. 3-Nucleation
Supersaturation -
rate in the presence of seed crystals (first test)

Some results in Table I1 are for tests with holding periods other than
five minutes. There seems no significant change in the numbers of nuclei
induced by the different times. The process seems a highly complex one,
with the initial burst of nuclei not appearing at a steady rate. As to the
effect of amount of seed crystals, the total crystal content was quite low
in all tests but there were some variations made. A regression of the log
of count rate against the seed crystal area was carried out for those
tests above the nucleating supersaturation level. The crystal area did
have an influence on the nucleating level significant at the one per cent
level, and the effect was in line with the prediction of the Bransom model.
TABLE Ill-Nucleation data for pure syrup (second test)

Con- Holding Crystal Over- Count

centration Temp. time content saturation No./ml
% "C min % (") 103
360 T H I R T Y - N I N T H CONFERENCE 1972

3.
E

vi
.E 2 -
E
m
.-
C

D -
W
Iii
0
L

'A5 1
U
3
E
L
0
L
W
n
S
*o-
1.00

Fig. 4-Nucleatton
1.20
Supersaturation - 1.40
1

7-60

rate In the presence of seed crystals (second test)

Using the same technique and equipment, a series of experiments
has also been carried out in which nuclei counts were carried out by a
microscope drop count method, as the Coulter Counter was unavailable
for this work. Appendix I contains an outline of this method. In these
experiments only a very low crystal content was used. Table I11 shows
the result of one run with pure sucrose at 64' C and 600 micron seed
crystals. This result is plotted in Figure 4.
In this case there is an effect of supersaturation as required by the
nucleation model of equation (1). The equation of the form
B, = 9 x 109 x A x (SS - 1.205) for SS > 1.205
= 0 for SS < 1.205 . . . (5)
where B, is the nucleation rate in nuclei/(ml min) and A is the area of
seeds in square metreslml of massecuite, gives a good multiple correlation
coefficient (0.961) on this data. The effect of supersaturation is significant
on the nucleation rate at better than the 0.1 per cent level. The dependence
on area of crystal seed has, however, only been assumed as linear as
suggested by the nucleation theory of Bransom et al.
Comparison of these two nucleation rate expressions shows similar
predictions of rate are made for a mother liquor supersaturation of
1.405. Equation (5) predicts higher rates than equation (4) for super-
saturation values greater than this and lower rates for lower supersatura-
tion values. Further work into the dependence of the nucleation rate on
supersaturation is necessary. In addition, these two rate expressions
indicate threshold supersaturation limits of 1.18 and 1.205. The curve
of Figure 2 extrapolated to high purity and low crystal content gives a
value for the critical supersaturation of 1.16. The discrepancy in these
results indicates that further investigation is required.
1972 THIRTY-NINTH CONFERENCE 36 1

No experiments on nucleation rate have been carried out on syrups

of lower purity. From experience in industrial boiling nucleation rates
would be lower at lower purity levels.

Conclusion
Empirical relationships have been developed under simulated
factory conditions for the threshold supersaturation limit (equation (3))
and for the rate of nucleation once this limit has been exceeded (equations
(4) and (5)). These appear to be the only rate expressions presently
reported for the sucrose-water system. As yet, only high purity solutions
have been considered in the nucleation rate experiments.
These expressions should be used with reservation, since numerous
aspects are still to be investigated. The effect of temperature on the
threshold limit of supersaturation in particular requires further con-
sideration. Systematic experimental work is now also needed to establish
the influence of the supersaturation, temperature, crystal surface area,
time and purity of syrups on the rates of nucleation.

REFERENCES
Bransom, S. H., Brown, D. E. and Heeley, G. P. (1969). Crystall/zation Studies in Con-
tinuous Flow Crystallizers. Proc. Symposium on Industrial Crystallization, Inst.
Chem. Eng., London.
Clontz, N. A. and McCabe, W. C. (1969). Contact Nucleation of Magnesium Sulphate
Heptahydrate. Proc. A.1.Ch.E. 62nd Meeting, Washington, D.C.
Davies.' J. G. and Yearwood. R. D. E. (1944. T r o ~Aer. . London, 31, No. 3. 43. R e ~ o r t e d
by Honig, P. ~ r i n c i ~ l of
e s ~ G g a r~echnology.2, 137 (1959).
Hesp, A. and Dunton, N. (1963). Further Experiments in the Nucleation of Sugar Syrups.
Internal Communication, Sugar Research Institute.
Miers, H. A. and Isaac, F. (1906). J. Chem. Soc., 89, 413 (1906).
Ostwald, W. (1903). Lehrbuch Der Allgemeinen Chemie, Engelmann, Leipzig, Germany.
Penklis, P. and Wright, P. G. (1963). Nucleation in Sugar Boiling. Proc. Qd. Soc. Sug. Cane
Technol. 30: 177.
Powers, H. E. C, (1963). Nucleation and Early Crystal Growth. Ind. Chem., 351, thirtieth
Conf. (July 1963).
Strickland-Constable. R. F. (1968). Kinetics and Mechanism of Crvstallization. Academic
Press, N.Y.; (1968).
Van Hook, A. (1971). Nucleation. In publication, Sugar Technology Reviews, Elsevier.
Van Hook, A. and Bruno, A. J. (1949). Disc. Faraday Soc., 5, 113, (1949).
Wright, P. G . (1971). A Model of Industrial Sugar Crystallization. Thesis for Ph.D., Uni.
of Qd.

Appendix I
Coulter Counter Method
A sample of the material was taken and quickly poured through a
150 micron screen to remove all the large seed crystals. About five m1 of
the liquid was then taken and after appropriate dilution with the Coulter
electrolyte (50 per cent aqueous ethanol saturated with sucrose and
common salt) count runs were made on a model Coulter Counter using
a 280 micron orifice aperture and two m1 count volumes. The counts
were estimated for a particle size in excess of about five microns, by
choosing the appropriate aperture currents and threshold voltages. The
count for the original sample was calculated by multiplication by the
appropriate dilution factor.
 THIRTY-NINTH CONFERENCE 1972

Microscopic Drop Count Method

A small drop of the syrup containing the nuclei was taken onto a
weighed glass slide and covered by a cover glass. The slide was re-
weighed and the drop pressed into a near circular cross-section. Using a
projection microscope fitted with a screen grid, the number of crystals in
different square areas was counted manually and the count was multiplied
by a relative area factor to give the total count in the drop. From this
value and the mass of the drop the count per m1 or gram of mother liquid
could be estimated.