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Sugar crystallization in food products

a a
Richard W. Hartel & Arun V. Shastry
a
Department of Food Science, University of Wisconsin, Madison, WI, 53706

Version of record first published: 29 Sep 2009.

To cite this article: Richard W. Hartel & Arun V. Shastry (1991): Sugar crystallization in food products, Critical Reviews in Food
Science and Nutrition, 30:1, 49-112

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 Critical Reviews in Food Science and Nutrition, 1(1):49—112 (1991)

Sugar Crystallization in Food Products

Richard W. Hartel and Arun V. Shastry
Department of Food Science, University of Wisconsin, Madison, Wl 53706

ABSTRACT: A review of the recent literature on crystallization of the commercial sugars (fructose, glucose,
lactose, and sucrose) is presented. Topics include:

Nucleation — The formation of the crystalline phase from supersaturated solutions can occur by either a
spontaneous or a forced nucleation mechanism. Recent work on the mechanisms, kinetics, and impact of both
heterogeneous and secondary (contact) nucleation is discussed.
Growth — Recent studies on the mechanisms and kinetics of crystal growth will be reviewed. This discussion
Downloaded by [North Carolina State University] at 15:00 13 October 2012

includes work on the growth rate dispersion exhibited by these sugars.

Effects of impurities and additives — The presence of impurities and additives (including mixed sugar systems)
affects both the nucleation and growth steps. A discussion of the recent work in this area is included.
Emphasis is placed on the relationship between these crystallization phenomena and the solution structure
for comparison purposes.

KEY WORDS: crystallization, sugars, nucleation, crystal growth.

I. INTRODUCTION phenomena while discussing the present state of

The formation of the solid crystalline phase
of sugars plays an important role in many food
products. While providing a sweet sensation to
the food products, the sugars also act to provide
certain characteristic textural properties desirable
in the foods. Crystallization of the sugars is con-
trolled in such a way that either the sugar is
maintained in the solution phase or the formation
of the solid crystalline phase is controlled to give
the desired textural properties. Many food prod-
ucts containing sugars are formulated in such a
way that the formation of sugar crystals is re-
tarded. For example, the graining of hard candies
is considered a defect and is avoided by the candy
maker by appropriate formulation and processing
procedures. On the other hand, some food prod-
ucts rely on the presence of a crystalline phase
to impart the desired texture. For example, the
fine crystals present in a fondant icing determine,
to a large extent, the ability of the icing to retain
its shape in a baked good or in center-type candy.
An understanding of the principles that control
the prevention or formation of the crytalline sugar
phase is thus quite important in developing sat-
isfactory food products. This review will attempt
to present the basic principles of crystallization
knowledge of sugar crystallization as pertains to
food products. While sucrose and lactose will
dominate the discussion due to the relative abun-
dance of basic work on these sugars, other sug-
ars, including glucose and fructose, will be
reviewed as well.
The sugars of main importance to the food
industry come from a variety of sources. Sucrose,
probably still the sugar used most frequently in
food products, is manufactured from either the
sugar cane or the sugar beet. In the U.S., sugar
cane is grown in the warmer states (such as Flor-
ida, Louisiana, and Hawaii), while sugar beets
are grown in the cooler, northern states (such as
Colorado, Minnesota, and Michigan). The sugar
refining process, while slightly different for the
two plant sources, employs several functional
steps for removing the sucrose from the plant and
converting it to a pure substance. An extraction
step removes the sucrose from the plant to gen-
erate a dilute liquid with many impurities. These
impurities, typically dissolved minerals and or-
ganic matter, differ between beet and cane and,
thus, the resulting clarification steps differ
slightly. For example, one step in cane sugar
processing involves addition of lime and phos-
phoric acid to floculate the organic matter re-

1040-8398/91/$.50
© 1991 by CRC Press, Inc. 49
 maining after the extraction step.1 Once clarified
juice is made, a concentration step is necessary.
This is usually done by evaporation to generate
a concentrated sucrose syrup. A controlled crys-
tallization process in a vacuum evaporator pan is
then used to separate the sucrose from the so-
lution. Several crystallization steps are usually
necessary to fully exhaust the solution, since the
solubility of sucrose in water is quite high. Cen-
trifuges are then used to separate the crystals from
the mother liquor, after which the crystals are
dried to make a powder. The solution remaining
from the last crystallization step contains a small
amount of sucrose and is highly concentrated in
the impurities present in the beet or cane source.
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This is molasses and will be significantly differ-
ent between the cane and beet processes.
A wide variety of crystalline sucrose products
are available from the refiners, with differences
based mainly on particle size. These range from
fondant icing sugar up to the large-particle-size
granulated sugar. Liquid sugar is also available
for those products that do not require the crys-
talline form. Pure crystalline sucrose should al-
ways be the same regardless of plant source, since
the molecular structure of the sucrose crystal is
determined by physical constraints. The sucrose
obtained from the normal refining process, how-
ever, is never totally pure since some of the mother
liquor remains on the crystals during centrifu-
gation and, thus, some of the impurities of the
solution are present in the dried sucrose product.
In addition, trace amounts of impurities are in-
corporated into the crystal lattice to differing de-
grees, depending on the crystallization process.2
The small amount of impurities in the dried prod-
uct will be different, depending on the plant
source. Therefore, some small differences be-
tween beet and cane sugar may be noticed in
processes that are sensitive to small levels of
impurities present during processing. Since these
impurities may play a large role in the crystal-
lization processes, these differences may become
quite important in controlling the formation of
sugar crystals in a food product.
The milk sugar, lactose, is generally refined ,
in a similar manner, although other techniques
are available.3-4 During the cheese-making pro-
cess, the proteins and fats in milk are separated
from most of the sugars, minerals, and water.
This is the whey that is separated from the cheese
50
curd. The whey contains the majority of the lac-
tose present in the initial milk. Lactose is then
refined by a crystallization process from the whey.
Some clarification processes may be utilized prior
to concentration. For example, whey proteins may
be removed by some method (ultrafiltration, ad-
sorption, etc.) and some of the minerals may also
be removed (ion exchange, dialysis, etc.). The
clarified whey is then concentrated in evaporators
prior to the crystallization step. The crystalliza-
tion is usually performed by a slow batch-cooling
process to form lactose crystals, which are then
centrifuged and dried to generate a dried powder
product similar to refined sucrose. Several var-
iations of refined lactose can be obtained, mostly
dependent on the level of purity of the dried prod-
uct. Edible-grade lactose contains a significant
level of nonlactose materials, as opposed to the
purer pharmaceutical grade.
Glucose and fructose occur naturally in many
plant products; however, they are not present in
any one product at a high enough level to warrant
refining the sugar directly from the source. In-
stead, these sugars are generally manufactured
through some starch-processing procedures. In
general, refined glucose and fructose are manu-
factured through the corn syrup process. That is,
the corn syrup process is modified to create a
high level of glucose or fructose in the syrup.
The sugar is then crystallized from this high-
concentration syrup in some refining process.
Dean and Gottfried5 detail the historical per-
spective on the manufacture of purified glucose
(dextrose) from a variety of sources.
There are a wide number of food products
that rely on the presence of sugars for organo-
leptic and textural characteristics. As mentioned
above, the presence of sugar crystals may be
either desirable or impart a negative characteristic
to the product: An understanding of the phenom-
ena involved in sugar crystal formation and growth
is important to the optimal development of these
products and the processes through which they
are manufactured. Sugars are present in countless
food products, ranging from naturally occurring
products, such as honey and maple syrup, to for-
mulated foods, including jams and jellies as well
as most confectionery products. Everyone is fa-
miliar with the formation of sugar crystals in
honey or maple syrup caused by prolonged stor-
age under conditions that permit crystallization
 processes. In these products, the syrups can sim-
ply be heated to redissolve the sugars and yield
the original product. In other products, such as
hard candies or ice cream, the formation of the
crystalline phase causes a defect that cannot be
remedied once the product leaves the manufac-
turing plant. In a hard candy, the sugars are pres-
ent in a noncrystalline solid phase (the amorphous
state), which has a tendency to crystallize or grain
under certain conditions of high moisture and
temperature. Proper product formulation as well
as proper handling and storage are required to
prevent the unwanted crystalline phase from
forming. The crystalline phase has significantly
different textural properties in addition to being
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unable to adequately disperse any coloring dyes
used in the candy. Therefore, graining of the
candy is to be prevented. Ice cream contains a
supersaturated solution of lactose under freezer
conditions that, given the chance, will crystal-
lize, yielding a "sandy" defect in the ice cream.
Proper product formulation and processing con-
ditons, again, have helped to reduce the occur-
rence of this defect.
The purpose of this review is to present the
basic principles of crystallization processes of
importance to food products containing sugars.
Previous work on sugar crystallization will be
reviewed, with special emphasis on how this un-
derstanding can be used to assist in food product
and process development. This review is not in-
tended to be a complete summary of every piece
of work on sugar crystallization; rather, it is in-
tended to compile the major works on each of
the topics of crystallization. Previous work on
sucrose and lactose will be emphasized, although
data on glucose and fructose will be included
where available. Much of the work on crystal-
lization of these sugars has been by industrial
concerns and, thus, is not available through the
open literature. The review will be broken down
into the major classifications of crystallization
phenomena. These include (1) solution structure,
solubility, and metastability, (2) nucleation pro-
cesses, and (3) growth and ripening processes.
Since sugars are seldom, if ever, used alone in
food products, the interactions of other compo-
nents (other sugars, proteins, starches, salts, etc.)
will be emphasized. The related, and quite im-
portant, topic of the amorphous phase transitions
will not be covered in this review. This topic
merits a separate review.
II. SUGAR SOLUTIONS
In order to understand the principles of crys-
tallization processes, it is necessary to develop
some basic principles regarding solution structure
and phase equilibrium. It is the physicochemical
nature of the solution that drives the crystalli-
zation processes; thus, these properties must be
understood in order to fully understand the for-
mation and growth of crystals. The following
section reviews the present knowledge of sugar
solutions and their structure, behavior, and re-
lationships to crystallization processes. This re-
mains an active area of research due to the
difficulties in defining such complex molecular
interactions that occur in sugar solutions. An un-
derstanding of how these molecular interactions
affect the crystallization processes is just begin-
ning to be developed.
A. Solution Structure
The interaction between sugar and water
molecules in a sugar solution is quite complex
and the understanding of this structure is far from
complete. As the solutions become more con-
centrated in sugars, the interactions between in-
dividual sugar molecules become more
significant. A recent study on sucrose solutions
ranging from 5 to 80% (w/w) using nuclear mag-
netic resonance (NMR) spectroscopy demon-
strates the changes that occur to the relative
mobility of the sucrose molecules.6 NMR spec-
troscopy allows observation of the relaxation rates
of the water molecules in the sugar solution. These
rates are directly related to the mobility of the
water molecule in solution. In general, the higher
the relaxation rate, the less mobile the molecule.
Figure 1 shows the change of this relaxation time
with sucrose concentration. The linear portion up
to about 40% (w/w) was attributed to the effects
of the viscosity increase on the relaxation rate.
Above this concentration, a nonlinear curve was
seen, suggesting that increased hydrogen bond-
ing and/or sucrose-sucrose interactions were oc-
51
 12
o

o 10
o Relaxation rate of
o
T- dissolved
X 8 sucrose solution
CC
rs
c 6
o Relaxation rate for
a dissolved sucrose
x solution in the
•S
o 4 presence of crystals

o
«*-
Downloaded by [North Carolina State University] at 15:00 13 October 2012

w 2-
c
CD

cc
z i
10 20 30 40 50 60 70 80

Total Solids of sucrose dissolved in D2 0 (%)

FIGURE 1. Effect of dissolved and crystalline sucrose content in D 2 0 on the
17
O NMR transfer relaxation rate. (Adapted from Richardson, S. J., Baianu, I. C ,
and Steinberg, M. P., J. Food Sci., 52(3), 806, 1987.)

curring, so that the relaxation rate was increased.
At very high concentrations, above 67% (w/w)
sucrose at 25°C, these interactions are seen to
increase further. After crystallization of the sugar
has been completed, the relaxation rate of the
solution phase has decreased to the equilibrium
value for the saturation concentration, indicating
that equilibrium between phases has been
reached. 17O NMR mobilities of lactose solutions
and various sugar mixtures of lactose, fructose,
and sucrose have recently been reported.7
These measurements provide an indirect in-
dication of the solution structure and molecular
interactions. The specific interactions between
molecules (both inter- and intramolecular) must
be inferred from these spectroscopic measure-
ments. Various experimental techniques have
been applied to the study of sugar solution struc-
ture. A comprehensive review of the molecular
associations occurring in the sucrose-water sys-
tem has been presented by Allen and co-workers.8
As noted above, NMR spectroscopy has been
used to investigate solution structure in sugar-
water systems.6-7-912 Other analytical techniques
used for studying these molecular interactions
have included X-ray diffraction of the sugar so-
lution,13 infrared spectroscopy,914-15 differential
thermal analysis, 9 - 16 - 17 Raman spectros-
copy,1415-18 and dielectric measurements.17-19 De-
spite this wide array of experimental techniques
and measurements, confusion remains as to the
exact nature of the molecular interactions in sugar
solutions. At very high concentrations, in partic-
ular, the sucrose molecule interactions that lead
to the nucleation phenomenon are quite poorly
understood. Much additional work will be re-
quired to fully understand these molecular as-
sociations that lead to the nucleation event.
Molecular modeling presents another alter-
native for developing an understanding of the
molecular nature of sugar solutions. The ad-
vancement of high-speed supercomputers has al-
lowed mathematical modeling of the physical
behavior of molecular systems by numerically
integrating the equations of motion of each atom
in the molecular system. In this molecular dy-
namics modeling scheme, a system energy equa-
tion must be developed that accounts for the forces

52
 acting upon each of these atoms. A simulation
involves following the molecular changes that
result from the net effect of these atomic forces
over time. Molecular dynamics simulations have
been used to investigate the solution structure of
several sugars, including glucose20 and mal-
tose.21 These studies can assist in developing an
understanding of the molecular structure and hy-
dration of sugar molecules in aqueous solutions
and as supercomputers become larger and faster
allow the complex nature of these molecular in-
teractions to be completely delineated.
From a more physical standpoint, evidence
for the clustering of sugar molecules into nu-
cleation centers in concentrated solutions would
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be extremely important to observe. Density dif-
ferences arising from gravitational forces in a
long vertical column may provide this evidence,
although questions still remain. Researchers22
have demonstrated that the density of the sucrose
solution at the bottom of the column is greater
than the density at the top of the column under
certain pH conditions (either <4.2 or >9). These
density variations did not appear under normal
pH conditions in sucrose solutions made with
distilled water (pH of 5 to 6). Density variations
also were not observed in undersaturated solu-
tions. The observed density differences in con-
centrated solutions were attributed to clusters in
solution that had a bulk density less than the
liquid phase (flotation rather than sedimentation).
These clusters may be either sucrose molecule
clusters surrounded by a higher number of water
molecules than the bulk or simply a higher con-
centration of water molecules in a local region.
Considerable controversy remains as to the phys-
ical importance of these clusters and whether or
not they represent the precursors to crystal nuclei.
In summary, increased molecular interac-
tions are observed as the concentration of sugar
molecules in solution increases. However, the
exact nature of these interactions has not been
clearly defined. In addition, the relationship be-
tween these molecular interactions and the crys-
tallization of sugars (particularly in terms of nuclei
formation) has not been studied in sufficient detail.
B. Mutarotation
Sugars in an aqueous solution undergo a
number of interactions, with both water mole-
cules and other sugar molecules. They may take
a variety of forms in a solution, depending on
the type of sugar and the conditions of temper-
ature, concentration, and pH. These variations
may include the transformation between the a-
and (3-anomers of reducing sugars as well as be-
tween the various ring-shaped tautomers. Each
of the anomeric forms has its own inherent optical
rotation (or the ability to rotate polarized light),
so that differences in the optical rotation of the
solution may be observed under different con-
ditions. For example, when a-lactose monohy-
drate crystals are dissolved in water, the fresh
solution has the optical rotation for this anomer,
a specific optical rotation of 89.40.23 When 0-
lactose crystals are dissolved, the solution has a
specific optical rotation of 35.0°. Each of these
solutions, however, will change with time as the
mutarotation reaction proceeds, until an equilib-
rium between the a- and 3-forms is attained. At
this point, the specific optical rotation will be
between the two anomeric forms and will depend
on the final concentrations of the two forms in
solution. For lactose at 20°C, the final equilib-
rium optical rotation is 55.3°. This value corre-
sponds to relative percentages of a- and fi-lactose
of 37.3 and 62.7%, respectively.23 Therefore, the
equilibrium optical rotation of a sugar solution
is determined by the equilibrium ratio of the ex-
isting molecular forms. Pigman and Isbell24 give
the equilibrium composition of several reducing
sugars. For D-glucose at 20°C, the equilibrium
composition is nearly the same as that for lactose
(36.2% a- and 63.8% 0-glucose). These equi-
librium values depend on the conditions in so-
lution, including the temperature, concentration,
pH, and presence of foreign substances. An
expression relating the optical rotation of lactose,
a, in solution in the range of 0.5 to 95°C and 5
to 35 g anhydrous lactose per 100 ml solution is
given as25
a D = 55.23 - (0.01688)
C - (0.07283)(T-25) (1)
Here, a D is the specific optical rotation observed
using a sodium lamp (5893 A), C is the concen-
tration of lactose (grams of anhydrous lactose per
100 ml of solution), and T is the temperature
53
 (°C). A similar expression, applicable when a
mercury lamp (5461 A) is used for measuring
optical rotation, is given as23
aHg = 61.77 - (0.007)C - (0.076)(T-20) (2)
where C is the concentration in grams of lactose
monohydrate per 100 ml of solution. In general,
the effects of temperature and concentration are
quite small on the equilibrium mutarotation.
However, pH and the presence of foreign con-
stituents may have a significant effect on the
equilibrium solution structure in sugar
solutions.24-26-27
Lactose and glucose show relatively simple
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mutarotation behavior, since the pyranose form
of the sugar predominates in solution. More com-
plicated mutarotations exist for other sugars,24
including fructose, due to the presence of sub-
stantial amounts of the furanose form in solution.
The tautomeric equilibria of fructose and glucose
have been delineated using polarimetry, gas-liquid
chromatography, and NMR spectroscopy. 2830
Optical rotations and mutarotation constants for
a wide range of reducing sugars has been com-
piled by Pigman and Isbell.24
The mutarotation rate is dependent on the
solution conditions (concentration, temperature,
pH, etc.) and the presence of additional com-
ponents. The velocity constant for mutarotation
of lactose was determined as a function of pH
by Troy and Sharp.31 Their results show a rela-
tively constant rate between pH 2 and 7, with
dramatically increasing rates either above or be-
low these values. Herrington26 determined that
the mutarotation rate of lactose in solution was
enhanced by the presence of weak acids and bases
as well as lactate ions, but that the effects of salts
were not as clear. KCl was found to have a slight
retarding effect on the rate of mutarotation, al-
though other salts (such as ammonium chloride,
potassium acetate, and ammonium acetate) had
a catalytic effect. Herrington32 also showed that
several additives affected the equilibrium con-
centrations of the lactose forms in solution, re-
sulting in different equilibrium optical rotations.
Specifically, the effects of glycerol and various
salts on the equilibrium optical rotation in lactose
solutions were detailed. Mutarotation rates in salt
solutions were also studied by Haase and Nick-
54
erson.25 Their results verified previous studies in
that salts were seen to increase the rate of mu-
tarotation. A temperature effect was also ob-
served, where the activation energy for
mutarotation was found to be 16 to 17 kcal/mol.
Salts increased the rate, but did not affect the
activation energy of mutarotation. Patel and
Nickerson33 outlined the effects of sucrose on the
mutarotation rate in the presence of various salts.
Sucrose alone significantly decreased the rate
constant for mutarotation. Whey salts were found
to catalyze the mutarotation velocity; however,
whey salts in the presence of sucrose resulted in
mutarotation velocities similar to those in dis-
tilled water.
C. Phase Diagrams
Phase diagrams delineate the different solid
and liquid phases that occur in equilibrium sugar
solutions. Sucrose, being a nonreducing sugar
that shows a relatively simple solution structure,
takes only one form in solution, and the phase
diagram shows a simple distinction between the
solid and liquid phases. The phase diagram for
sucrose-water34 is shown in Figure 2. The ap-
proach to the eutectic point (the temperature and
concentration at which a solid water-sucrose so-
lution is formed) is somewhat misleading in these
data. Although sucrose should hypothetically
show a eutectic point, crystallization of sucrose
is dramatically hindered at the viscosities asso-
ciated with these low temperatures and the so-
lution becomes amorphous. Therefore, the actual
eutectic point has not been well defined.
Slightly more complicated is the lactose sys-
tem, which can crystallize in either the a-mono-
hydrate or 3-anhydrous form and exists in solution
as an equilibrium mixture of the anomeric forms.
The equilibrium solid phase depends on the tem-
perature and concentration of the solution. Below
93°C, lactose crystallizes in the a-lactose mono-
hydrate form, meaning that the crystal lattice
structure incorporates one water molecule with
every lactose molecule. Above this temperature,
the 3-lactose (anhydrous) form is crystallized un-
der equilibrium conditions. Under other condi-
tions, an anhydrous form of a-lactose can be
created that can exist as either an unstable or a
 o
o

¥
2
Q.
Downloaded by [North Carolina State University] at 15:00 13 October 2012

-50

Composition (% sucrose by weight)

FIGURE 2. Sucrose-water phase diagram. (Adapted from Young, F. E.

and Jones, F. T., J. Phys. Chem., 53, 1334, 1949; Pancoast, H. M. and
Junk, W. R., Handbook of Sugars, Vol. 2, AVI Publishing, Westport, CT,
1980, 264.)

stable form, depending on the conditions of
formation.
The phase diagrams for glucose 35 and
fructose36 are even more complicated. These are
shown in Figures 3 and 4, respectively. Several
hydrated forms of a-D-glucose and a-D-fructose
crystals exist as well as the p-anhydrous form.
Oftentimes, other forms of sugars may be
crystallized under unusual operating conditions.
For example, anhydrous forms of lactose, which
do not crystallize directly out of solution, can be
made by special processing of the monohydrate.23
If a-lactose monohydrate crystals are heated above
100°C under controlled pressures to drive off the
water of hydration, this anhydrous form can be
produced in one of two varieties. If the heating
occurs under vacuum, an unstable form is created
that has the same crystalline properties as the
monohydrate without the water. This unstable
form is quite hygroscopic and will pick up mois-
ture readily from normal, ambient air and return
to the hydrate crystalline form. A stable form of
anhydrous cx-lactose may be made by heating
under controlled relative humidity conditions so
that moisture equilibration may take place. This
stable anhydrous form is not hygroscopic and will
remain in the anhydrous form under normal air
conditions. When this stable anhydrous form is
redissolved in water, a concentrated a-lactose
solution is created with very little P-lactose pres-
ent, at least initially. This stable anhydrous form
has a higher solubility than a-lactose monohy-
drate, but is still lower than that of p-lactose.
Solutions made from the anhydrous form are very
Unstable and a-lactose monohydrate readily crys-
tallizes. Van Kreveld37 has used this unique prop-
erty to study the growth of a-lactose monohydrate
from solutions with very low levels of p-lactose.
The anhydrous forms can also be made using
alcohol to dry the monohydrate.23
D. Solubility
The chemical potential difference between a
sugar solution (liquid phase) and a large sugar

55
 60
40
20
o
o
o a-D-Glucose
3 Monohydrate
2
0) 0 /
Q.
—iP^
Downloaded by [North Carolina State University] at 15:00 13 October 2012
ice
•20
•40
' 1
20
Composition (% D-glucose by weight)
FIGURE 3. D-Glucose-water phase diagram. (Adapted from Young, F. E. and
Jones, F. T., J. Phys. Chem., 53, 1334, 1949.)
crystal (solid phase) is zero when the two phases
are in equilibrium. This point is defined as the
solubility point, and the concentration of the sugar
in solution at this point is defined as the solubility
concentration. Solutions with sugar contents be-
low this concentration are undersaturated and will
allow further dissolution of sugar crystals. So-
lutions with sugar contents higher than the sol-
ubility concentration are called supersaturated
solutions. Any crystals present in a supersatur-
ated solution will not dissolve, but, rather, will
grow larger as the solution attempts to approach
its equilibrium condition. Supersaturated solu-
tions are necessary for the crystallization pro-
cesses of nucleation and growth.
The solubility concentration varies as the
temperature of the solution varies. Sugars gen-
erally demonstrate a normal solubility curve, that
is, the solubility concentration increases with in-
creasing temperature. Figure 5 shows the solu-
bility curves for pure sucrose, lactose, glucose,
56
Anhydrous /I I
a-D-Glucose. / I /
/ /
Anhydrous ^ s .
p-D-Glucose N.
' 1 ' l
40 60 80
and fructose as well as invert sugar (an equimolar
mix of glucose and fructose) over a wide range
of temperatures of interest to the food proces-
sor.38 One can see that fructose has an extremely
high solubility, in excess of 80% (w/w), while
lactose exhibits the lowest solubility of these sug-
ars. The discontinuities in the solubility curves
for the nonreducing sugars arise due to the oc-
currence of various forms of the sugars occurring
at different conditions. For example, below 93°C,
a-lactose is the least soluble component and the
solubility curve gives the a-lactose concentration
at equilibrium. Above 93°C, however, 3-lactose
is the least soluble and the solubility curve re-
flects the concentration of this different
component.
The curves in Figure 5 show the total solu-
bility of the least soluble component. However,
each of the individual constituent anomers in so-
lution also has its own solubility. For example,
at 15°C a-lactose has a solubility concentration
 40

20

B-D-fructose
p Anhydrous
dihydrate
B-D-
fructose
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B-D-fructose
hemihydrate

-40
i
20 40 60 80 100

Composition ( % D-fructose by weight)

FIGURE 4. D-Fructose-water phase diagram. (Adapted from Young, F. E.,
Jones, F. T., and Lewis, H. J., J. Phys. Chem., 56,1093,1952.)

of about 7%, while B-lactose has a solubility
concentration of about 50%. 39 The final total sol-
ubility of lactose is about 15%, between the two
solubility values of the different anomers. Visser
et al.4 give an expression that relates the solubility
of total lactose to the temperature and show a
graph of the solubility of both a- and B-lactose
with changing temperature up to 90°C. This is
shown in Figure 6.40 This type of information
can also be obtained from the phase diagrams
shown previously.
Sugars are only very slightly soluble in
alcohols41 and some work has been done in crys-
tallizing sugars out of aqueous solutions through
the addition of alcohols.42 Domovs and Freund43
discuss the solubility of lactose in methanolic
calcium chloride solutions. Lactose is insoluble
in pure methanol.41 However, with the addition
of calcium chloride, a soluble complex is formed
such that the solubility levels can become sig-
nificant. Domovs and Freund43 also discuss the
solubilities of other sugars (glucose, fructose, etc.)
in methanolic calcium chloride. Different crystal
forms can be obtained through crystallization from
alcoholic media. These can range from the an-
hydrous form of a-lactose to crystalline mixtures
with varying a:P ratios.44
E. Metastability
When a supersaturated sugar solution is cre-
ated, a driving force exists for the formation of
the crystalline phase. However, even though a
sugar solution is supersaturated, it generally will
not crystallize until the driving force exceeds some
critical value. This critical supersaturation is re-
lated to the energy requirements for formation of
the solid phase, or the energy barrier to nuclea-
tion. The region of concentrations between the
saturation concentration and this critical concen-
tration is called the metastable region of super-
saturation. This region varies with such
parameters as temperature, agitation rate, and,
of course, level of additives or impurities. Each

57
 Fructose-^^

80 -

O)

i 60 -
" / /
\ / \
\S Glucose /
40 •
' Invert /
o
u \
sugar /
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CO Lactose
20 -

n
i i i i i i i
i • i
25 50 75 100 125 150

Temperature ( ° C )

FIGURE 5. Solubility of fructose, glucose, invert sugar, lactose, and su-

crose in water. (Adapted from Pancoast, H. M. and Junk, W. R., Handbook
of Sugars, Vol. 2, AVI Publishing, Westport, CT, 1980, 264.)

of these parameters influences the energy barrier
to the formation of the solid phase.
A supersolubility diagram is generally em-
ployed to demonstrate the region of metastable
supersaturations. Typical curves for sucrose and
lactose are shown in Figures 7 and 8, respec-
tively.45-46 These figures show several curves that
are related to the types of nucleation mechanisms
that can occur. The supersolubility curve, at higher
supersaturations, represents the boundary at which
spontaneous nucleation will occur. That is, above
this value of supersaturation, nuclei will form
spontaneously by some heterogeneous mecha-
nism. In a narrower region of supersaturation
conditions at lower concentrations, nucleation will
only occur when existing seed crystals are pres-
ent. This is commonly called secondary, or
forced, nucleation. At even lower supersatura-
tions, nucleation will not occur under any con-
ditions; however, existing seed crystals will still
grow.
The concentration boundaries for these re-
gions are not clearly defined and will vary with
changes in such parameters as agitation rate and
additives. For this reason, the values for the met-
astable range reported in the literature are quite
variable. The typical curve for sucrose metasta-
bility shown in Figure 7 was developed for stag-
nant solutions. Under agitated conditions, the
critical supersaturation for nucleation may be
lowered.47 This will be discussed further in a
subsequent section.
•The metastability of sucrose, glucose, and
fructose solutions has been studied in detail by
Vasatko and Smelik.48 Their experimental tech-
nique involved the visual determination of the
occurrence of nucleation as an unstirred sugar
solution was concentrated by evaporation at con-
stant temperature. The concentration at the point
of first observation of nuclei was measured as
the metastable limit. Figure 9 for sucrose shows
that a constant concentration limit for the meta-
stable region existed for temperatures less than
40°C. Above 40°C, the metastable concentration

58
 70
r
60
'3
50

Initial solubility
c 40
o of p-forrn^«--
2 30
4-1
C Final solubility ./
o
o
c 20 - at equilibrium/*^
o _
u
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0)
o 10 Initial solubility
o ^ of a-form
n
20 40 60 80 100

Temperature ( ° C )
FIGURE 6. Solubility of individual and combined anomers of lactose in
water. (Adapted from Jenness, R. and Patton, S., Principles of Dairy Chem-
istry, Robert E. Krieger, New York, 1967, 77.)

increased with temperature to maintain a rela-
tively constant supersaturation limit for metast-
ability. Vasatko and Smelik48 attributed this
behavior to a change in sucrose molecule hydra-
tion at about 40°C.
While the metastable region for commercial
glucose has been reported to be extremely small
by Dean and Gottfried,5 metastable zones for pure
glucose solutions that are significantly larger than
sucrose have been demonstrated experimentally
by Vasatako and Smelik48 and Horn.49 The de-
tailed experiments of Vastako and Smelik48 show
a significant metastable zone. Their results (Fig-
ure 10) for glucose show that the region of me-
tastability depended on the equilibrium form of
the glucose crystal that was present at a particular
temperature and concentration. At lower tem-
peratures and concentrations, a relatively wide
metastable region was observed for the glucose
hydrate forms. At higher temperatures and con-
centrations, the anhydrous glucose had a slightly
reduced zone of metastability. However, in gen-
eral, the metastable zone for glucose was similar
to that observed for sucrose. A narrow range of
metastable conditions was measured for fructose
between 0 and 60°C, as shown in Figure 11.
The exact metastable boundary for supersa-
turated sugar solutions remains an open question
due to the complexity of the nucleation process
and interactive effects of the numerous parame-
ters that impact the metastable condition. Future
research in this area is warranted to define the
effects of various parameters of commercial sig-
nificance on the nucleation event. The effects of
such parameters as agitation or energy input, tem-
perature, and types and concentrations of addi-
tives and impurities on the metastable limit would
be of great significance to the food processor with
strict requirements for crystallization control.
F. Supersaturation
A solution that contains more sugar mole-
cules than is thermodynamically allowed is said
to be supersaturated. Several methods are avail-
able for generating a supersaturated solution. The
first is by cooling an undersaturated solution. A

59
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Temperature ( ° C )
FIGURE 7. Approximate supersolubility curves for sucrose. (Adapted from
Van Hook, A., Principles of Sugar Technology. Crystallization, Honig, P.,
Ed., Elsevier, New York, 1959, 2,113.)

simple example of this is making rock candy on
a home stove. Sugar is added to a volume of
water that has been heated to some elevated tem-
perature. The amount of sugar added is less than
the saturation value at that temperature. Once all
the sugar has been dissolved, the solution is re-
moved from the heat and allowed to cool. As it
cools, the total amount of sugar that the solution
can hold decreases. If cooled far enough, the
concentration of the solution will pass over the
solubility line and the solution will be supersa-
turated. This is shown by line AB on Figure 12.
The degree of supersaturation depends on the
initial concentration and the extent of cooling.
Another means of generating supersaturation is
by removing some of the water to increase the
relative content of sugar molecules in solution.
This is done by evaporation and is shown as line
AC in Figure 12. This method is utilized by the
sugar refiners when making pure sugar. A third
method is to add a second solvent in which the
sugar is not soluble. Alcohols are convenient sol-
vents for sugars due to their low solubility values.
The solution mixture, following addition of sol-
vent, has a lower solubility for sugar than the
initial solution. Thus, the concentration, even
though diluted slightly by the solvent addition,
becomes supersaturated with respect to the sol-
vent mixture. This is shown in Figure 12 by the
line AD in combination with the new solubility
curve (dashed line). This last method of super-
saturating is not commonly used in the food in-
dustry, although some liqueurs and liqueur-type
confections may be prone to crystallization from
this mechanism.
Supersaturation levels may be expressed in
many ways. Thermodynamically, the driving
force for crystallization is the difference in chem-
ical potential between the solution phase and the
solid (crystalline) phase.50 At the equilibrium sol-
ubility concentration, these chemical potentials
are the same and the driving force (supersatur-
ation) is zero. The chemical potential can be re-
lated directly to the solution activity. The

60
Downloaded by [North Carolina State University] at 15:00 13 October 2012

20 40 60 80 100

Composition (% lactose by weight)

FIGURE 8. Metastable and solubility regions for lactose solution.
(Adapted from Hunziker, O. F. and Nissen, B. H., J. Dairy Sci., 10,
139, 1927.)

supersaturation driving force for growth of crys- However, neither the activities nor the activity
tals in a concentrated solution can then be ex- coefficients are generally known or measured for
pressed thermodynamically as sugar solutions, particularly those of commercial
importance at high concentrations. Van Hook51
<p = RT ln(a/aeq) (3) reviews the data for activity coefficients of con-
centrated sucrose solutions and applies these lim-
where <$> is the chemical potential difference (or ited data to crystal growth kinetics. His
"affinity of reaction"), R is the ideal gas con- conclusions emphasize the need for extending
stant, T is the absolute temperature, and a and these activity coefficient measurements into the
a^, are the activities of the supersaturated and supersaturated region. Since detailed measure-
saturated solutions at that temperature, respec- ments are unavailable, simplifying assumptions
tively. The activity can be expressed in terms of are generally made that allow the use of measured
mole fraction or molar (moles per liter of solu- concentrations as an indication of supersaturation
tion) or molal (moles per kilogram of water) con- values. The errors associated with these assump-
centration of solute in solution through the use tions may be large enough that conclusions re-
of activity coefficients for nonideal solutions. garding the mechanisms of crystallization
Thus, the thermodynamic driving force can be processes cannot be accurately made with con-
related to measured solution concentrations centration values. These errors are discussed in
through the use of activity coefficients. Alter- general terms by Mullin and Sohnel.50 Dunning52
natively, the driving force can be expressed di- reviews the errors associated with using concen-
rectly in terms of the activity of the solution. trations to replace activity coefficients to define

61
 90

Labile region
sz
•5
5 80 -\ Metastable
limit

c
o
o Undersaturated
70 - Metastable
o region
a> region
w
2
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o
3
Solubility limit

60 I i I
10 20 30 40 50 60 70 80 90
Temperature ( ° C )

FIGURE 9. Metastable and solubility limit for sucrose solution. (Adapted

from Vasatko, J. and Smelik, A., Zucker, 21(6), 144, 1968.)

90
Anhydrous form
metastable limit

80 Type II hydrate
metastable limit

"55 70- e I hydrate

metastable limit Anhydrous form
solubility limit
60.
c
*-»
Type II hydrate
o
u solubility limit
d>
W
o
u
_3 40.
O
Typee I hy
hydrate
30 solubility
bilit limit

0 10 20 3Q 40 50 60 70 80 90 100

Temperature ( ° C )

FIGURE 10. Metastable and solubility curves for o-glucose solution.

(Adapted from Vasatko, J. and Smelik, A., Zucker, 21(6), 144,1968.)

62
 100

x:
D)
I 90-
Metastabie region
limit

c
Si
o
u 80
« Saturation
o limit
u
3
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70 i i
10 20 30 40 50 60 70

Temperature (°C)

FIGURE 1 1 . Metastabie and solubility curves for D-fructose

solution. (Adapted from Vasatko, J. and Smelik, A., Zucker, 21 (6),
144, 1968.)

Supersaturated solution
for pure solvent system

o B
—— A
2
c Undersaturated
a> solution in pure
o i
c solvent and D1
o supersaturated
o
soiution in solvent
m mixture system

W Under saturated
solution
in pure solvent
and solvent
mixture system

Temperature

FIGURE 12. Supersaturation of sugar solution by evaporation, solution cool-

ing, and solvent addition. AB: supersaturation by solution cooling, AC: super-
saturation by evaporation of solvent, AD: supersaturation by addition of a second
solvent.

63
 TABLE 1
Sucrose Supersaturations Expressed in Different Units

a. T = 20°C, TS = 70%

Solution composition C C. AC

g Sucrose/kg water 2333.3000 2039.0000 294.3000 1.1443 0.1443

g Sucrose/kg solution 700.0000 670.9000 29.1000 1.0434 0.0434
g Sucrose/I solution 943.1000 891.7000 51.4000 1.0576 0.0576
Mol sucrose/I solution 2.7550 2.6073 0.1477 1.0566 0.0566
Mol fraction sucrose 0.1093 0.0969 0.0124 1.1277 0.1277

b. T = 20°C, TS = 80%

Solution composition C C. AC
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g Sucrose/kg water 4000.0000 2039.0000 1961.0000 1.9617 0.9617

g Sucrose/kg solution 800.0000 670.9000 129.1000 1.1924 0.1924
g Sucrose/solution 1129.4000 891.7000 237.7000 1.2666 0.2666
Mol sucrose/I solution 3.2990 2.6073 0.6917 1.2653 0.2653
Mol fraction sucrose 0.1738 0.0969 0.0769 1.7932 0.7932

c. T = 40°C, TS = 80%

Solution composition C C. AC

g Sucrose/kg water 4000.0000 2381.0000 1619.0000 1.6800 0.6800

g Sucrose/kg solution 800.0000 704.2000 95.8000 1.1360 0.1360
g Sucrose/I solution 1120.2400 963.5429 156.6971 1.1626 0.1626
Mol sucrose/I solution 3.2727 2.8174 0.4553 1.1616 0.1616
Mol fraction sucrose 0.1738 0.1114 0.0624 1.5607 0.5607

supersaturations of sucrose solutions. He rec-
ommends that mole fractions be used to represent
sucrose concentrations in order to minimize the
errors associated with the use of the nonther-
modynamic measure of concentration.
Despite the above concerns, the use of con-
centrations to calculate supersaturation is widely
practiced due to the relative simplicity of mea-
surement. While mechanistic understandings may
not be obtainable with these values, the use of
concentrations allows comparison of crystalli-
zation phenomena under varying conditions.
Several methods of comparing supersaturations
based on concentrations are used. These are (1)
the concentration difference, AC = C — Cs, (2)
the supersaturation ratio, S = C/Cs, and (3) the
relative supersaturation ratio, o- = AC/CS = S
— 1. Differences in these values are observed
when using different units for the solution con-
centration. That is, supersaturation values may
be expressed relative to concentrations based on
grams of sugar per 100 g solution or on grams
of sugar per 100 g water. When specifying a
supersaturation, it should be clear as to which
units are used as a basis. Table 1 compares these
supersaturation values at several concentrations
and temperatures of sucrose solutions. Any of
these forms will give a measure of the extent of
supersaturation, and the use of one over another
is dependent on the end use of the desired in-
formation as well as the available techniques for
concentration measurement.
In solutions of reducing sugars (lactose, glu-
cose, and fructose), the presence of the various
anomers may have some effect on the solubility
of each of the other anomers. For example, in
lactose, it has been determined that the presence
of p-lactose in solution has a negative effect on
the solubility of a-lactose.53 In order to accu-
rately express a supersaturation as the driving
force for a-lactose crystallization, the effects of
p-lactose on the solubility of a-lactose must be

64
 taken into account. Visser53 derived an expres-
sion for supersaturation of a-lactose that accounts
for this effect over a range of temperatures. This
was given as
S = C o (C p ,T)/C al (C p ,T)
= C/{CS - FKm (C - Cs)} (4)
where C a and C p are the concentrations of a- and
3-lactose, respectively, C as is the equilibrium
concentration of a-lactose, T is the temperature,
C is the total lactose concentration in solution,
Cs is the total equilibrium concentration of lactose
in solution at that temperature, Km is the ratio of
Downloaded by [North Carolina State University] at 15:00 13 October 2012
p/a in mutarotation equilibrium, and F is a tem-
perature-dependent factor relating the depression
of the solubility of a-lactose by fj-lactose. Visser53
developed a table giving values of F at various
temperatures based on the depression of lactose
solubility by sucrose, since the depression caused
by P-lactose could not be directly measured. This
correction was found to be fairly small over a
range of temperatures and supersaturations, so
that inaccuracies in F resulted in negligible (or
at least more tolerable) errors in determining su-
persaturation. This analysis points out the diffi-
culties in determining the actual driving force for
crystallization processes due to the confounding
effects of anomeric forms in solution.
G. Effects of Additives/Impurities on
Solubility
The presence of many additives of impor-
tance in foods will significantly alter the equilib-
rium solution conditions. In particular, the
solubility concentration may be dramatically
changed. Most components of foods have been
observed to have a negative effect on the equi-
librium solubility concentration of sugars. Using
sucrose as an example, the presence of such ma-
terials as corn syrup, invert sugar, gelatin, pro-
teins, starches, etc. generally causes a decrease
in the saturation concentration. Mullin54 sum-
marizes data showing how the saturation con-
centration of sucrose is altered in the presence of
various additives where the solubility coefficient
is the ratio of the saturation concentration of the
mixed system to that of pure sucrose at the same
conditions. It can be seen that the sugars gen-
erally cause a decrease in solubility, while some
salts may cause an initial increase in solubility.
In addition, food components such as proteins
and starches have been observed to decrease the
solubility of sucrose similarly to the other sugars.
These solubility changes are related to the mo-
lecular interactions between the solutes and the
water. It is thought that, in general, solutes that
form a hydrate in solution tend to lower the sol-
ubility of sucrose, whereas solutes that do not
form hydrates tend to increase the sucrose
solubility.
Figure 13 shows the change in sucrose sol-
ubility as the concentration of invert sugar in the
solution increases.38 It can be seen that the equi-
librium level of sucrose in solution decreases dra-
matically at all temperatures as the level of invert
sugar goes up (also see Reference 55). Fructose,
glucose, and corn syrup have a similar effect.
The solubility of glucose/sucrose mixtures is given
by Horn49 as a function of temperature. Raffi-
nose, a natural impurity present in sugar beets,
plays an important role in the refining of beet
sugar, since it has a large effect on sucrose crys-
tallization. The change in equilibrium solubility
of sucrose in the presence of raffinose has been
studied in some detail.55 Recently, Liang et al.56
have delineated this solubility depression effect
over a wide range of temperatures and concen-
trations. This solubility decrease might suggest
that the sucrose would nucleate more readily in
the presence of additives for a constant level of
sucrose in solution since the supersaturations are
higher under similar conditions. However, this
is not the case since there is an inhibition effect
on the formation of nuclei from these additives.
This will be discussed in greater detail in a later
section.
Smythe55 showed the effects of some salts
on the solubility of sucrose. Salts such as KC1
and urea were seen to increase the solubility of
sucrose at lower concentrations (<30 g salt per
100 g water). Na2HPO4 was seen to have no
effect, while CaCl2 initially decreased the solu-
bility at low concentrations (<20 g salt per 100
g water). At higher CaCl2 concentrations (>20
g salt per 100 g water), the sucrose solubility
increased again. The solubility of lactose in salt
65
 260

1
220 -
Temperature = 50°C
O)

so
3 180 -
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140
200 300 400

Invert sugar (g/100 g water)

FIGURE 13. Influence of invert sugar on the solubility of sucrose.

(Adapted from Pancoast, H. M. and Junk, W. Ft., Handbook of Sugars,
Vol. 2, AVI Publishing, Westport, CT, 1980, 264.)

solutions has been studied by Herrington.57 His
results show that lactose becomes more soluble
in the presence of calcium chloride and calcium
nitrate. The formation of a more soluble molec-
ular compound with calcium chloride (a-lactose-
calcium chloride-heptahydrate) was thought to be
responsible for this increased solubility.
As mentioned previously, anomeric forms of
reducing sugars may have a negative effect on
the solubility of another anomeric species in so-
lution. This has been demonstrated in the lactose
system by Visser,53 where P-lactose has been
shown to decrease the solubility of a-lactose in
solution. Other sugars have also been found to
decrease the solubility of lactose in solution.
Nickerson and Moore58 give solubility values for
lactose in the presence of sucrose between 25 and
85°C. These results are shown in Figure 14.
Talley and Hunter59 developed an expression re-
lating the solubility of lactose to the presence of
glucose and galactose at 25°C. Both sugars were
shown to significantly decrease the total solubil-
ity of lactose in solution. Bourne et al.60 studied
the solubility of mixtures of lactose and its hy-
drolysis products (glucose and galactose) over the
range of 45 to 95°C and demonstrated that the
hydrolysis products decreased the amount of lac-
tose that could be solubilized.
For solutions that were saturated with lac-
tose, the following equation was derived for re-
lating the effects of temperature and hydrolysis
product content on lactose solubility.60
Cs>La = (0.7)T-(0.311 +0.013T)CGa (5)
Here, concentrations are in weight percent, T is
in °C, and it is understood that glucose and gal-
actose concentrations are equal in the hydrolyzed
solution.
One final point to be made concerning sugar
mixtures is the maximum total solids level that
can be attained from solution mixtures. Figure
15 shows the total solids level for the most sol-
uble mixture of sucrose and invert sugar.38 The
concentration of this mixture exceeds the indi-
vidual concentrations of either sucrose or invert

66
Downloaded by [North Carolina State University] at 15:00 13 October 2012

20 40 60
Sucrose ( g / 1 0 0 g w a t e r )

FIGURE 14. Influence of sucrose on the solubility of lactose. (Adapted

from Nickerson, T. A. and Moore, E. E., J. Food Sci., 37, 60, 1972.)

90

— 80 -
D)

1
70 -

o
o
n
3
60 -

50
10 20 30

Temperature (°C)
FIGURE 15. Total solids of most soluble mixtures of sucrose-invert
mixtures. (Adapted from Pancoast, H. M. and Junk, W. R., Handbook of
Sugars, Vol. 2, AVI Publishing, Westport, CT, 1980, 264.)

67
 sugar at these conditions, with a total solids level
greater than 76% under normal operating tem-
peratures. This high level of sugar in solution
may lower the water activity enough to stabilize
the solution to microbial growth. This is critical
to the stable storage of many food products and
contributes to the importance of sugar mixtures
in the food industry.
The solubility of sugars in solvents other than
water has been studied in some detail. Sucrose
is only slightly soluble in alcohol.41 Thus, when
alcohols are added to aqueous sucrose solutions,
the mixture has an overall solubility much lower
than the original aqueous solution and the solu-
tion is easily supersaturated. Numerous studies
Downloaded by [North Carolina State University] at 15:00 13 October 2012
have investigated the effects of alcohols on the
crystallization parameters for sugars.42-44-61-63
III. NUCLEATION
Nucleation is the formation of a solid crys-
talline phase from a supersaturated sugar solu-
tion. Crystal nuclei are formed when sufficient
energy is available for formation of the solid phase
from the solution structure at a given concentra-
tion and temperature. In food products containing
high concentrations of sugars, this energy barrier
to nucleation may be easily overcome and the
formation of sugar crystals may occur. Under-
standing the mechanisms of this phenomenon and
the parameters that influence the nucleation step
is crucial to the control of the texture of the final
product. In some cases, crystal formation is de-
sired, while in other food products, the product
is considered defective when crystal nucleation
takes place. This section will review the basic
mechanisms of sugar nucleation and discuss the
effects of the important parameters on this event.
A. General Nucleation Theory
A typical classification of crystal nucleation
mechanisms is shown in Figure 16. These mech-
anisms are described in great detail in reference
books on crystallization processes. 546466 A brief
description of these processes will be given here.
Nucleation mechanisms may be divided into two
broad categories. Primary nucleation mecha-
68
nisms are those in which nuclei are formed in
systems that do not contain crystalline centers of
the crystallizing material. The primary nucleation
processes require an energy barrier associated with
the formation of the new nucleus to be overcome.
This is the energy required to form the crystal
surface and the crystal mass. Thermal fluctua-
tions or mechanical agitation can cause local en-
ergy levels of sufficient energy to promote
nucleation. The phenomenon of secondary nu-
cleation is different in that the presence of an
existing crystal surface is required for generation
of nuclei.
1. Primary Nucleation
Homogeneous nucleation is the classic pro-
cess of particle formation described by a molec-
ular accretion mechanism. That is, molecular
collisions lead to the creation of clusters of mol-
ecules that become large enough to exceed the
energy barrier to nucleation and become stable.
It is thought that individual molecules continually
collide with each other and with other clusters in
the solution. At high solution energy levels (su-
persaturations), accretion of molecules is favored
over dissociation (caused by convective forces
and molecular motion) and the clusters build to
a sufficient size to become stable at the existing
supersaturation. There is a certain probability,
depending on solute molecule concentration and
solution energy, that some of the clusters will
reach a size greater than the critical nucleus size.
A cluster with a size less than the critical size is
more likely to break up, whereas, a cluster of
greater size is more likely to grow and remain a
stable nucleus. The energy barrier required for
the nucleation process has been estimated by clas-
sic nucleation theories developed by accounting
for the surface and volume energy terms. Mul-
lin,54 Van Hook,64 and Zettlemoyer65 give ex-
cellent reviews of this topic, including the
historical developments of the theories.
The following theoretical development for
homogeneous nucleation is based on the conden-
sation of droplets from the vapor phase. This
theory is generally extrapolated to apply to the
nucleation of crystals from solutions. The free
energy for formation of the crystal surface is po-

PRIMARY
-
NUCLEATION
Downloaded by [North Carolina State University] at 15:00 13 October 2012
SECONDARY
FIGURE 16. Classification of crystal nucleation mechanisms.
sitive.and proportional to the surface area (size
squared) and interfacial tension of the nuclei,
while the free energy associated with the volume
formation is negative (latent heat generation) and
proportional to the volume (size cubed). The net
free-energy change during the nucleation process
is the sum of these terms where the surface term
dominates at small size and the volume term
dominates at larger nuclei sizes. This yields a
critical nucleus size at which the free-energy bar-
rier is a maximum (as shown in Figure 17). Nu-
clei above this critical size are more likely to
grow and become stable, while clusters below
this size are unstable and are more likely to dis-
sociate. Classical homogeneous nucleation the-
ory allows the calculation of this critical size for
spherical nuclei.54-64 It is given as
rc = 2asv/[kT(ln S)] (6)
where crs is the interfacial energy, v is the mo-
lecular volume, k is Boltzman's constant, T is
the absolute temperature, and S is the supersa-
HOMOGENEOUS
1 HETEROGENEOUS
INITIAL
BREEDING
NEEDLE
BREEDING
FLUID
SHEAR
CONTACT
NUCLEATION
turation ratio based on the appropriate concen-
tration units. The critical free energy, AGcrit,
required for nuclei formation at a given temper-
ature and concentration is found as
, = 16TTo^v2/{3[kT(ln S)]2} (7)
From this expression, the rate of homogeneous
nucleation, J, can be found using a simple Ar-
rhenius form of the rate equation. This is given
as
J = Aexp{-AG crit /kT}
= A e x p { - 16mxsV/[3k3T3(ln S)2]} (8)
where A is a frequency factor for nucleation. This
expression demonstrates that the temperature, su-
persaturation, and interfacial tension are the main
variables that influence the rate of homogeneous
nucleation in a given system. As the temperature
goes up, for a given supersaturation, the nuclea-
tion rate will also go up. The effect of supersa-
turation on the rate of nucleation is quite dramatic,
69

+ ve
o '
A yS^
I 0
0>
Volume excess
Downloaded by [North Carolina State University] at 15:00 13 October 2012
free energy, A C^
- ve
0 Critical nucleus radius, r.
Size of nucleus, r
FIGURE 17. Gibbs free energy as a function of the nucleus size.
as represented by Figure 18. The rate of nuclea-
tion is quite low until some critical value of nu-
cleation is attained, at which time it becomes
quite rapid and nucleation occurs almost spon-
taneously. Mullin54 has calculated the time re-
quired for spontaneous homogeneous nucleation
of liquid droplets in supercooled water vapor. A
time of 1000 years is required for nucleation at
S = 3.0, while a time of 0.1 s is calculated when
S = 4.0. The critical nucleation point, thus, is
slightly less than S = 4.0, although there is a
finite probability that nucleation will take place
at lower supersaturations.
For viscous systems, such as sugar syrups,
organic acids, or melts, Equation 8 has been em-
pirically modified to account for mass transfer
effects.67 A modification of the classic homo-
geneous nucleation equation of the form given
below is normally employed.
J = A'exp
{ - 16iTo^v2/[3k3T3(ln S)2] + AGv/kT} (9)
Here, AGV' is the activation energy for molecular
motion between the cluster and the bulk solution
70
/Surface excess
/ free energy, A G s
r
Free energy of
formation, A G
j <
and represents the energy barrier to nucleation
based on molecular motion or viscosity limita-
tions. Nucleation is inhibited due to viscosity
limitations at high concentrations in sugar solu-
tions. These high concentrations and low nu-
cleation rates lead to the formation of the
amorphous phase.
The applicability of the theoretical devel-
opment leading to Equation 9 may be questioned
due to the large number of assumptions and ex-
trapolations that must be made to apply the theory
to crystallization from solution. In particular, what
is the definition of an interfacial tension for a
small cluster of molecules may be questioned.
That is, how does one define the interfacial ten-
sion of a cluster of molecules that may or may
not have a crystal lattice structure? At what point
in the molecular accretion process does the clus-
ter transform into a crystal lattice structure? Fur-
thermore, how does one define the molecular
accretion process for a system of molecules that
exhibits significant molecular interactions in the
fluid phase, as evidenced by the solution structure
work discussed previously? These questions and
others cause the classic homogeneous nucleation
 c
E
=«:
0)
ra
C
o
CO
o
3
Downloaded by [North Carolina State University] at 15:00 13 October 2012
0.0
1.0
Supersaturation, C / Cs
FIGURE 18. Primary nucleation rate as a function of solution supersaturation.
theory to be of limited value when investigating
crystal nucleation from solution. Modifications
of the basic theory to account for some of these
questions are discussed in Reference 65.
An empirical approach to nucleation theory
involves the use of an induction time period to
predict the onset of nucleation. Christiansen and
Nielsen68 related the time required for homoge-
neous nucleation, Th, to the solution concentra-
tion, C, as
xh = kC1 (10)
where p was considered to be the number of
molecules in a critical nucleus or "germ". The
lag time represents the time required for the for-
mation of stable nuclei. This model was used by
Christiansen and Nielsen68 to relate the incidence
of nucleation to the operating parameters, such
as concentration and temperature for the precip-
itation of sparingly soluble salts.
Nucleation by a strict homogeneous mech-
anism as described above rarely occurs in su-
persaturated sugar solutions due to the presence
of impurities that act as nucleation sites. Certain
impurities, such as dirt or dust particles, rough
or pitted container surfaces, etc., may catalyze
the formation of the crystal nucleus and allow
nucleation at much lower supersaturations than
are required for homogeneous nucleation. It is
nearly impossible to remove sufficient numbers
of these nuclei sites, even in careful laboratory
experiments, in order to study homogeneous nu-
cleation. Certainly, in any practical application
relating to sugar syrups, heterogeneous nuclea-
tion will be the main source of nuclei. Since
heterogeneous nucleation is the most important
mechanism of nucleation on many occasions in
sugar syrups, the number of nucleation centers
present will determine, to a large extent, the onset
of spontaneous nucleation. Syrups that have been
filtered to remove some of these impurities may
undergo nucleation at higher supersaturations than
less clean solutions.
A detailed understanding of what makes an
impurity active as a nucleation site for a particular
system is still quantitatively lacking. Some sub-
stances may act as nucleation promoters in one
crystal system and nucleation inhibitors in a dif-
ferent system. Qualitatively, the degree of lattice
similarity between the impurity and the crystal
system is thought to be important in determining
71
 the effectiveness of a nucleator. For example, the
match in lattice structure between ice and silver
iodide makes this an effective nucleator for water
vapor (as used for cloud seeding to induce rain-
fall). The interfacial energies between the crystal
and solution, crcl, between the foreign solid and
solution, CTS1, and between the crystal and the
foreign solid, o-cs, can be used to develop an
expression for modifying the critical energy for
nucleation based on the homogeneous nucleation
theory. That is,
crit = 9AG c r i t (11)
Downloaded by [North Carolina State University] at 15:00 13 October 2012
where AG'crit is the critical energy for hetero-
geneous nucleation and
<p = (2 + cos 0)(1 - cos 6)2/4 (12)
cos 8 = (CTS1 - o j / i p c (I 3 )
The closer the degree of matching between the
surface tension of the crystal and foreign solid,
the lower the energy barrier for nucleation. The
two extreme cases are (1) when 6 = 180°, there
is no wetting of the solid surface (2) when 0 =
0°, there is complete wetting. Case 1 indicates
no affinity between the foreign surface and the
crystalline structure, so that no nucleation occurs.
At the other extreme, case 2 indicates a complete
match, which occurs when the solution is seeded
with the crystals of the solute itself. The affinity
of any particular foreign surface lies somewhere
between these two extremes and determines the
ability of the foreign surface to promote heter-
ogeneous nucleation.
Catalysis of nucleation by foreign solids has
also been related to the lattice matching at the
crystal-solid interface.54 The extent of this match-
ing is related to the strain that would be induced
in a crystal formed with the same structure as the
nucleation site of the foreign object. The interface
is considered coherent when the crystal lattice
can accomodate this strain, and is considered in-
coherent when the strain is excessive to the point
that the crystal lattice cannot propogate due to
the lattice mismatch.
While the exact mechanisms of primary nu-
cleation in food products are generally unknown,
it is apparent that the presence of these hetero-
72
geneous nucleation sites, whether insoluble for-
eign matter or the surfaces of the holding vessel,
is the main cause of nucleation in most instances.
The variability of the nucleation event may be
related to the nucleating activity of the hetero-
geneous nucleation sites present during process-
ing. It is probably safe to say that conditions
under which nucleation is promoted sponta-
neously include either high supersaturations or a
high number of active sites, or both. Control of
these sites is important to the control of the nu-
cleation event. The exact relationship between
the nucleation process and the solution structure
at the point of nucleation is also poorly under-
stood. Much additional fundamental research in
this area will be necessary to fully understand
the molecular concepts underlying the nucleation
event.
a. Sucrose
Of all the sugars, sucrose has been the most
extensively studied with respect to primary nu-
cleation. However, questions still remain as to
the exact mechanism of the nucleation step as
well as to the kinetics of the formation process
under a variety of conditions.69 In addition, the
nucleation mechanisms and kinetics in commer-
cially applicable situations for food products are
still only poorly understood.
The studies on primary nucleation processes
in sucrose have generally involved either deter-
minations of the time required for the appearance
of nuclei under certain conditions or the visual
counting of the number of nuclei appearing after
a certain period of time at supersaturated con-
ditions. Typical nucleation experiments involv-
ing the formation of nuclei in increasingly small-
diameter droplets have allowed the observation
of homogeneous nucleation of sucrose solu-
tions.70 These experiments operate on the prin-
ciple that if a solution is divided finely enough
by separation into many small droplets, then a
number of droplets will be free of contaminant
nucleating particles and, thus, homogeneous nu-
cleation will be observed. From these studies as
well as from studies involving well-filtered or
cured sucrose solutions,45'71-72 it has been found
that homogeneous nucleation occurs at supersa-
 turation ratios (based on concentrations in grams
of sucrose per grams of water) in excess of 1.5
to 1.6. Below this value, supersaturated sucrose
solutions with no active nucleation centers are
relatively stable for long periods of time and no
nucleation will occur.
Under normal conditions in the laboratory or
plant, spontaneous nucleation of sucrose solu-
tions occurs at a supersaturation ratio (based on
grams of sucrose per grams of water) of between
1.2 and 1.3.45>7° This was seen in the superso-
lubility diagram shown in Figure 7. However,
kinetic theory69 as well as data presented by Dun-
ning and Shipman72 and Van Hook and Bruno71
demonstrate that this metastable limit is time de-
Downloaded by [North Carolina State University] at 15:00 13 October 2012
pendent, since supersaturated solutions of down
to 1.1 supersaturation ratio have been observed
to nucleate, given sufficient time (over 150 h).
Solutions prepared at a supersaturation ratio of
1.3 were seen to nucleate quite rapidly (on the
order of minutes rather than hours). An expo-
nential decrease in induction period prior to the
onset of nucleation was observed between these
supersaturation ratios. These results demonstrate
that the kinetic nature of the nucleation process
must be considered as well as the equilibrium
condition.
The results of Van Hook and co-workers, as
well as a number of Russian investigators,73 in-
dicate that the classic model of nucleation (Equa-
tion 8) describes the nature of the formation of
sucrose crystals by a primary nucleation process
at least qualitatively,73 and that the mechanism
is essentially a diffusion-controlled process. This
contention is supported by the apparent activation
energy for the nucleation process being approx-
imately the same as that for the viscosity and
diffusion of sucrose molecules as well as from
the profound influence of the solution viscosity
on the nucleation process. Equation 8 has been
used to estimate the number of sucrose molecules
in a critical nucleus as 80 to 100, with a critical
radius of 20 A.64 That is, the critical nucleus size
is reached (at 25°C) when between 80 and 100
sucrose molecules have accumulated (for a ho-
mogeneous nucleation mechanism). The inter-
facial tension value can also be approximated as
6 erg/cm2 for this process.70 Kharin et al.74 were
able to calculate the number of molecules in the
critical nucleus from their experimental data and
found the number to be in the range of 50 to 80
molecules, depending on the initial supersatur-
ation. The number of molecules in the critical
nucleus was higher at lower initial super-
saturations.
Van Hook73 also discusses heterogeneous nu-
cleation of sucrose solutions. His work, dis-
cussed previously, on homogeneous nucleation
of sucrose solutions was based on careful prep-
aration of the solutions to minimize potential for-
eign nucleators. This was done by either careful
filtering or centrifuging of the solutions to phys-
ically remove foreign material or by curing of
the solution prior to experimental observation of
nucleation behavior. Curing the solution in-
volved heating to a temperature at least 20°C
above the saturation temperature for 20 to 30
min. This process performs several functions,
including the dissolution of any fine crystalline
sucrose particles, the destruction of any ordering
of sucrose molecules within the solution, and the
possible thermal deactivation of any foreign par-
ticle nucleators. Without such careful solution
preparation, only heterogeneous nucleation could
be studied. In further experimental work, careful
studies on the nucleating ability of various for-
eign substances added to supersaturated sucrose
solutions, including mannite, lactose, glucose,
fructose, tartaric acid, calcium carbonate, and
lithium sulfate monohydrate crystals, resulted in
no enhancement of nucleation.73 That is, none of
the above-mentioned substances in their pure state
were capable of nucleating sucrose solutions from
the metastable supersaturation zone. Van Hook's
comments regarding nucleation of sucrose re-
main appropriate to this date: "These topics —
the structure of the crystal nucleus and hetero-
geneous nucleation of sucrose syrups — remain
virtually untouched domains for both theoretical
and practical investigation and are extremely
promising since heterogeneous theory avoids most
of the statistical difficulties encountered in ho-
mogeneous nucleation theory, and macroscopic
concepts may be employed since the particles
generally contain many, many crystals."73
The induction time for the onset of nucleation
of pure sucrose solutions has been correlated to
supersaturation by a number of researchers.
Kuijvenhoven75 found the following relationship
to apply
73
 Th = 170(S - I)-113 (14)
over the supersaturation ratio (based on grams
per 100 g water) range 1.1 < S < 1.6 for the
spontaneous formation of sucrose conglomerates.
Experimental data of Kharin et al., 74 evaluated
by Kuijvenhoven,75 resulted in the following
expression for the induction time for nucleation
as a function of the initial supersaturation
Th = 11.9(S - I)- 1 - 25 (15)
over the range 1 . 0 7 < S < 1 . 1 6 . These induction
times were based on visual observations of nuclei
formation and not corrected for the rate of growth
Downloaded by [North Carolina State University] at 15:00 13 October 2012
of the nuclei to visible sizes. Kuijvenhoven75 pro-
vides an excellent comparison of these equations.
The exponent of the supersaturation may be re-
lated to the number of molecules necessary to
form a stable nucleus, as mentioned previously.
However, this cannot be a direct relation as sug-
gested by Christiansen and Nielsen68 and de-
scribed above. Based on their theory (Equation
10), the number of molecules in a critical nucleus
would only be 2 to 3 rather than the 80 to 100
predicted by classic nucleation theory.64 Further
work is necessary to relate the induction time
required for nucleation to the theories presented
previously. Ideally, the effects of crystal growth
times on any nucleation induction time must also
be taken into account when deriving these
relationships.
b. Lactose
Herrington76 studied the time for supersatur-
ated lactose solutions to crystallize at various
temperatures and concentrations. These results
show that lactose can exist in the metastable state
over a wide range of conditions and that this
metastable state, again, represents a dynamic
equilibrium. That is, the time required for the
onset of nucleation was seen to decrease with
increasing concentration. However, as a solution
of lactose was supercooled, the rate of nuclei
formation was seen to pass through a maximum
(time required for nucleation passed through a
minimum). The effects of mass transfer or vis-
cosity limitations on molecular motion resulted
74
in a decrease in nucleation rate at higher con-
centrations and lower temperatures, as predicted
by Equation 9. These results are plotted in Figure
19. This effect can be seen at higher lactose lev-
els, 50 and 60 g lactose per 100 g water. At
higher temperatures (40 to 50°C), the time re-
quired for the onset of nucleation is long, indi-
cating the lower supersaturation and the presence
of the metastable region. At intermediate tem-
peratures (20 to 30°C), the induction time reaches
a minimum, while at lower temperatures (0 to
10°C), the induction time begins to increase again.
Therefore, at lower temperatures, mass transfer
is beginning to limit the onset of nucleation, as
predicted by Equation 9. At the lower lactose
concentrations (30 to 40 g lactose per 100 g water),
the solutions are metastable at all temperatures
if an induction time of 1 h is used to define
metastability. Even within the metastable zone,
however, significant differences in induction time
exist. This emphasizes the kinetic equilibrium
aspects of the metastability concept.
c. Glucose
The spontaneous nucleation behavior of glu-
cose monohydrate from solutions has been dis-
cussed by Horn.49 The supersolubility diagram
for glucose monohydrate was developed with su-
persaturation units given as grams of glucose per
100 g water. Here, the boundary for metastability
is given as somewhere between S = 1.7 and 2.6
over the temperature range from 0 to 90°F. These
results are in agreement with those of Vasatako
and Smelik,48 as shown in the previous section.
At supersaturations in this metastable range, nu-
cleation can only occur by a secondary nucleation
mechanism, whereas supersaturations of 4.0 are
required for spontaneous nucleation. This com-
pares to the value of supersaturation for spon-
taneous nucleation of sucrose based on these units
of 1.4. Obviously, glucose monohydrate can
withstand considerably higher supersaturations
before undergoing nucleation. Unpublished data
cited by Horn49 also demonstrate qualitatively the
dependence of nucleation on temperature (0 to
90°F) and supersaturation (up to S = 14.7 at
0°F). These results are shown graphically in Fig-
ure 20. As supersaturation increases, the extent
 1000

40 50

Temperature ( °C )
Downloaded by [North Carolina State University] at 15:00 13 October 2012

IH Lactose = 30g/100g water E2 Lactose = 50g/100g water

W Lactose = 40g/100g water S Lactose = 80g/100g water

FIGURE 19. Mass transfer limitation effects on the induction periods for nudeation
of lactose solutions. Note: Induction times over 1000 h indicate cases where no
crystals were observed after 3000 h. (Adapted from Herrington, B. L , J. Dairy Sci.,
17,501,1934.)

Temp= 0°F Temp=45°F

Temp=32°F Temp=70°F
Complete
crystallization
• Temp=90°F

c Moderate
.2 crystallization
to
"o

£ Slight
° crystallization
c
»

No
Crystallization

63.1 74.5 76.7 82.7 89.3

Glucose concentration (% by weight)

FIGURE 20. Extent of glucose solution nudeation rate with change in total
solids. (Adapted from Horn, H. E., Manuf. Confecl, June, 79,1977.)

75
 of nucleation initially increases. As supersatur-
ation is further increased, the effects of viscosity
(mass transfer) slow down the extent of nuclea-
tion until, at extremely high supersaturations, nu-
cleation is totally inhibited. This condition leads
to the formation of a glucose glass. The super-
saturation boundaries for these different mecha-
nisms of nucleation depend on the temperature
at which nucleation occurs.
d. Fructose
No specific data on the kinetics of fructose
primary nucleation are available in the literature.
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The specific boundaries for the metastable region
have been presented previously in Figure 11, 48
While it is apparent that considerable effort
has gone into the study of sugar crystal nuclea-
tion, particularly for sucrose, many questions re-
main as to the exact mechanism of nucleation
under a variety of conditions. For example, the
exact role of active heterogeneous nucleation
centers has not been completely detailed, al-
though this may help in understanding the spo-
radic nucleation behavior of commercial syrup
formulations. The exact mechanism by which
these nucleation centers act to promote crystal
formation remains in question. More impor-
tantly, the kinetics of these processes have only
been qualitatively understood under most con-
ditions and more sophisticated experimental tech-
niques for studying this complex phenomenon
must be developed. The effects of the isomers of
reducing sugars on the nucleation process has
also not been addressed in sufficient detail. In
summary, significant gaps in understanding exist
with respect to primary nucleation processes.
2. Secondary Nucleation
The process of nuclei formation due to the
presence of existing crystals is called secondary
nucleation. This may occur by several mecha-
nisms; however, these mechanisms are generally
related to the removal of some component of the
crystal or its associated structure by physical
means. For example, new nuclei may form from
existing crystals due to the growth of dendritic
76
structures on the surface, followed by subsequent
shearing off of these dendrites by fluid forces.
The dendrites will grow into nuclei if their size
is greater than the critical size for stable nuclei
under the bulk conditions. Alternatively, sec-
ondary nuclei can be generated due to collisions
between existing crystals and the other compo-
nents within the crystallizer (other crystals, walls
of the vessel, or any agitation device). The col-
lision energy causes either a small piece of the
crystal to be chipped away and distributed into
solution (a microattrition mechanism) or some
ordered layer associated with the growing crystal
to disperse an embryo of stable size into the so-
lution (adsorbtion layer disruption mechanism).
Generally, the above mechanisms only apply in
stirred suspension crystallizers, where a signifi-
cant contact energy or shear force may be im-
parted to the crystal. Secondary nucleation in
stagnant syrups has not been reported, nor would
it be expected. This mechanism of nucleation
generally becomes important when a suspension
of crystals is being agitated in a vessel or exten-
sive beating of a crystalline product occurs. The
formation of "false grain" in a sugar refiner's
pan is an excellent example of nucleation by a
contact mechanism. In this case, the refiner tries
to avoid secondary nucleation in order to main-
tain the integrity of the product crystal size dis-
tribution by maintaining a sufficiently low
supersaturation. Larson77 provides a review of
the secondary nucleation phenomenon.
• The kinetics of secondary nucleation are often
correlated with the important processing condi-
tions using an empirical power-law model, due
to the lack of any theoretical understanding.66
This model, for the nucleation rate, B°, given as
the number of particles produced per unit volume
per unit time (#/ml/min), is written as
B° = AsN exp{-E sN /RT}' (16)
where AsN is a frequency factor for secondary
nucleation, EsN is the activation energy for sec-
ondary nucleation, e is the power input into the
suspension (sometimes related by stirrer RPM),
M T is the suspension density (mass of crystals
present in suspension), and S is the supersatur-
ation ratio. The parameters AsN, EsN, 1, j , and q
are determined for a particular system by fitting
 the above equation to the experimental nucleation
rate data.
a. Sucrose
The occurrence of secondary nucleation or
"false grain" in the refining industry has been
known for many years. Powers78 gives a brief
review of the study of fluid movement around a
sugar crystal, which results in the formation of
secondary nuclei. A significant amount of work
on the secondary nucleation of sucrose has been
performed in recent years.4247-7989 This work has
involved studies of both suspension crystallizers
Downloaded by [North Carolina State University] at 15:00 13 October 2012
and single crystal contact experiments.
Secondary nucleation in suspension crystal-
lizers can potentially arise from the collisions
between sugar crystals and each other, the crys-
tallizer walls, or the stirring impeller. In addition,
fluid shear around a growing crystal has been
found to generate secondary nuclei. For sucrose,
these suspension studies have generally involved
determination of nucleation rates from experi-
mental crystal size distributions using the pop-
ulation balance technique. 66 This technique
requires experimental size-distribution measure-
ment followed by theoretical analysis of the con-
tinuity equation for particle size to determine the
nucleation rate representative for the average
product crystals. Further details of this technique
may be found in Randolph and Larson.66 In brief,
the theory predicts a semilogarithmic size distri-
bution when nucleation at zero size is considered
for an ideally mixed continuous crystallizer. That
is, the predicted exponential size distribution is
given as
n = n°exp(-L/GT) (17)
where n is the population density function and is
found from the experimental distribution, n° is
the population density function extrapolated to
zero size, L is the crystal size, G is the linear
crystal growth rate (|xm/min), and T is the av-
erage residence time within the crystallizer (min).
If the experimental size distribution fits this ex-
ponential model, the growth rate is determined
from the slope and the population density func-
tion at zero size is found from the intercept of a
straight line on a semilogarithmic plot of popu-
lation density vs. crystal size. The nucleation rate
for the suspension under the experimental con-
ditions is then found as
B° = n°G (18)
The nucleation rate at a variety of conditions is
found in this way to determine the nucleation
kinetics, which are then determined as given in
Equation 16. At times, a modified nucleation rate
expression is used where the nucleation rates are
correlated with the growth rate rather than with
the supersaturation. This expression is given as
B° = AsN (19)
Kuijvenhoven75 summarizes the kinetic work
available to date for secondary nucleation of su-
crose using this technique. From these results, it
is apparent that significant differences exist be-
tween experimental observations. Variations in
agitation rate or energy input may cause some of
these inconsistencies. The extent of nonlinearity
in the semilogarithmic population balance plot
may also contribute to these variations. Liang and
Hartel87 have recently addressed this problem and
concluded that disagreement with the exponential
distribution at the small sizes (less than 80 (un)
may cause differences in the kinetic expressions
obtained. Their final conclusion was that the pop-
ulation balance technique may not be sensitive
enough to determine the true kinetics and that
alternative experimental techniques must be
brought to bear on the problem of determining
secondary nucleation kinetics.
Secondary nucleation of sucrose crystals has
also been studied by observation of contacts be-
tween a large parent crystal and another surface.
Gwynn88 observed the nuclei generated from con-
tact of a large sucrose crystal with a brass rod
dropped from a height above the crystal. The
crystal was growing in a supersaturated solution
at a controlled temperature. The number of nuclei
formed for each contact was determined by
counting, using an automatic particle counter. A
piezoelectric crystal mounted beneath the sucrose
crystal was used to measure the energy of con-
tact. These results demonstrate that the number
of nuclei generated increased with increasing su-
77
 persaturation above some critical point and in-
creased with increasing contact energy. The
contact energies between sucrose crystals and the
stirring impeller in a suspension crystallizer were
determined in a similar way using a piezoelectric
element built into the impeller.75 The energies
determined in this way suggest that the actual
contacts in suspensions between crystals and im-
peller had very low energy levels and would not
be expected to generate large numbers of crystals.
Kuijvenhoven75 attributed the shearing as crystals
passed through a small gap between the impeller
and the crystal wall to be the main source of
nuclei from a secondary contact mechanism in
stirred tanks. Pot et al.89 concluded that attrition,
Downloaded by [North Carolina State University] at 15:00 13 October 2012
abrasion, or breakage of crystals were not im-
portant sources of contact nuclei in stirred sus-
pensions unless the clearance between the impeller
tip and the wall was small compared to the av-
erage crystal size. Their results also indicated that
secondary nuclei are formed predominately at the
surface of small crystals.
Single crystal contacts performed in a pho-
tomicroscopic cell under controlled temperature
conditions have shown that a simple sliding con-
tact between a large parent sucrose crystal and a
glass cover slip results in the generation of a large
number (hundreds) of contact nuclei.84-85 Al-
though the actual energy of this type of contact
has not been measured, it is likely to be quite
low compared to the contact energy of a direct
collision. That is, a low-energy sliding contact
results in a large number of contact nuclei being
generated. This may be attributed to the shearing
of a surface layer on the growing crystal resulting
in the dispersion of a large number of molecular
clusters into the bulk solution. At some critical
supersaturation, these clusters are stable and sur-
vive in the bulk solution. It is possible that this
type of contact exists in a suspension crystallizer
where the existing sucrose crystals slide along
the vessel walls for a period of time and generate
a number of contact nuclei. Further studies in
this area are necessary to verify the mechanism
for the generation of secondary nuclei under a
variety of conditions.
b. Lactose
Much less work has been done on lactose
78
nucleation compared to sucrose, particularly on
the mechanism of secondary nucleation. Griffiths
et al.90 and Shi et al.91 have studied the contin-
uous crystallization of lactose in a cooling crys-
tallizer using the population balance technique to
determine the nucleation kinetics. Again, there
are significant differences in these kinetic expres-
sions, although the bases for comparison for su-
persaturation are slightly different. Shi et al.91
incorporate a dependence of supersaturation on
the presence of p-lactose, so that some differ-
ences in kinetics may be expected. Liang et al.92
evaluate the effectiveness of using the population
balance technique for determining the secondary
nucleation kinetics of lactose and conclude that
this technique is not sensitive enough to deter-
mine the actual kinetics for this system. While
these expressions for secondary nucleation ki-
netics may be useful for process modeling and
design of continuous crystallizers, very little
meaningful kinetic mechanism information is ob-
tained.
Shi et al.93 have also studied the formation
of contact nuclei of lactose in the photomicros-
copic experiments described previously. Their
results demonstrate an abundance of nuclei being
generated by a low-energy sliding contact, re-
sulting in the formation of hundreds, sometimes
thousands, of secondary nuclei. In addition, the
critical supersaturation for the onset of secondary
nucleation was found to be quite low, in contrast
to existing information on the metastable region
of lactose supersaturation. In fact, conditions of
low supersaturations were found where contact
nuclei were generated, yet growth of these nuclei
was not observed. It is apparent that lactose be-
haves differently from sucrose with respect to
secondary nucleation behavior, although further
research will be necessary to clearly define the
secondary nucleation processes in both systems.
c. Glucose
The occurrence of secondary nucleation is
readily observed in glucose crystallization.49 A
recent patent94 involves the crystallization of a-
glucose monohydrate by continuous-cooling
crystallization, where nucleation and growth of
glucose crystals are maintained in the same ves-
 sel. According to data presented in the patent,
nucleation occurs by a secondary nucleation
mechanism, although no kinetic results are pre-
sented. Dean95 discusses the formation of an un-
usual form of glucose during secondary nucleation
under certain conditions. From this analysis, it
is postulated that an unstable form, thought to be
a hydrated form of p-glucose, results from sec-
ondary nucleation. This unstable form then is
transformed into small, thin crystals of the com-
mon form. Definitive X-ray diffraction experi-
ments were not performed.
Photomicroscopic observation of contact nu-
clei generated from a sliding contact of a parent
glucose crystal (a-anhydrous) has been per-
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formed by Elankovan and Berglund.96 Their re-
sults are similar to those found for sucrose and
lactose in that a gentle sliding contact resulted in
generation of significant numbers of contact nu-
clei. In these.experiments, contact nucleation was
studied over the range of 41 to 50°C with sub-
coolings ranging from 2 to 4°C. No results on
the kinetics of the nucleation process were ob-
tained from this study. Some interesting results
were obtained when the anhydrous parent crystal
was contacted at 41°C and a subcooling of 4°C.
Under these conditions, the presence of two dis-
tinct crystal forms was detected. These appeared
as prisms and needles. The nuclei formed from
this contact were analyzed using Raman spec-
troscopy, which determines the vibrational activ-
ity of the molecular structure. The prisms were
identified as pure a-glucose anhydrous, while the
needles were found to be primarily made up of
a-glucose monohydrate. Some other phase may
also have been present in these needles due to
the appearance of an additional vibration in the
Raman spectra. Elankovan and Berglund96 sug-
gest that this additional phase may be similar in
nature to the unstable form of glucose found by
Dean95 and described above. Further analysis of
this phenomenon is warranted. These contact nu-
cleation results provide an interesting basis for
determining the mechanism of contact nucleation
under these conditions. Since two different forms
of glucose crystal nuclei were created by con-
tacting an anhydrous glucose parent crystal, it is
unlikely that simple microattrition is the mech-
anism of contact nucleation. That is, breaking off
of small pieces of the parent crystal cannot ac-
count for the presence of the monohydrate needle-
shaped nuclei. Disruption of a semiordered sur-
face growth layer is the most likely mechanism,
although Elankovan and Berglund96 do not dis-
count the possibility of epitaxial growth of the
monohydrate phase on the anhydrous nuclei. The
mechanism of contact nucleation is, therefore,
still in question.
d. Fructose
Shiau and Berglund97 studied contact nu-
cleation of fructose using the photomicroscopic
observation technique described above. Similar
results were obtained in that fructose nuclei were
generated following a sliding contact between
parent crystal and a glass cover slip in a con-
trolled microscopic environment. A distribution
of sizes for these contact nuclei was observed
ranging from 1 to 2 |xm up to 25 to 30 ujtn. No
kinetic data for nucleation were determined in
these experiments.
B. Operating Parameter Effects on
Nucleation
There are many parameters that affect the rate
of nucleation in sugar syrups. These include the
supersaturation, temperature, rate of cooling,
viscosity, agitation rate or energy input, pH, and
the presence of additives of impurities. Control
of the factors that influence the rate and extent
of nucleation determine whether or not a given
syrup formulation nucleates as well as determin-
ing, to a large extent, the form of the product
crystal size distribution following a nucleation
event. Since the shape, average size, and distri-
bution of crystal sizes plays an important role in
food texture, controlling the rate and extent of
nucleation is quite important to the final product
quality.
1. Supersaturation
The effect of superannuation on nucleation
rate is defined in Equations 9 and 16 for primary
and secondary nucleation, respectively. For pri-
mary nucleation, as the supersaturation is in-
79
 creased due to concentration increases, the
nucleation rate initially increases sharply once the
critical supersaturation has been exceeded. This
critical supersaturation may be defined function-
ally as the boundary between the metastable and
labile zones. Below this critical supersaturation,
the solution is metastable and nucleation does not
occur. If the supersaturation is increased suffi-
ciently by increasing the concentration, eventu-
ally the viscous barrier to nucleation, in Equation
9, becomes dominant and the rate of nucleation
begins to decrease. This dependence on super-
saturation can be seen in Figures 19 and 20 for
lactose and glucose, respectively.
For secondary nucleation of sucrose, the de-
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pendence of nucleation rate on supersaturation
has been studied by Hartel47 and Kuijvenhoven,75
among others. Their results show that the sec-
ondary nucleation rate increases with increasing
supersaturation, although the exact dependence
differs between studies. Since the exact mecha-
nism of the formation of secondary nuclei is still
unclear, the dependence of the nucleation rate on
supersaturation must also remain empirical. In
similar experiments on the continuous crystalli-
zation of lactose, Shi et al.91 and Griffith et al.90
have found a corresponding dependence of sec-
ondary nucleation rate on supersaturation.
In the processing of foods containing high
levels of sugars, supersaturation plays a dominant
role in determining the extent of crystal forma-
tion. In general, as the supersaturation of sugar
in the product is increased, the greater the like-
lihood of nucleation occurring. This increased
extent and rate of nucleation occurs as the su-
persaturation is increased up to the optimal point
for nucleation at a given set of conditions. Once
this optimal nucleation point has been exceeded,
by too high a concentration or too low a tem-
perature, the nucleation rate will begin to de-
crease. This nucleation inhibition is due to the
increased resistance to mass transfer of sugar
molecules in the solution, resulting in a decreased
ability for the molecules to form into a crystal
lattice structure. As the supersaturation is in-
creased above these levels, nucleation will de-
crease to the point where, eventually, no
nucleation can occur. At this point, the sugar
product will form an amorphous solid structure
of varying stability dependent on the tempera-
80
ture, water content, and presence of other addi-
tives or impurities.
2. Temperature
The temperature of a sugar solution may af-
fect the rate of primary nucleation in several ways.
If a sugar solution of a certain concentration is
cooled to various temperatures and allowed to
equilibrate, nucleation will occur by a hetero-
geneous mechanism and the rate will be defined
by Equations 9 and 11, based on the existing
supersaturation. As the temperature is lowered,
the nucleation rate will increase since the super-
saturation has been increased (solubility value is
lowered). Lowering the temperature too far,
however, will result in a decrease in nucleation
due to the importance of the mass transfer term
in Equation 9. That is, the viscosity of the so-
lution will become large enough to significantly
impede the onset of nucleation and the rate will
decrease. Again, this can be seen from Figures
19 and 20 for lactose and glucose, respectively.
No consistent data of this sort are available in
the literature for sucrose.
If the effect of temperature on nucleation is
separated from the supersaturation effect, a
slightly different picture emerges. For a constant
level of supersaturation, Equation 9 would pre-
dict that the nucleation rate would increase as the
temperature was increased. Of course, this is lim-
ited in a practical sense by the level of super-
saturations that can be obtained at higher
temperatures. Nevertheless, the nucleation rate
will be increased at elevated temperatures for a
constant level of supersaturation. In heteroge-
neous nucleation of sucrose solutions, the effect
of temperature on nucleation over the range from
— 10 to 40°C yields an activation energy on the
order of 4.4 kcal/mol.70 Since this is on the same
order of magnitude as the activation energy for
the temperature dependence of the viscosity and
diffusion of molecules in these solutions, it has
been suggested that mass transfer processes play
an important role in the primary nucleation
mechanism.
From this analysis on temperature effects, it
is apparent that a balance exists between the rate
of primary nucleation expected and the level of
 supersaturation attained. In the manufacture of a
product in which sugar nucleation (by a primary
mechanism) is desired at a high level (as in fon-
dant), the temperature at which nucleation occurs
must be balanced by the level of supersaturation
attainable at that temperature. This is most often
done empirically due to the lack of quantitative
data on the effects of temperature and supersa-
turation on nucleation in product formulations.
That is, the optimum temperature for nucleating
is most often found by experimentation with a
specific product and formulation.
The temperature effect on secondary nuclea-
tion in stirred suspensions of sucrose crystals has
been studied by Randolph and Ziebold,42 Har-
Downloaded by [North Carolina State University] at 15:00 13 October 2012
tel,47 and Liang and Hartel.87 Randolph and
Ziebold42 found an activation energy for second-
ary nucleation of — 4.3 kcal/mol for sucrose nu-
cleated by mixture with alcohol, indicating that
the nucleation rate decreased with increasing
temperature. On the other hand, Hartel47 and
Liang and Hartel87 found the activation energy
in a continuous cooling crystallizer to be ap-
proximately 18.4 kcal/mol. Here, the nucleation
rate increased with increasing temperature in the
range of 30 to 60°C. Since the activation energies
determined in these studies were apparent acti-
vation energies for the secondary nucleation pro-
cess, it is difficult to find any mechanistic meaning
for these values. However, these values may be
useful for modeling purposes, given equivalent
crystallization conditions. Shi et al.91 have also
determined the rate of secondary nucleation of
lactose in a continuous cooling crystallizer and
found an activation energy of 17.0 kcal/mol be-
tween 30 and 60°C.
3. Rate of Cooling
When a highly concentrated sugar solution
is made by evaporation to remove water, and then
the temperature of that solution is quickly re-
duced, no nucleation will take place due to the
lack of sufficient mobility of sugar molecules to
form into a crystal lattice. Since nucleation is a
kinetic event, a certain time scale is required for
the reorientation of sugar molecules into the crys-
tal lattice structure. If cooling of the syrup is so
rapid that temperatures below the glass transition
point are attained prior to the onset of nucleation,
then a stable amorphous solid will be formed.
The supersaturation, final temperature, and types
and concentrations of additives contribute to the
determination of the extent of nucleation inhi-
bition and the occurrence of the amorphous tran-
sition. Due to the complex interactions between
these parameters, there has been very little quan-
titative data published on the boundaries between
the formation of the amorphous solid and crystal
nucleation.
4. Energy Input or Agitation Rate
The amount of energy input into a sugar so-
lution can also have a marked influence on the
rate of nucleation. The story of a stable super-
saturated solution that can be caused to nucleate
by a mere tap on the side of the vessel is an
example of the result of an external energy input
causing the onset of nucleation. In general, it is
thought that, as the energy input increases (i.e.,
the rate of agitation into a stirred tank), the rate
of nucleation increases and the supersaturation
required for the onset of nucleation decreases.
This is most likely attributable to the random
energy fluctuations imparted to the solution by
the degree of energy input causing local concen-
trations of sugar to exceed the critical value for
nucleation. In addition, any limitations due to
mass transfer may be reduced by the agitation of
the solution. One aspect of this effect of energy
input on nucleation can be seen in the superso-
lubility curve. The supersolubility line is affected
by the rate of energy input, as shown in Figure
21. Here, the line of demarcation between the
metastable and labile zones of supersaturation is
seen to occur at lower supersaturations in the
presence of agitation.
Van Hook and Bruno,71 however, observed
a slightly different dependence of nucleation rate
on agitation. Their results indicate that there was
no dependence on agitation rate or energy input
up to a specific stirrer speed and below a specific
supersaturation ratio (1.4). Above these limits,
their results do indicate that the onset of primary
nucleation occurs more rapidly as the agitation
level is increased. Van Hook and Frulla70 have
also observed the increase in rate of nucleation
81
 c
o
I
U
8
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Temperature
FIGURE 21. Effects of agitation rate on the nucleation rate.
under the influence of ultrasonic energy input.
Pulsed irradiation of low-frequency (8 kHz) ul-
trasonic waves at supersaturation ratios of 1.1
showed significantly increased seed densities,
compared with the nonirradiated samples.
For secondary nucleation, the rate of nu-
cleation is directly proportional to the energy in-
put into the solution, as shown in Equation 16.
The energy associated with crystal collisions is
increased as the energy input due to agitation is
increased. Controlled crystal contact experiments
on large single crystals demonstrate the effects
of contact energies on the numbers of nuclei gen-
erated. Gwynn88 has demonstrated the depen-
dence of number of nuclei generated on contact
energy between a brass rod and a large parent
sucrose crystal. Increasing numbers of nuclei were
generated at higher contact energies. In addition,
Kuijvenhoven and de Jong83 demonstrated that
the rate of secondary nucleation in a suspension
crystallizer increased with increasing stirrer speed
to the 0.5 power, while Petri and Bennett79 pre-
dict an exponent of 1.6 for the energy input term.
In summary, the rate of nucleation, either
from a primary or secondary mechanism, gen-
erally increases with increasing energy input or
agitation. The onset of nucleation is also en-
hanced by agitation and certain types of energy
input can cause significant reductions in the crit-
82
ical supersaturation necessary for nucleation to
occur.
5. Suspension Density
For secondary nucleation, the presence of
existing crystals is required for the further gen-
eration of new nuclei. The greater the number of
crystals, the greater the likelihood of collisions
due to the energy input or agitation. This is ac-
counted for in the kinetic model for secondary
nucleation (Equation 16) via the suspension den-
sity (or the third moment of the crystal size dis-
tribution) term. Correlation of secondary
nucleation with the specific number of crystals
present (zeroth moment of the size distribution),
the specific surface area of the existing crystals
(second moment of the size distribution), or even
the fourth moment of the size distribution79 can
also be used in this model. However, most of
the recent work in this area has utilized the third
moment of the distribution (i.e., the suspension
density) due to the ease of measurement and the
success in modeling experimental results. There-
fore, it is generally acknowledged that the greater
the mass of crystals in suspension, the greater
the rate of formation of additional nuclei by a
secondary nucleation mechanism.
 C. Effects of Additives/Impurities on
Nucleation
In most food products, the sugar does not
exist as a pure solution, but, rather, as some
complex mixture of a variety of ingredients. These
ingredients fall into the following categories: other
sugars, proteins, starches, salts, and other minor
additives (color, flavor, surfactants, etc.). Each
of these categories causes certain effects on the
nucleation rate of the sugars in the food product.
These influences arise partly due to the effects
on the sugar solubilities, but may also be partly
due to inherent effects on the mechanisms of
nucleation. An understanding of these effects is
Downloaded by [North Carolina State University] at 15:00 13 October 2012
critical to understanding whether or not nuclea-
tion of sugar occurs in a certain formulation, as
well as how to control the rate of nucleation to
yield the desired textural properties of the final
product.
In general, the rate of nucleation of sugars
is inhibited by the majority of food ingredients
used in sugar-containing products. This inhibi-
tion can be seen by the change in metastability
of a sugar solution in the presence of impurities
and additives.49-64 Typically, the critical super-
saturation for spontaneous nucleation increases
with increasing impurity level. For example, Van
Hook64 reports that 0.5% added invert suppresses
nucleation of sucrose solutions in excess of S =
1.8 (at 70°C). In comparison, the effects of im-
purities on glucose crystallization, whether as
monohydrate or anhydrous, have been shown to
be relatively small.49 The addition of 40% im-
purity (maltose) results in an increase in the crit-
ical supersaturation for secondary nucleation (or
false grain) of only 3.5 to 5%, whereas sucrose
shows an increase of 30 to 40%. However, mal-
tose at 20% addition was found to effectively
inhibit the growth of glucose crystals. Several
mechanisms may be operative in determining the
inhibition of nucleation by impurities or addi-
tives. These include mass transfer limitations to
bulk molecular motion, molecular charge effects,
or steric hindrance effects.
1. Other Sugars
Mixtures of sugars are quite common in the
formulation of food products, since a combina-
tion of the properties of each sugar is generally
obtained from the mixture. This allows some con-
trol over the textural and functional properties of
the food. For example, humectancy properties of
a food product will also be affected by variation
of the sugar mixtures in a formulation. Different
mixtures of sugars will also affect the extent and
rate of nucleation.
2. Surfactants
The addition of surfactants to the solution
has long been thought to reduce the energy re-
quirements for nucleation (primary) due to the
dependence of the nucleation rate on the inter-
facial tension. However, carefully performed
experiments64 demonstrate that addition of many
surfactants does not affect the rate of nucleation
as expected, despite the decrease in surface ten-
sion of the solution. This is most likely due to
the fact that the interfacial tension is not strongly
affected by the solution surface tension during
the dynamic process of formation and growth of
nuclei. On the other hand, Van Hook98 states that
surfactants may have some effect on the rate of
secondary nucleation. This would potentially be
caused by changes in the structure of the adsorbed
surface layer, which may be responsible for the
formation of secondary nuclei. Further work in
this area is necessary to verify these effects.
3. Salts
Salts may be an important component in a
food product and will have a significant effect
on the rate of nucleation of the sugars. For ex-
ample, the presence of milk salts, such as calcium
and phosphate, have a large effect on the crys-
tallization of lactose from whey. However, the
effects of these salts on the nucleation rate have
not been quantitatively studied in sufficient detail.
4. Macromolecules
The presence of macromolecules, such as
proteins, starches, pectin, etc., is quite common
in food formulations. These macromolecules, due
to their large size, tend to impose a significant
effect on the mass transfer of the sugar molecules
through the solution. Therefore, incorporation of
83
 these large molecules in a sugar syrup will ef-
fectively reduce the occurrence of nucleation.
The effects of organic colorant material on
sucrose crystallization has been reported by Nicol
and Farmer." Their results on a "lysine color"
(2% glucose solution boiled for 5 h at pH 9.5 in
the presence of lysine) demonstrate the enhance-
ment to nucleation of sucrose crystals due to the
presence of this impurity. This study observed
the change in crystal size distribution in a steady-
state continuous-cooling crystallizer due to the
presence of the lysine colorant. Nucleation rates
were enhanced by a factor of 4 when the lysine
colorant was present at a level of 2% (v/v). Since
the conditions studied represented secondary nu-
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cleation conditions, a specific conclusion on the
mechanism for this increase in nucleation rate
was not elucidated. One possible effect was that
the lysine colorant was acting as a nuclei site for
heterogeneous nucleation, which then out-
weighed the effects of secondary nucleation. More
likely, the lysine colorant may have had some
influence on the surface of the growing crystals
such that greater numbers of clusters were dis-
persed into the solution and the rate of secondary
nucleation was enhanced. This is an area where
further research is necessary to define the mech-
anisms of impurity effect on nucleation.
In summary, the effects of various additives
and impurities on the nucleation step has not been
adequately detailed, particularly for complex food
formulations. The specific effects of several im-
portant additives have been outlined to some ex-
tent; however, the interactive effects of each of
the important additives in food formulations have
not been studied. At this time, nucleation is a
phenomenon that is controlled essentially by ex-
perience and trial-and-error-type procedures. A
significant amount of experimental work will be
required before a full understanding of this phe-
nomenon in food products is achieved.
IV. CRYSTAL GROWTH
After a stable crystal nucleus has been formed,
further growth of that nucleus depends on the
conditions existing in the solution. In order for
that nucleus to grow, several processes need to
84
be accomplished. These generally include some
or all of the following:
1. Diffusion of the sugar molecules from the
bulk solution to the solid interface
2. Mutarotation of sugar molecules to appro-
priate anomeric growth form
3. Removal of all or some of the waters of
hydration associated with the solution form
of the sugar molecule
4. Counterdiffusion of the water molecules
away from the crystal surface
5. Orientation of the sugar molecule with other
molecules in the adsorbed layer between the
solution and crystalline phases
6. Surface diffusion of the sugar molecules to
: an appropriate lattice incorporation site
7. Incorporation of the growth unit into the
crystal lattice (surface incorporation)
8. Removal of any heat generated during the
above phase change
In any particular situation, some or all of the
above processes may occur during growth, with
one or two generally being the rate-limiting
step(s). Determination of the rate-limiting step
enables one to understand the mechanism gov-
erning the crystal growth process and is the goal
of much experimental work on crystal growth.
A. General Growth Theory
Growth theories tend to be categorized into
two main groups based on two of the above steps,
which are most often rate limiting. First are the
adsorption layer theories, sometimes referred to
as surface integration theories. These theories de-
scribe the incorporation of growth units into the
crystal lattice. Second, the mass transfer-limiting
theories account for the movement of molecules
through the bulk solution to the crystal interface,
where incorporation into the crystal lattice is con-
sidered to occur instantaneously. Heat transfer
may be of importance in controlling crystal
growth, as in the ice-water system. However, the
latent heat of fusion for sugar crystallization is
generally low enough (the enthalpy of sucrose
crystallization is given as —2.5 kcal/mol at 30°C
and - 7 . 8 kcal/mol at 57°C)100 that heat transfer
 effects are largely ignored. The concentration dif- solution. The rate of growth under mass transfer-
ferences around a growing crystal distinguishing controlled conditions is given as
the adsorption layer from the diffusion layer are
shown in Figure 22. ih = k, A(Cb - Q) (20)

where rh is the rate of mass deposition onto a

1. Diffusion Theory
Molecular diffusion due to concentration dif-
ferences may become the rate-limiting step for
crystal growth under conditions of either rapid
surface incorporation or limited mass transfer.
The driving force for this diffusional step is the
difference in concentration between the bulk, Cb,
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crystal surface area, A. In terms of linear growth
rate, G, this expression can be rewritten as66
G = k.k.CQ - Q) (21)
where kj involves terms of importance in con-
verting crystal volume to crystal size. The mass
transfer coefficient, k,,, can be found from mass

and the interfacial, Q , concentrations, as shown
in Figure 22. The rate of mass transfer by dif-
fusion also depends on the mass transfer coef-
ficient, kj, under the specific operating conditions.
This mass transfer coefficient depends on such
parameters as the level of agitation between bulk
and interface, the viscosity of the bulk solution,
and the diffusivity of the molecule through the
transfer correlation equations that take the gen-
eral form
Sh = 2 + dRebScc (22)
where Sh is the Sherwood number (kd L/Dv), L
is the characteristic crystal dimension, Dv is the
diffusivity of the solute in the solvent, Re is the

Crystal

Adsorption Layer
Bulk solution
concentration, C b

- tt
- *y

Interfacial solution
concentration, Cj

Equilibrium
concentration, C s

Boundary layer

FIGURE 22. Concentration differences around a growing crystal surface.

85
 Reynolds number (u L p/fji), u is the velocity
between crystal and solution, p is the solution
density, JJL is the solution viscosity, and Sc is the
Schmidt number (|x/p Dv). The parameters b, c,
and d are determined based on the range of op-
erating conditions and are generally correlated
for various conditions. Correlations of the form
given in equation 22 can generally be found in
literature references.41>54-101 Mass transfer corre-
lations for sucrose crystal dissolution are given
by Heffels et al.102
2. Adsorption Layer Theory
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Surface incorporation or adsorption layer the-
ories require the integration of the growth unit
into the crystal lattice to be the rate-limiting step
for growth (bulk mass transfer is rapid). This
generally involves formation of the growth unit
in the adsorption layer, diffusion of the growth
unit across the surface to some appropriate lattice
site, and then incorporation of the unit into the
lattice structure at that site. Alternatively, the
growth unit may be thought of as a two-dimen-
sional nucleus that must be formed on the surface
of the growing crystal, which then diffuses to an
incorporation site and is then finally integrated
into the lattice structure. These different aspects
of adsorption layer theories can result in different
growth dependencies. More detailed descriptions
of these theories can be found in Mullin54 and
Strickland-Constable.103
a. Two-Dimensional Nucleation
The formation of two-dimensional nuclei can
be thought of in the same manner as the classic
nucleation mechanisms mentioned previously. In
this case, however, one side of the nucleus is
bounded by the crystal surface, resulting in a
decreased energy requirement, when compared
with the three-dimensional nucleation process.
That is, the balance between energy requirements
for forming the nuclei surface vs. the energy lib-
erated in forming the nuclei volume is affected
by the influence of the crystal surface itself.
Physically, one can think of a molecular asso-
ciation forming on the crystal surface and be-
86
coming the basis for future growth of that surface.
Several aspects of the two-dimensional nuclea-
tion theory may be considered, depending on the
relative rate of two-dimensional nucleation and
the rate of subsequent growth based on surface
diffusion of growth units in the adsorption layer
to that site. The growth of the surface may be
based entirely on the formation of these nuclei
at each lattice site on the growing surface. In this
extreme case, growth does not occur at all by
surface diffusion of growth units in the adsorption
layer. At the other extreme for this model, growth
of a step on a crystal face can be initiated by
formation of a single two-dimensional nucleus
and then the step is filled out by instantaneous
surface diffusion of sufficient growth units around
the two-dimensional nucleation site. Any com-
bination of two-dimensional nucleation and sur-
face diffusion processes may also be postulated,
depending on the growth environment.
These two-dimensional nucleation theories
suffer from the disadvantage that a relatively high
supersaturation level is still required for the for-
mation of the two-dimensional nuclei. This would
suggest that the rate of growth would be quite
small at very low levels of supersaturation. How-
ever, many crystal systems exhibit significantly
higher growth rates at low supersaturations than
can be predicted by the two-dimensional models.54
b. Surface Diffusion Theory
The most common theory of surface diffu-
sion-based growth depends on the existence of
regenerating spiral dislocations on the crystal sur-
face.104 These spiral dislocations act as incor-
poration sites for growth units diffusing across
the surface in the adsorption layer. The regener-
ative nature of the spiral dislocation results in a
continuous source of incorporation sites that do
not depend on the two-dimensional nucleation
mechanism. This theory predicts more significant
growth rates at lower supersaturations dependent
mainly on the activity of the spiral dislocations.
The growth rate kinetics can be expressed by the
following equation:54
G = A, (S - I) 2 tanh(A2/S - 1) (23)
 where S is the supersaturation ratio (C/Cs) and
A, and A2 are constants that depend on temper-
ature and the spiral dislocation properties (step
height, activity, etc.). At low supersaturations,
Equation 23 can be simplified so that growth is
proportional to the supersaturation squared, while
at higher supersaturations, the dependence of
growth rate on supersaturation is linear. Crystals
that grow by this mechanism typically demon-
strate a parabolic depression in the plot of growth
rate vs. supersaturation, demonstrating the tran-
sition from second-order to first-order depen-
dence on supersaturation.
In general, the growth kinetics for adsorption
layer theories can be expressed empirically as
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G = - Csy (24)
where k, is the rate constant for the surface in-
tegration step and z is some empirical exponent
for supersaturation dependence. Equations 21 and
24 are not very useful for practical purposes,
since the interfacial concentrations are generally
not known. Therefore, most researchers in this
area either use a specific growth model, such as
the Burton, Cabrera, and Frank (BCF) model, or
they use a combined empirical expression of the
form
G = - Cs)n (25)
where Equations 21 and 24 have been combined
through elimination of the unknown Q. Equation
25 is suitable for a general growth condition in
which both volume diffusion and surface incor-
poration mechanisms are important in the overall
crystal growth process. Kinetic determinations
for crystal growth then involve determination of
the exponent of supersaturation and the rate con-
stant for growth, ko, which generally is a function
of temperature, agitation rate, and levels of ad-
ditives or impurities.
3. Growth Rate Dispersion and Size-
Dependent Growth
Some researchers in the past have found evi-
dence for the size dependence of growth.102'105
That is, it was found that small crystals grew at
a different rate than large ones. Several of the
above growth mechanisms predict a size-depen-
dent growth, including the mass diffusion-limited
case under certain conditions (in particular, when
the mass transfer boundary layer is larger than
the crystal size). In addition, extremely small
crystals may be influenced by a solubility (Gibbs-
Thomson) effect that would result in lower growth
rates for smaller crystals.54 Verification of these
mechanisms in the cases where size-dependent
growth has been observed has not been ade-
quately proven in many instances. At times, ap-
parent size-dependent growth has actually been
shown to be due to another phenomenon called
growth rate dispersion. Here, crystals grow at
some inherent rate based on the surface energetics
(surface incorporation step), but each crystal may
have a different inherent rate of growth. Some
experimental evidence for this mechanism84"86-106
has been presented, although this area remains a
current topic of research. Crystals that grow pre-
dominantly by a diffusional mechanism might not
be expected to demonstrate significant growth
rate dispersion, although it appears that this may
not always be the case.85-102 These results suggest
that the surface incorporation effect can never be
completely ignored during crystal growth, even
under the most diffusion-limited growth condi-
tions. Further experimental and theoretical work
is necessary to verify this hypothesis for the
mechanism of growth rate dispersion.
4. Dissolution
Many researchers in the past have considered
that crystal growth and dissolution were inverses
of the same process, particularly when growth
was controlled by a mass transfer process. How-
ever, current research shows that the dissolution
process occurs much more rapidly than the cor-
responding growth process, with the relative ratio
of dissolution rate to growth rate being anywhere
between 2 and 5. 54 Van Hook107 has studied the
dissolution of sucrose and demonstrated that this
process is essentially a mass transfer-limited pro-
cess. The activation energy for mass transfer (as
found from diffusivity or viscosity data) is the
same as the activation energy for dissolution,
while this is not always true for sucrose crystal
87
 growth. In addition, the process was found to be
diffusion controlled over the range of tempera-
tures from 0 to 80°C and demonstrated a signif-
icant viscosity effect. The relative rate of
dissolution to growth ranged from 1.1 to 11, de-
pending on temperature and roughness of the
crystal surface. In another work, Van Hook108
determined that diffusion of sucrose molecules
to or from a crystal surface was kinetically im-
portant at all temperatures for dissolution, but
only important at higher temperatures during
growth.
B. Growth of Sugars
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1. Sucrose
Significant effort has gone into quantifying
the rate of sucrose crystal growth and to under-
standing the mechanisms that govern that growth
under a variety of conditions. Nevertheless, su-
crose crystal growth studies remain an active topic
for current research due to its molecular com-
plexity and assymetric crystal nature.109 The im-
portant studies on sucrose crystal growth will be
reviewed here, with emphasis on determining the
mechanism of growth as well as quantifying the
effects of various operating parameters on the
growth kinetics. Several excellent reviews of su-
crose crystal growth can be found in Dunning,52
Van Hook,110-111 and Smythe.112 Powers113 gives
a quite readable summary of sucrose crystal
growth, with a variety of pictures of the various
forms that sucrose crystals can take when grown
under different conditions. Aquilano and Rubbo114
and Aquilano et al.115 give the growth rates of
individual faces of sucrose crystals grown under
various conditions. These growth rates are related
to the morphology or habit of the crystal. The
morphology of sugar crystals is described in many
references, including Kelly,116 while Vavrinecz117
has cataloged the variety of forms that sucrose
crystals may take.
One of the earliest reported studies on su-
crose crystallization, and perhaps one of the most
thorough, was that of Kucharenko.118 Large, sin-
gle crystals were grown under free-fall condi-
tions, with growth rates determined by weight
measurements of many individual crystals. A
88
temperature range of 0 to 70°C was investigated.
A relationship between crystal surface area, Ac
in square centimeters, and mass, W, in grams,
was derived and is given as
Ac = 4.12 W2* (26)
Kelly and Mak119 reviewed Kucharenko's data
by constructing cardboard models of the growing
crystals based on Kucharenko's measurements.
Their results suggest that Kucharenko's data were
quite accurate and that individual face growth
rates could be determined by analysis of the
changes in crystal size with time.
Smythe55 developed a technique for measur-
ing the change in crystal mass with time during
growth under controlled conditions where the fluid
velocity across the crystal surface could also
be investigated. A single crystal was suspended
in a supersaturated solution while fluid motion
was controlled by the speed of an agitator. Com-
prehensive crystal growth rates were deter-
mined at high agitation rates (3000 rpm) over a
wide range of temperatures (21.0 to 70.5°C) and
supersaturations (AC = Cb - Cs from 0 to 84.3
g/100 g H2O). In addition, stirring rates from 0
to 3000 rpm were investigated. A slight increase
in growth rate was found as stirring rate in-
creased, although a maximum level of growth
was reached when agitation was between 1000
and 2000 rpm, depending on the temperature and
supersaturation. Slightly higher overall growth
rates were found, when compared with Kuchar-
enko,118 due to the differences in agitation levels
between the two studies (Kucharenko studies at
free-fall relative velocity conditions and Smythe
at 3000 rpm55). Smythe's results indicate a linear
dependence of growth on supersaturation (AC)
at higher supersaturation values, but a higher-
order dependence at lower supersaturations, in
accordance with the surface diffusion model of
growth of Burton et al.104 A complicated tem-
perature dependence of growth rate was found
with the activation energy, as shown by the Ar-
rhenius relation changing with temperature. The
Arrhenius relation based on the growth constant,
kc, in Equation 25 can be written as
(27)
 where ko0 is a frequency factor, E a is the acti-
vation energy for the growth process, R is the
gas constant, and T is the absolute temperature.
A changing value of the activation energy is con-
strued as a changing mechanism for the reaction
being described. Thus, Smythe's results55 indi-
cate that the mechanism for sucrose crystal growth
changes over the range from 0 to 70°C. Below
40°C, the activation energy corresponds to a value
of 15 kcal/mol while above this temperature, the
activation energy was determined to be about 8
kcal/mol.
The above results, as well as the results of
other researchers,109 lead to the conclusion, clearly
stated by Van Hook,110 that the mechanism of
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sucrose crystal growth is comprised of more than
one step. Based on the relative activation energies
and the influence of the agitation level, both mass
transfer effects and the surface incorporation step
must be accounted for in sucrose crystal growth.
At elevated temperatures, mass transfer effects
tend to dominate and this becomes the rate-lim-
iting step for growth. However, below 40°C or
so, the surface incorporation step becomes more
important and the effects of mass transfer on the
overall crystal growth rate are reduced
significantly.
Mass transfer rates to sucrose crystals grow-
ing under a variety of conditions have been stud-
ied by Heffels et al.102 Correlation equations
similar to Equation 22 are given for crystals of
different sizes growing under different agitation
conditions. The influence of mass transfer of su-
crose molecules to a growing crystal surface has
also been studied by Schliephake and co-work-
ers,120"123 with an emphasis on the practical con-
ditions of importance in commercial sucrose-
refining operations. Their results show that mass
transfer of sucrose molecules through the bulk
solution becomes more important in determining
growth kinetics as the temperature is increased.
The effects of this increased resistance to growth
due to mass transfer at higher temperatures can
be minimized by increasing the relative velocity
between crystal and solution.
A significant amount of effort has gone into
studying the mechanism of the surface incorpo-
ration step. Most recent work has concluded that
the surface diffusion model of Burton et al.104
(BCF) based on spiral dislocation growth ade-
quately describes this step.124-125 The existence
of spiral and other dislocations on the surface of
growing crystals has been visually documented
microscopically by Albon and Dunning. 126
Valcic127 has identified crystals with differing
dislocation activities and demonstrated the dif-
ferences in growth kinetics. Van Hook128 shows
similar results using crystals classified as either
' 'good'' o r ' 'poor''. The good crystals were quite
clear, with prominent faces, while the poor crys-
tals were cloudy and showed unusual facets and
truncations. The poor crystals were seen to grow
faster and to demonstrate a parabolic depression
(change from second to first order) in the growth
vs. supersaturation curves, suggesting that spiral
or dislocation growth is more important in the
poor crystals. Dunning52 describes the different
forms of dislocations arising on a sucrose crystal
surface and discusses their effects on crystal
growth.
However, the work of Aquilano and Rubbo114
suggests that a simple one-step mechanism for
the surface incorporation mechanism does not
adequately explain the growth kinetic data, par-
ticularly when the growth of an individual face
is studied. Their growth isotherms (growth vs.
supersaturation) for individual faces, as deter-
mined by following the advancement of a crystal
face under microscopic examination, show some
reproducible deviations from either a first- or sec-
ond-order process. These growth isotherms did
not fit the BCF growth rate equation for surface
diffusion. Additional studies, both experimental
and theoretical, are suggested to further quantify
these deviations and to outline the operating
growth mechanisms.
In addition, several investigators have at-
tempted to delineate the surface incorporation
mechanism by operating under growth conditions
where mass transfer was rapid relative to the rate
of surface integration. Van Hook129 performed
growth experiments at very low temperature
(0°C), where mass transfer was shown to have
negligible effect. His results show that a linear
relationship between growth rate and supersatur-
ation exists at all supersaturations down to very
low levels. In other words, no parabolic depres-
sion or change to second-order dependency oc-
curred. This suggests that a surface incorporation
mechanism other than the BCF model was dom-
89
 inant. Maurandi109 discusses this nonagreement
with the BCF model at various conditions and
concludes that further investigations in this area
are required.
Van Hook130 suggests that the above dis-
crepancies can be reconciled by considering the
manner in which sucrose crystals grow. It was
observed that sucrose crystals became more im-
perfect as they grew under normal conditions, so
that larger crystals were generally more imperfect
than smaller crystals. When the dislocation den-
sity was large, the dependence of growth on su-
persaturation was linear. This occurred for larger
crystals due to the high level of dislocations.
However, when the number of dislocations was
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smaller, the kinetic order changed from second
order at lower supersaturations to first order at
higher supersaturations, as predicted by the BCF
model. This hypothesis has some basis in the
literature127 but has not been adequately verified
experimentally. No consensus has yet been
reached as to when the BCF model strictly applies
and when some other mechanism of surface in-
corporation is active.
Heffels and de Jong131 suggest that, at high
temperatures, sucrose crystal growth can be de-
scribed by a combination of volume diffusion and
surface incorporation based on the BCF model
of spiral dislocation growth. Their results suggest
that both supersaturation and crystal size influ-
ence the dependence of growth rate on supersa-
turation. Larger crystals, which are faster
growing, demonstrate a linear dependence on su-
persaturation at all concentration values. How-
ever, smaller crystals, which have inherently
lower growth rates, demonstrate the second-order
dependence at lower supersaturations, as pre-
dicted by the BCF model. Their conclusion is
that small crystals grow differently than larger
crystals, although one might also suggest that
small crystals are small because they grow dif-
ferently (slower) than large crystals (faster grow-
ers). This connects the dependence between
growth and supersaturation with the concept of
growth rate dispersion. The change in growth
characteristics may be due to inherent differences
in dislocation activities between crystals resulting
in different growth rates. Alternatively, it may
be due to the effect of low-level impurities that
essentially have the same effect in producing
90
crystals with varying dislocation activities. The
combination of growth theories with growth rate
dispersion has not received sufficient study to this
point.
The majority of the previous studies on su-
crose follow the growth of a single crystal or an
individual face on a single crystal. Several studies
have also investigated the average growth prop-
erties of a distribution of crystals growing in either
a batch or a continuous crystallizer.42-47-79-83-102-132
In general, these studies corroborate the above
single crystal results, showing a linear relation
between growth and supersaturation at higher
supersaturations4779 and a second-order depen-
dence at lower supersaturations.132
These studies also demonstrate the existence
of growth rate dispersion as an important phe-
nomenon in sucrose crystal growth. That is, each
crystal has been seen to grow at a different rate
to yield a growth rate distribution for an initially
similar population of seed crystals. One of the
earliest works on size or growth dispersion in
sucrose crystals is attributed to White and
Wright,133 although qualitative evidence for this
phenomenon existed for many years. White and
Wright133 demonstrated that a uniform seed dis-
tribution of sucrose crystals growing in a super-
saturated solution tends to widen in its size
distribution. That is, an initially narrow seed-size
distribution will grow ever wider as crystal growth
proceeds, since some of the seeds grow faster
than others. Their results show that this disper-
sion was independent of temperature and crystal
size (initial seed size), but dependent on the av-
erage growth rate. From these experiments, it
was unclear whether this phenomenon was at-
tributable to some basic growth mechanism or
was simply due to fluctuations in supersaturation
in the growth vessel. Subsequent work has dem-
onstrated that, under certain conditions, the phe-
nomenon of growth rate dispersion is indeed
related to the basic mechanism of crystal growth.
Berglund132 continued these experiments and fur-
ther quantified the extent of growth rate disper-
sion during sucrose crystal growth in a batch
crystallizer.
Shanks and Berglund84 performed a series of
experiments in a photomicroscopic cell that al-
lowed the study of the change in the size of grow-
ing sucrose crystals. These crystals were actually
 formed by a sliding contact mechanism, but their
growth showed significant differences attribut-
able to growth rate dispersion. It was found that
each individual nucleus grew at some inherent
rate, but that a distribution of growth rates was
evident. That is, some crystals grew faster than
others. Liang et al.86 extended this work by look-
ing at the growth of large (>100 |xm) seed crys-
tals using a similar experimental technique. Their
results also demonstrate the existence of growth
rate dispersion for larger crystals and that the
extent of this dispersion increases as the average
growth conditions (temperature and supersatur-
ation) increase. Hartel et al.134 summarize the
effects of growth environment (static vs. dy-
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namic), crystal origin (secondary nuclei vs.
seeds), and impurity content (raffinose level) on
growth rate dispersion in sucrose crystals.
2. Lactose
Other than sucrose, the study of lactose crys-
tallization has received the most attention from
researchers, particularly in the dairy industry.
Several excellent reviews on lactose crystalliza-
tion exist, including Nickerson23 and Nickerson
and Moore.135-136 Much experimental work has
been done on lactose crystallization from com-
mercial cheese whey, since this is the primary
source of refined lactose. These studies generally
include some or all of the impurities present in
the initial whey and, thus, experimental work on
pure lactose is somewhat limited. Visser53 has
recently studied the rate of lactose crystallization
from deionized lactose and derived significantly
different growth rates from these pure solutions
than have been obtained even from pharmaceut-
ical grade (USP, 99.85% pure) lactose. The spe-
cific effects of these impurities remain in question.
Visser137 studied the growth of lactose crys-
tals from pharmaceutical-grade lactose supplied
from various sources using a single-crystal pho-
tomicroscopic technique. Here, the advance of
various faces of the lactose crystals were mea-
sured and converted to a linear growth rate. Sev-
eral sources of lactose were tested, with
significantly different results in growth rate. These
differences stemmed from marked differences in
pH and conductivity of the lactose samples as
obtained from the supplier. After considerable
effort to purify these lactose solutions, Visser137
concluded that an ionic impurity existed in these
lactose samples that resulted in the observed ac-
idity of the lactose solutions (3.5 to 4.5) and had
an inhibitory effect on the rate of lactose crystal
growth. The extent or type of this impurity de-
pended on the source of the lactose (which sup-
plier the lactose came from). When this impurity
was removed from the lactose solution by ion
exchange, a neutral solution was obtained (pH
6) with low conductivity. Growth studies per-
formed in this deionized lactose ranged from three
to six times higher than those in the correspond-
ing pharmaceutical-grade lactose solutions. His
conclusion was that all previous work on lactose
crystallization actually involved the effects of this
ionic impurity and, thus, were not indicative of
pure lactose crystallization rates. In a subsequent
study, Visser138 isolated and identified this nat-
urally occurring substance as dilactose phosphate
complexes that are incorporated into the crystal
lattice. Recrystallization and washing for up to
14 times was necessary to purify the pharma-
ceutical-grade lactose, taking the pH from 3.1 to
6.1. However, it was found that ion exchange of
the lactose solution removed nearly all of this
impurity.137 Further studies4 have clarified that
the anions of the dilactose phosphate impurities
in the a-form adsorb onto several of the lactose
crystal faces, thereby inhibiting the incorporation
of a-lactose molecules into the crystal lattice.
Various aspects of a-lactose crystallization
have been studied by Whittier and Gould,139 van
Kreveld and Michaels,140 Haase and Nickerson,25
Michaels and van Kreveld,141 Jelen and Coul-
ter,142-143 Nickerson and Moore,135 Thurlby and
Sitnai,144 Valle-Vega and Nickerson,145 and Vis-
s e r 4,53.138 jjjg a _i ac tose monohydrate crystal
grows in a wedge or tomahawk shape when grown
under low supersaturation conditions.23 At higher
supersaturations, different shapes are observed,
with the habit changing to a more prism-shaped
characteristic at very high supersaturations.146
These habit modifications arise due to differ-
ences in the growth rates of the individual faces
and the changes in these relative growth rates
with supersaturation. 140141 Van Kreveld and
Michaels140 also showed that the tomahawk-
shaped crystal grows only in one direction —
91
 from the apex of the tomahawk. This apex is the
site of the original nucleus. Growth has been
found to increase with increasing supersaturation
with an exponent greater than one, dependent on
the particular face. Average growth rates for lac-
tose crystals as determined from the population
balance approach in a continuous-cooling crys-
tallizer increased with supersaturation (expressed
as concentration difference) to the 3.55 power.90
Whittier and Gould139 followed the decreas-
ing concentration of lactose in solution during
batch growth of seed crystals. This desupersa-
turation curve varied in shape with the temper-
ature of crystallization between —5 to 30°C. The
initial rates of desupersaturation increased with
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decreasing temperature due to the increased con-
centration. However, higher temperatures showed
greater decreases in concentration at longer times,
due to the effects of mutarotation on growth. The
rate of mutarotation decreases significantly with
decreasing temperature, resulting in lower con-
version to the a-form at these lower tempera-
tures. These changes in concentration were
converted into a rate over a narrow range of con-
centrations during the middle of the experiment
at each temperature. The resulting rate constants
increased linearly with temperature; however, this
dependence would most likely depend on the con-
centration region used in the calculation.
The mechanism of growth of a-lactose
monohydrate crystals has been stated to be sur-
face incorporation controlled since diffusion is
unimportant.140 The relative effects of mutaro-
tation on the rate of crystal growth depends on
several parameters, including the temperature,
pH, and presence of impurities or additives. Twieg
and Nickerson147 state that the rate of mutarota-
tion is quite rapid compared with the rate of crys-
tal growth, and thus should not influence the rate
of growth unless the available surface area is
exceedingly large. Brinkman,148 however, states
that at temperatures (>75°C) mutarotation is so
rapid that no effect on growth should be ob-
served, while at temperatures less than 30°C
the mutarotation rate is slow enough to affect the
rate of growth. A more appropriate comparison
would be between the rate of mass deposition
onto the available surface area and the rate of
mutarotation at the specific conditions under
study. Some unpublished work currently under-
92
way in the author's laboratory suggests that, even
during growth of seed populations with low sur-
face areas, some change in the ratio of a/p-lac-
tose in solution occurs, as evidenced by changes
in the optical rotation. Constant optical rotation,
indicating that equilibrium solution conditions
were being maintained, was found only when
extremely small amounts of seeds were used.
Under most growth conditions, the optical rota-
tion was found to decrease as the crystal mass
developed during growth, followed by an in-
crease in the optical rotation until the equilibrium
was attained after crystallization had been com-
pleted. Further work is underway to quantify the
conditions under which mutarotation limits the
rate of crystal growth.
Increasing temperature has also been seen to
increase the rate of lactose crystal growth. Jelen
and Coulter143 demonstrated this temperature de-
pendence for growth between 30 and 70°C. When
the supersaturation ratio (C/Cs) was used to show
the growth kinetics, growth increased continually
between 30 and 70°C. However, when the con-
centration excess (AC = C — Cs) was used to
define the supersaturation, it was found that
growth increased from 30 to 50°C, and that no
further increases in growth were observed be-
tween 50 and 70°C. No conclusion regarding this
temperature dependence was drawn by Jelen and
Coulter,143 although this is an excellent example
of the manner in which the expression of super-
saturation can affect the definition of growth ki-
netics. The effect of supersaturation on growth
was found to vary with temperature over this
range. At 30cC, the supersaturation dependence
was 2.5 (using AC), while at higher tempera-
tures, the dependence became second order. An
activation energy for growth has been determined
by Shi et al.91 using the population balance method
to analyze lactose crystallization in a continuous-
cooling crystallizer. This activation energy was
determined to be 22.1 kcal/mol over the range
of 30 to 60°C. No change in mechanism was
observed, since the activation energy was con-
stant over this temperature range. These results
suggest a growth mechanism based on the surface
incorporation step. That is, diffusion is most likely
negligible under these growth conditions, veri-
fying previous results. The dependence of growth
on supersaturation, where supersaturation was
 defined by Visser53 using Equation 4, was also
found to result in an exponent of 2.5 over this
temperature range.
Thurlby and Sitnai144 studied the crystalli-
zation of a-lactose monohydrate by following the
change in mass of a seed distribution during
growth at various supersaturations and temper-
atures (15 to 50°C). Growth was found to in-
crease with increasing temperature and
supersaturation. No activation energies for the
temperature dependence of growth were calcu-
lated. The growth rate was found to depend on
the relative a-lactose supersaturation to a power
between 3 and 4, depending on the temperature.
In general, the power was seen to increase with
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increasing temperature.
The inhibitory effects of (3-lactose on the
growth of a-lactose monohydrate have been dem-
onstrated from a molecular standpoint by Visser
and Bennema.149 Their molecular approach to
lactose crystal morphology leads to the correct
prediction of the equilibrium shape of a-mono-
hydrate lactose crystals only when fj-lactose is
considered to block part of the intermolecular
bonds during crystal growth.
In recent years, the interest in developing
forms of lactose other than the a-monohydrate
has increased due to the different properties that
may be obtained. These forms impart different
textural or sensory properties in foods, resulting
in new products. The crystallization of (3-lactose
has been reviewed recently by Olano et al.15° The
formation of P-lactose from both aqueous and
alcohol solutions is detailed. Itoh et al.151 discuss
a technique of crystallizing p-lactose based on
heating a supersaturated solution of lactose under
reflux conditions. Very little information regard-
ing the fundamental mechanisms of P-lactose
crystal growth is available.
3. Glucose
The desupersaturation curves for batch growth
of a-anhydride glucose crystals were studied by
Whittier and Gould.139 Temperatures between 0
and 30°C were studied. The growth of these crys-
tals was exceedingly slow, compared to sucrose,
but was on the same order of magnitude as the
growth of lactose crystals. The rate was seen to
increase slowly with increasing temperature over
this range. Whittier and Gould139 also studied the
growth of sucrose, lactose, and galactose in the
same way. Their results demonstrate the relative
speed for growth of the nonreducing sugar, su-
crose, compared to the reducing sugars. These
differences in growth rates were attributed to the
presence of anomeric forms of the reducing sug-
ars in solution and their inhibition on growth.
Van Hook64 shows growth rate data for a-
glucose monohydrate over the temperature range
of 25 to 43CC and at varying supersaturations
(expressed as concentration difference). These
results demonstrate that the growth of glucose
monohydrate is essentially independent of tem-
perature and increases approximately linearly with
increasing supersaturation. From these results,
Van Hook64 concluded that diffusion of glucose
molecules is the rate-limiting step for crystal
growth under these conditions. This result was
also confirmed by Edwards,94 who showed that
increasing the stirring speed in suspension crys-
tallization increased the rate of growth up to some
critical agitation rate. Above this rate, crystal
growth was constant, indicating that diffusion
was no longer the limiting mechanism.
4. Fructose
The growth kinetics of fructose crystals gen-
erated from sliding contact were determined by
Shiau and Berglund97 over the range of 30 to
50°C and subcoolings from 1 to 9°C. These con-
tact nuclei were seen to exhibit growth rate dis-
persion. The average growth rates of nuclei
created at any given temperature and subcooling
were calculated and growth kinetics developed.
These kinetics showed that the average growth
rate increased with both temperature and super-
saturation. Growth increased with the relative su-
persaturation to the 1.25 power and an activation
energy for growth of 6.1 kcal/mol was found.
These results suggest that mass transfer plays an
important role in the growth process for these
nuclei grown in a stagnant environment on a pho-
tomicroscope stage. However, surface incorpor-
tation of fructose molecules must also be important
in determining the overall rate of fructose crystal
growth, as demonstrated by the occurrence of
93
 growth rate dispersion. Watanabe152 claims that
the viscosity of fructose solutions at high con-
centrations inhibits the rate of fructose crystal
growth. Both Watanabe152 and Chu et al.153 dem-
onstrated the effects of heat treatment in reducing
the rate of fructose crystal growth due to the
formation of fructose polymers. The polymeri-
zation of fructose was enhanced by low pH con-
ditions and high-temperature treatment, as may
occur during the evaporation of syrups.152
C. Operating Parameter Effects on
Crystal Growth
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An understanding of the parameters that in-
fluence the rate of crystal growth in a sugar sys-
tem is important in controlling the process to
maintain optimal results. That is, since the tex-
tural quality of a food product depends on the
crystal size distribution, the rate of growth of the
sugar crystals is critical to the final product char-
acteristics. Of utmost importance to crystal growth
is the supersaturation in the syrup phase of the
product. However, a number of other factors also
play an important role in the final growth prop-
erties. These include the agitation rate in the syrup
phase, the temperature at which growth occurs,
the viscosity of the solution (dependent on the
concentration and temperature), pH, the source
of nuclei, and the types and concentrations of
impurities or additives. This last parameter plays
a critical role in the formulation of a food product
and the resulting textural properties.
1. Supersaturation
The driving force for sugar crystal growth is
the excess concentration in solution over the sat-
uration concentration at that temperature (Cb -
Cs). The greater this driving force, the higher the
rate of crystal growth, all other conditions being
equivalent. The dependence of growth rate on
supersaturation depends on the underlying mech-
anism for the growth process, as described in
Section IV. 1. For sucrose, this dependence ranges
from a first-order to a second-order power of
supersaturation. Experiments in which these
growth kinetics are determined can aid in defin-
94
ing the growth mechanism; however, caution must
be used since other parameters also affect the rate
of crystal growth. For example, sucrose crystal
growth has been found to exhibit a linear depen-
dence on supersaturation at higher levels, of su-
persaturation. At lower supersaturations, the
dependence has been found by many researchers
to be nearly second order. This suggests that the
growth mechanism proposed by Burton et al.104
based on surface diffusion to spiral dislocations
may adequately describe the growth of sucrose
crystals. This has been found to be true for larger
crystals that are dominated by imperfections, but
perhaps does not hold true for small crystals that
may have many fewer dislocations present on the
crystal surfaces.127 For lactose, the dependence
of crystal growth on supersaturation ranges be-
tween 2 and 3, depending on the temperature and
other conditions.143
In a food product, the supersaturation value
is dependent on both the level of sugar in the
syrup phase and the types and levels of additional
additives, such as other sugars, starches, and pro-
teins. These other components alter the saturation
concentration of sugar (generally lowered), thus
affecting the supersaturation value. These com-
ponents may also affect the inherent rate of crys-
tal growth. Predicting the rate of crystal growth
in a food product is very difficult due to the many
parameters that impact the growth of sugar crys-
tals. Further experimental work is generally re-
quired to determine the specific effects on crystal
growth in complex food products.
2. Temperature
Raising the temperature generally increases
the rate of crystal growth, as shown by the po-
sitive value of the Arrhenius activation energy.
However, different mechanisms of growth may
dominate, depending on the temperature at which
growth is occurring. In sucrose, for example, the
mechanism of crystal growth changes as the tem-
perature changes. At lower temperatures, less than
about 40°C, the crystals grow predominantly by
a surface incorporation mechanism, while at
higher temperatures the mass transfer or volume
diffusion effects become the dominating mech-
anism. This temperature dependence is interest-
ing when one considers the effects of temperature
 on the viscosity of sugar solutions. As the tem-
perature goes up, at a constant concentration, the
viscosity decreases.45 The viscosity increases
dramatically as the temperature decreases, yet
mass transfer effects are most dominant at the
lower viscosity conditions of higher temperature.
This is attributable to the temperature dependence
of the surface incorporation step (activation en-
ergy of 16 to 18 kcal/mol) vs. that for diffusion
(activation energy of 6 to 8 kcal/mol). At lower
temperatures, the rate of surface incorporation is
considerably depressed, causing this step to be
the rate-limiting step. At higher temperatures, the
surface incorporation step occurs more rapidly
than mass transfer (due to the increased temper-
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ature dependence) and, thus, the volume diffu-
sion step becomes rate limiting. These results
apply for a well-mixed growth environment where
agitation effects are negligible. A stagnant syrup
environment will cause considerably more de-
pendence on mass transfer conditions at lower
temperatures.
3. Viscosity of Solution
In past years, people have considered the
viscosity of the syrup phase to be a primary pa-
rameter in the determination of crystal growth
rates. However, viscosity effects can generally
be accounted for by considering the changes in
concentration and temperature, which directly
determine the viscosity in most instances. Studies
in which the viscosity of solution was changed
by the addition of additives that had no effect on
the inherent rate of crystal growth, yet altered
the solution viscosity, have verified this conten-
tion.64 That is, a viscosity change alone does not
necessarily alter the rate of crystal growth. This
viscosity change is usually related to a change in
some other growth-dependent parameter (con-
centration or temperature).
4. Agitation Rate
The effects of agitation rate on growth de-
pend on the mechanism of growth under the con-
ditions being studied. If surface incorporation is
the rate-limiting step for growth (as with lactose
under normal conditions), then an increase in
agitation will not influence the rate of growth.
On the other hand, agitation rate is important
when mass transfer influences the rate of crystal
growth. As the relative velocity between crystal
surface and solution is increased, the hindrance
to growth caused by mass transfer limitations will
be reduced and the rate of growth will be in-
creased. This will continue up to the point where
mass transfer again does not impact the rate of
growth. This influence is seen quite clearly by
the work of Smythe55 and Van Hook154 on sucrose
crystal growth. An increasing growth rate was
seen when low agitation rates were used, with
that increase tapering off at high agitation rates
until a constant growth rate was reached at very
high agitation rates. This effect will be most no-
ticed under higher-temperature growth conditions
(>40 to 50°C), where mass transfer is the more
important growth mechanism.
Another phenomenon related to agitation is
the final average size of a crystalline product
grown in a batch system. Apart from the above
effects on the crystal growth mechanism, agita-
tion can influence the final product size through
its influence on the nucleation rate. The rate of
secondary nucleation is dependent on the rate of
agitation, as described previously. Thus, if a
crystal suspension is grown under agitated con-
ditions, additional nuclei will continually be added
to the crystal size distribution. Since the nuclea-
tion step also depletes the available supersatur-
ation, in direct competition with the growth
process, each of the crystals will grow to a slightly
lower extent. This results in smaller crystals when
nucleation takes place. This has been verified
experimentally on lactose crystals by Valle-Vega
and Nickerson,145 among others.
S.pH
The effect of pH on the rate of sucrose crystal
growth is tied intimately to the process of inver-
sion and formation of invert sugar. Invert sugar
has a marked effect on the rate of crystal growth,
to be discussed in a subsequent section on ad-
ditives. From a molecular viewpoint, changing
the hydrogen ion concentration in a sugar solution
may cause changes in the hydrogen bonding char-
acteristics of the sucrose molecule, which may
95
 have some effect on the rate of crystal growth.
For reducing sugars, pH changes also result
in mutarotation equilibrium changes, which may
further affect the rate of crystallization. Twieg
and Nickerson147 demonstrate the different rates
of desupersaturation of lactose from pharma-
ceutical-grade lactose solutions at pH 1 and 4
during seed growth in a batch crystallizer. Then-
results show a more rapid decrease in concentra-
tion at the lower pH, indicating a more rapid rate
of growth. However, different results were found
by Visser,137 who studied the growth rate of dif-
ferent faces of a single lactose crystal from phar-
maceutical-grade lactose solutions as a function
of the pH. The growth of all faces was seen to
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decrease to near zero at pH values below 2, and
a maximum growth rate was found at a pH value
of about 7. These changes are dependent on the
form of the disaccharide phosphate impurity in
the pharmaceutical-grade lactose solution. When
similar pH studies were done using nonionized
lactose (passed through an ion exchange col-
umn), quite different results were obtained. Here,
the growth rate at pH 1.5 was only slightly lower
for most of the faces studied than the correspond-
ing growth rate at pH 3.5 or 7.5. The exception
to this was the large basal face (010), which
showed a slight increase in growth rate at pH
1.5. From this, it appears that pure lactose ex-
hibits only a small dependence of growth on pH,
while impurity effects may play a significant role
for impure solutions. One factor that needs to be
considered when making comparisons regarding
the effects of pH on lactose crystal growth is the
effect on the equilibrium mutarotation conditions
for a-lactose. That is, any effects of pH on the
a-lactose supersaturation and the subsequent ef-
fects of (3-lactose on growth must also be
determined.
Commercial aspects of pH change in whey
on the lactose crystal product, including com-
position, crystal size, and yield, were studied by
Modler and Lefkovitch.155 Many of the observed
effects arose due to changes in protein denatur-
ation and salt solubility in whey with pH. Whether
or not these pH effects on lactose crystallization
can be directly related to the direct effect of pH
96
on the lactose crystal growth mechanism remains
in question.
6. Source of Nuclei
In general, it has been understood that, the
smoother the crystal surface, the slower the crys-
tal growth. Conversely, crystals that have a sig-
nificant surface roughness, from a grinding
process, for example, will grow more rapidly, at
least initially. This has been shown by Van
Hook,106 where the difference in growth rates and
kinetics for "good" and "poor" crystals was
demonstrated. The poor crystal, which was cloudy
and had faceted and truncated faces, grew at a
higher rate than a good crystal of high quality.
A difference in kinetic dependencies on super-
saturation between these classifications of crys-
tals was also found. The poor crystal showed a
linear dependence of growth on supersaturation,
while the good crystal showed a dependence that
changed from second order at low supersatura-
tions to first order at higher supersaturations.
Whether a crystal grows out of its inherent im-
perfections depends on many factors, including
the supersaturation level and the nature of these
imperfections. If the imperfections can be ov-
ergrown, then the growth of the crystal will grad-
ually decrease until only the inherent dislocations
control the rate of growth. For this reason, one
sometimes can observe an initially rapid rate of
growth followed by a levelling off of the growth
rate at some inherent value.102-156
The manner by which a crystal nucleus is
formed may have important consequences on how
that particular crystal grows. Some interesting
experimental results93 have shown that lactose
nuclei can be formed under contact nucleation
conditions and that a high proportion of these
nuclei do not grow. These contact nuclei seem
to require some activation, perhaps by a thermal
shock, in order to grow at any substantial rate.
This type of behavior has also been observed for
sucrose crystals formed by a secondary nuclea-
tion mechanism.78102 The mechanism for this
growth anomaly is probably related to the effects
 of surface dislocations and internal stresses within
the crystal that do not allow molecular deposi-
tion. More experimental and theoretical work is
required in this area.
7. Suspension Density
The higher the number of crystals in a so-
lution, the greater the competition for available
supersaturation. This can result in decreased
growth due to mass transfer effects. This has been
studied in sugar refining, where very high crystal
densities are attained.157 Zagrodski157 developed
a correlation expression relating the crystal con-
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tent to a mass transfer coefficient correction fac-
tor that was used to modify some unaffected
growth rate obtained at low crystal densities at
the same conditions. The effects of high crystal
numbers on the growth mechanisms of sugar
crystals in food products has not been investigated.
Another result of high numbers of crystals,
or a large surface area available for growth, is
that the final product size is generally decreased.
The available excess concentration (supersatur-
ation) is divided equally among all the crystals
present, resulting in less growth for an individual
crystal when there are large numbers of crystals.
Thus, a distribution with few crystals will grow
to a larger average size than a distribution with
many crystals. This difference, of course, de-
pends on the total surface area, the total number
of particles, the difference in initial seed size,
and the supersaturation.
8. Electric/Magnetic/Sonic Fields
Some work in the past has demonstrated the
effects of external field applications on sugar
crystal growth. For example, Gonzalez and
Ramirez158 studied the effects of electrical fields
and found that sucrose crystal growth rates in-
creased by almost 70% when a constant field of
125 V/cm was applied. The growth rate was found
to increase linearly as electric field increased to
this level. The mechanism for this increase was
not determined, although their conclusion was
that the mechanism involved phenomena that take
place at the solid-liquid interface rather than in
transport phenomena through the bulk solution.
One can find many references in the crys-
tallization literature about the effects of ultrasonic
irradiation on nucleation and growth rates.64159160
Many of these references claim a significant ef-
fect due to the input of ultrasonic energy; how-
ever, the specific effects are not clear, due to
several apparent effects that may cause erroneous
results. The increase in temperature associated
with an ultrasonic field, for example, can cause
an apparent increase in the rate of crystal growth.
An apparent effect of ultrasonic energy on mass
transfer rates has led researchers to suggest that
growth rates of crystals growing under diffusion-
controlled conditions will also increase. This has
been verified in some cases,160 although ques-
tions still remain about the validity of this hy-
pothesis for all situations.
D. Effects of Additives/Impurities on
Growth
A complex mixture of ingredients in a food
product causes a complex pattern of growth of
sugar crystals due to the many interactions. Some
of the ingredients (other sugars, etc.) added to a
sugar syrup formulation may influence the sol-
ubility of the sugar at the processing conditions,
resulting in changing supersaturations. At the
same time, many added ingredients or impurities
present (other sugars, proteins, starches, etc.) may
directly affect the rate of crystal growth by in-
fluencing the mechanism of growth. This may
occur due to mass transfer limitations or from
inherent influences on the surface incorporation
step. A complete understanding of the effects of
a particular ingredient on the rate of crystal growth
requires an understanding of the effects on both
solubility and inherent growth rate. In addition,
many ingredients show synergistic effects with
other ingredients. Therefore, detailing the exact
effect of an ingredient in a food formulation may
be quite complex. The end result is that empirical
or experimental investigations are generally nec-
essary. However, some general understanding can
be developed by looking at the individual effects
of each ingredient. In general, most of the im-
purities or additives of importance in food prod-
ucts will cause a decrease in the rate of sugar
crystal growth.
97
 1. Other Sugars
Perhaps most important of all combinations
for sugar-based food products are mixtures of
various sugars. Sugars are generally mixed to
take advantage of the properties of each of the
sugars involved, to increase the total level of
solids in solution for microbiological concerns or
to control the rate of sugar crystallization.
Smythe55 studied the effects of a variety of
sugars on sucrose crystal growth, including invert
sugar, raffinose, and other oligosaccharides
(stachyose, neo-kestose, gentianose, melezitose,
and kestose). Invert sugar between 17 and 220
g/100 g water addition level decreased sucrose
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crystal growth significantly over a range of su-
persaturations. The decrease in growth rate in-
creased as the invert sugar level increased. At a
concentration of 100 g invert per 100 g water,
the growth rate was decreased to merely 25% of
the pure sucrose growth rate at a given super-
saturation. The inhibitory effect of raffinose was
found to be even stronger. When invert sugar and
raffinose were studied in combination, it was
found that a small concentration of raffinose (2.8g/
100 g water) in a larger concentration of invert
sugar (100 g/100 g water) produced a further
decrease in growth rate over the invert sugar alone.
The effects of these sugars was additive, but not
in the same proportions at different temperatures,
with a greater inhibition effect demonstrated at
higher temperatures.
Vaccari et al.161 reviewed the effects of raf-
finose on the growth of sucrose crystals from a
face-by-face analysis. Their results confirm that
the trisaccharide raffinose (galactose-fructose-
glucose) affects the rate of sucrose crystal growth
by a selective adsorption to the crystal surface,
thereby preventing further motion of the spiral
dislocations on which growth depends. This
slowing of the advancement of spiral steps has
been observed microscopically by Albon and
Dunning.162
The effects of various additives (salts, glu-
cose, raffinose, and amino acids) on growth of
sucrose have been studied by Moritsugu.163 his
results show that glucose enhanced the rate of
sucrose growth when the effects of solubility were
not accounted for. This effect increased slightly
98
as the glucose content in solution was increased
up to 9%.
Nickerson and Patel164 studied crystallization
of sucrose and lactose from mixed sugar solu-
tions. They followed the decrease in concentra-
tion of both lactose and sucrose in solution during
batch-seeded crystallization, studying a range of
mixtures from 100% sucrose to a 50:50 mixture
of sucrose and lactose. Their results show that
different proportions of lactose and sucrose crys-
tallized out of solution based on the initial sugar
concentrations, the altered solubility levels of the
two sugars, and whether lactose, sucrose, or
mixed seed crystals were used to initiate growth.
The crystal habit, solution viscosity, proportion
of lactose to sucrose in the crystal product, and
hardness of the crystalline mass were studied as
a function of the starting sugar composition. No
quantitative data on crystal growth kinetics were
obtained from these studies.
The effects of lactose hydrolysis (into glu-
cose and galactose) on the crystallization of lac-
tose from solutions that had undergone various
extents of hydrolysis was studied by Shah and
Nickerson.165 In fully hydrolized solutions, gal-
actose was the sugar found to crystallize out of
solution. At 70 or 90% hydrolysis, lactose crys-
tallized with increasing yield at lower tempera-
tures and higher dissolved solids. The glucose
and galactose acted as nucleation and growth in-
hibitors. Similar results were found by Bourne
et al.60
Van Kreveld37 studied the effects of various
sugars on the growth of a-lactose monohydrate
from purified solutions made from the stable an-
hydrous form. These solutions had low levels of
P-lactose (<2%). The effects of P-lactose on a-
lactose monohydrate crystal growth were studied
in this way. It was found that p-lactose did indeed
have major inhibiting effect on the growth of
lactose crystals, decreasing the rate of growth of
seed crystals by over an order of magnitude. The
effects of other sugars, including glucose, su-
crose, fructose, maltose, and raffinose, were also
studied. These sugars had varying inhibition ef-
fects, but not nearly to the extent of p-lactose.
Further study on the effects of P-lactose on the
growth of a-lactose monohydrate136 showed that
P-lactose did not have a major effect on crystal
 growth rate under normal conditions yielding to-
mahawk morphology. Their work suggest that
the previous results of van Kreveld37 had not
accounted for varying levels of a-lactose in so-
lution. From these results, it appears that (i-lac-
tose has an inhibitory effect at higher
supersaturations, where needle-shaped crystals
grow. However, at normal supersaturations, re-
sulting in tomahawk morphology, the {3-lactose
has very little effect. This is indicative of an
effect of (3-lactose on only some crystal faces,
resulting in different results at different super-
saturations. Definitive experiments on the effects
of 3-lactose on the individual face growth rates
have not been performed to date and some ques-
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tion still remains on the exact nature of the effect
of p-lactose on a-lactose growth.
The effects of other sugars on lactose crystal
growth have also been investigated.136 These re-
sults show that, at least at relatively low con-
centrations (5%), sugars such as glucose and
maltose have only a slight effect on the overall
growth of a-lactose monohydrate. In fact, Nick-
erson and Moore136 found glucose and maltose
to increase slightly the rate of lactose crystal
growth. On the other hand, Michaels and van
Kreveld141 found no effect from these sugars on
lactose crystal growth. However, it is not clear
whether the solubility effects of these sugars were
accounted for in these studies.
Some work has been done recently on the
effects of added sugars and natural polymeriza-
tion products on the growth of fructose crystals.
Chu et al.153 studied the effects of glucose ad-
dition on fructose crystal growth and found a
slight inhibition, although the effects of glucose
on fructose solubility were not taken into ac-
count. The presence of difructose dianhydrides
in solution was seen to markedly decrease the
growth rates due, most likely, to incorporation
into the crystal lattice. Similar results were re-
ported by Watanabe.152
2. Macromolecules
The presence of large macromolecules, such
as proteins, starches, dextrans, etc., can cause
significant influences on the rate of mass transfer
of sugar molecules through the solution and, thus,
have a significant effect on the rate of crystal
growth. In addition, these macromolecules may
adsorb to the crystal surface and influence the
manner by which sugar molecules attach to the
crystal lattice. The mechanism of action of each
particular impurity must be studied individually,
and rarely will an additive act by solely one
mechanism of growth inhibition.
Smythe55 shows data on the growth inhibition
of sucrose in the presence of several macromol-
ecules, including dextrin, pectin, and dextran.
His results demonstrate the magnitude of growth
inhibition resulting from the presence of these
additives during sucrose crystal growth at 41°C.
Pectin at 5 g/g water and dextrin at 10 g/g water
were found to reduce the growth rate of sucrose
crystals by about 16% over the range of AC from
10 to 60 g sucrose per 100 g water. Dextran, at
a level of 7.4 g/g water, had a larger effect,
slowing down the rate of growth by over 30%.
Parrisch and Clarke166 summarize results on dex-
trans and other oligo- and polysaccharides of im-
portance in sugar refining. They discuss the
changes in crystal growth rate as well as changes
in crystal habit resulting from these impurities.
The mutual effects of these polysaccharides and
salts are also discussed in some detail.
Michaels and van Kreveld141 demonstrate the
inhibition effect of various surface-adsorbing
agents on the growth of lactose. For example,
the addition of 10 ppm gelatin reduced the growth
rate by 25 to 66%, depending on the face ob-
served. They conclude that the effect of gelatin
is nonselective with respect to individual faces
and that a general adsorption of the gelatin onto
the lactose crystal surfaces causes the growth
inhibition.
3. Salts
Several salts have been shown to decrease
the rate of sucrose crystal growth. These include
CaCl2, KC1, and disodium hydrogen phosphate.55
Inhibition was seen to increase with increasing
salt concentration and was generally similar in
magnitude to equivalent levels of invert sugar
addition. CaCl2 addition, however, showed no
effect on growth at a level of 15 g/g water. Ad-
dition of 32 and 52 g CaCl2 per g water showed
99
 an inhibition on growth that was significantly
larger than the equivalent level of invert sugar.
Mak167 studied the effects of a wide variety
of salts on sucrose growth in order to determine
the effects of ionic impurities on crystal growth
processes. Included in the list of salts studied
were LiCl, RbCl, CsCl, SrCl2, BaCl2, NaCl, KC1,
and KI. Each of these salts was found to decrease
the rate of growth of several individual faces of
the sucrose crystal. The magnitude of the inhi-
bition was dependent on the specific salt and the
face under observation. Since each salt affected
different faces to different extents, the shape of
the crystals grown in the presence of these ad-
ditives was quite different from the normal su-
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crose crystal habit. The mechanism of this growth
inhibition was related to the effect of these ionic
impurities on the hydrogen bonding sites of the
sucrose molecules, thereby preventing incorpo-
ration of sucrose molecules into the crystal lattice.
The effects of KC1 on growth of sucrose were
also studied by Moritsugu.163 Concentrations of
up to 5% KC1 in sucrose solution were shown to
cause a 25% decrease in the rate of growth, when
compared with a pure solution at the same su-
persaturation. Moritsugu163 also shows the effects
of a variety of additives on sucrose growth from
solutions with constant sucrose content. Here, the
supersaturation changes due to the changing sol-
ubility concentration with additive addition. The
salts KC1, Na2CO3, and K2CO3 gave a decreasing
rate of growth as the addition level was increased.
However, CaCl2, MgCl2, K2SO4, and, to a lesser
extent, NaCl gave an initial increase in growth
rate before falling off to levels below those of
the initial pure solution. The actual effect of these
salts must be separated from the solubility effects
to determine mechanism changes; however, some
interesting practical results are obtained in this
way. Similar studies on combination of salts in
solution resulted in varying degrees of growth
enhancement or inhibition. Their conclusion was
that the effects of individual salts in combinations
were not additive, although the effects of solu-
bility were not separated.
The effects of various salts on lactose crystal
growth have been studied in some detail,142 par-
ticularly those salts that are present in cheese
whey from which commercial lactose is refined.
100
Jelen and Coulter142 studied the effects of calcium
chloride, sodium phosphate, and potassium chlo-
ride on the relative rates of growth of a-lactose
monohydrate crystals from cheese whey (protein
removed) at 50°C. Under these conditions, it was
found that each of the salts caused a significant
initial increase in the rate of lactose crystal growth,
as measured by the weight change of single crys-
tals. For calcium chloride and potassium chlo-
ride, higher salt concentrations (>5 to 10% TS
addition) resulted in subsequent decreases in
growth rate. That is, the growth rate effect was
dependent on the salt concentration, with a max-
imum rate of growth occurring between a 5 to
10% addition of these salts. Sodium phosphate,
on the other hand, showed a continually increas-
ing function of relative growth rate on salt con-
centration, up to 20% addition. In this work, the
effects of these salts on lactose solubility was not
considered.
4. Surfactants
Van Hook168 summarizes past work on the
effects of surfactants on sucrose crystallization.
He concludes that surfactants have no effect on
the rate of growth, as shown by single crystal
growth experiments, but may have some effect
on the overall crystal population due to the effects
on secondary nucleation. These effects have not
been clearly defined.
Surfactants have been found to have some
effect on lactose crystal growth when the solu-
bility effects were not considered. Michaels and
van Kreveld141 studied several surface-active
agents for their effects on lactose crystal growth
at 30°C and lactose concentrations of 41.5 and
60 g lactose monohydrate/100 g water. One sub-
stance (trimethyl octa decyl ammonium chloride)
was found to nearly halt the lactose growth, while
another (sodium dodecyl (tetrapropylene) ben-
zene sulfonate) was found to enhance the rate at
lower addition levels, but then to decrease the
rate of growth at higher addition levels. These
results were slightly dependent on the supersa-
turation level. The effects of these additives on
solubility were not investigated.
 5. Others
The effects of organic compounds, such as
urea, aconitic acid, mannitol, sorbic acid, iso-
butyric acid, and mixed amino acids, on the rate
of sucrose crystal growth at various supersatur-
ations was studied by Smythe.55 His conclusions
were that these compounds inhibit growth on the
same order of magnitude as similar concentra-
tions of invert sugar. Organic coloring agents,
naturally present in cane and beet juice, have also
been shown to inhibit the rate of sucrose crystal
growth,169 although solubility effects were not
taken into account. In this study, sucrose crystal
growth was seen to decrease by about 25% upon
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increasing the coloring matter content by 400%
over that normally found in refiner's syrups.
Naturally occurring constituents of whey also
have an important impact on the crystallization
process for refining lactose. Riboflavin has been
found to affect both growth rate and product mor-
phology.170 The riboflavin adsorbs to the lactose
crystal surface and thereby slows down specific
faces in such a way that thin plate-like crystals
are formed. Michaels and van Kreveld141 also
observed a decrease in the growth rate of specific
faces in the presence of riboflavin. At 10 ppm
addition of riboflavin, no growth inhibition effect
was observed. However, addition of 50 or 100
ppm riboflavin to lactose solution was seen to
decrease the growth rate of the individual faces
to varying extents. This resulted in the formation
of the plate-like crystals observed previously due
to the addition of riboflavin.170
6. Summary of Effects of Additives/
Impurities on Crystal Growth
The effects of additives and impurities may
be broadly categorized into those compounds that
affect the viscosity or mass transfer conditions in
the solution and those compounds that inhibit the
incorporation of sucrose molecules into the lattice
structure. The former compounds include invert
sugar, dextrans, and pectin, while the latter group
is represented by salts, raffinose, and other oli-
gosaccharides with a structure comparable to that
of sucrose. The former group inhibits mass trans-
fer of the sucrose molecule through the solution
to the crystal surface and thereby slows down the
volume diffusion rate. The latter group inhibits
growth by disrupting the incorporation of sucrose
molecules into the lattice. They may either adsorb
to the crystal surface or become incorporated into
the lattice kink sites themselves, thereby pre-
venting any further incorporation of sucrose mol-
ecules due to the mismatch caused by the
nonsucrose portion of the molecule (the galactose
moiety in raffinose). Alternatively, they may act
to modify the sucrose molecule in such a way as
to prevent incorporation, i.e., the salt ionic ef-
fect. The magnitude and overall effect of an ad-
ditive may change, depending on the conditions
of growth. That is, additives that affect the rate
of mass transfer may be expected to have a greater
influence at higher temperatures where volume
diffusion plays an important role in the growth
mechanism of pure sucrose.
Smythe55 quantified the influence of addi-
tives on the rate of mass transfer by accounting
for the change in viscosity. He was able to derive
an expression that related the rate of growth to
the viscosity of the solution at a given supersa-
turation. The expression resulted in the rate of
growth being inversely proportional to the vis-
cosity raised to the 1.4 power. This exponent
may be dependent on the agitation rate during
growth, as other researchers have found slightly
different results. Some compounds, such as dex-
tran and CaCl2, gave exceptions to this viscosity
rule. This is because mass transfer is affected by
both viscosity and the diffusion coefficient. Dex-
tran and CaCl2 were seen to have less of an effect
on the diffusion coefficient than invert sugar for
conditions giving similar viscosities. Therefore,
the effects of a given impurity on both viscosity
and the diffusion coefficient must be considered
in determining the overall effect on sucrose crys-
tal growth. For the class of additives that mainly
affects the incorporation of sucrose molecules
into the lattice structure, the rate of growth could
be related to the inverse of the additive/water
ratio (I/W in grams of additive per 100 grams of
water) raised to the 0.67 power at 41°C. Raffi-
nose is a primary example of this class of com-
pound, although many additives may affect the
rate of growth from both mechanisms.
101
 V. APPLICATIONS OF
CRYSTALLIZATION THEORIES TO
FOOD PRODUCTS
The crystallization of sugars in foods may
play an important role in determining the quality
of the product.171 The presence or absence of
crystals as well as their number, average size,
and size distribution are critical to the develop-
ment of the desired textural properties. Due to
the many complexities that influence the crys-
tallization of sugars in food products, much of
the available information is either qualitative or
not directly applicable to specific food products.
More information probably exists on this impor-
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tant topic; however, many companies with ex-
pertise in this area choose not to publish results
in order to maintain a competitive edge.
A. Confectionery Products
1. Grained Confections
172 175
Cakebread " presents a series of articles
on candy chemistry specifically related to grained
confections. In this series, he discusses the prac-
tical aspects of sugar crystallization in grained
confections as it relates to the development of
the texture. His discussion deals mostly with fon-
dants and creams, the simplest of grained con-
fections; however, the principles can generally
be extended to cover more complicated formu-
lations. Other summaries of note on sugar crys-
tallization processes in confectionery products
may be found in Lees,176 Mullineaux,177 and
Hartel.178
a. Fondants and Creams
In the first paper of the series, Cakebread172
discusses the solubility and viscosity parameters
for the individual sugars and their mixtures. These
parameters play an important role in determining
the crystallization phenomena in a confection, as
well as the final texture from both a solid-phase
and liquid-phase" standpoint. The second paper173
discusses the relative extent of solid vs. liquid
phase for a given fondant formulation made with
102
mixtures of sucrose and 42 DE corn syrup. Table
2 shows the solid- and liquid-phase percentages,
along with total dissolved solids remaining in the
liquid phase, as functions of the ratio of sucrose
to nonsucrose components at 80 and 90% initial
total solids. The extent of solids in the product
increases with an increasing sucrose-to-nonsuc-
rose ratio, as one would expect, since there is
more sucrose in the formulation at higher ratios
for a given initial total solids content. This results
in higher supersaturations and, thus, greater crys-
tallization rates. In addition, at higher ratios of
sucrose to nonsucrose, the inhibitive effects of
the additives are less, resulting in greater crys-
tallization. The combination of lower supersa-
turation and increased inhibition results in lower
solids in the product as more nonsucrose addi-
tives are added to the fondant formulation. When
the total solids of the initial formulation is in-
creased at a constant sucrose-to-nonsucrose ratio,
the relative percentage of the solid phase also
increases. This is, again, due to the higher
supersaturations.
The supersaturation ratios found in typical
confectionery formulations may be exceedingly
high. Cakebread174 states that the supersaturation
ratio (S = C/Cs in weight percent) for a 10:1
sucrose:corn syrup fondant with 10% moisture at
20°C can be calculated as 1.67. Most sucrose
refining occurs at a supersaturation ratio of about
1.1 to 1.2, so the value of 1.67 is exceedingly
high. Very little published data exist on the nu-
cleation and growth rates of sucrose crystals at
these high supersaturations, and the effects of
normal confectionery components (corn syrup,
invert sugar, etc.) are essentially only known
qualitatively.
Since the texture of a confection is dependent
on the size of the crystals formed as well as the
amount of solid phase, the nucleation and growth
kinetics during candy manufacture will play a
critical role in the development of the final tex-
tural properties and quality of the product. As
Cakebread174 notes, supersaturation alone does
not determine the crystallization kinetics, since
several other factors can influence the final crys-
talline product. These other parameters include
the viscosity of the liquid phase (which itself is
a function of the concentration, temperature, and
additive contents), the agitation or beating rate,
 TABLE 2
Effects of Nonsucrose Additives on Solid- and Liquid-Phase Contents in Fondants

Total solids ou/o

(%) Sucrose: TS in liquid TS in Liquid

Nonsucrose Solid (%) Liquid (%) (%) Solid (%) Liquid (%) (%)

2:1 28.1 71.9 72.7 53.3 46.7 78.6

5:1 31.0 69.0 71.0 59.3 40.7 75.4
7:1 33.3 66.7 70.0 62.2 37.8 73.6
9:1 34.7 65.3 69.4 63.8 36.2 72.4
11:1 35.6 64.4 68.9 64.9 35.1 71.5
13:1 36.3 63.7 68.6 65.7 34.3 70.9

Adapted from Cakebread, S. H., Manuf. Confect, December, 38,1970.

TABLE 3
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Relationship between Fondant Composition, Beating Temperature, and Crystal Size for 90%
Initial Total Solids

Percentage of total crystal

Total numbers*
Beating
Confectioners temperature solids 0—10 10—20 20—30 >30
glucose (%) CO Solid* (%) Liquid* (%) (liquid, %) fim (Jim \xm |im

10 40 60.2 42.0 76.2 92.3 7.4 1.1

10 55 54.9 45.1 77.6 89.1 9.7 1.1 1.1
10 70 53.6 46.4 78.5 83.2 12.2 3.6 1.1
25 40 50.9 49.1 79.6 99.9 0.2 — —
25 55 50.1 49.9 80.0 96.2 3.5 0.3 —
25 70 44.6 56.0 82.2 89.5 7.7 1.8 0.4

• Percentages may not total 100% due to inaccuracies in original work.

Adapted from Lees, R., Factors Affecting Crystallization in Boiled Sweets, Fondants and other Con-
fectionery, BFMIRA Scientific and Technical Survey 42,1965.

the temperature at which beating takes place, and
the formulation of the sugar syrup (since many
additives are crystallization inhibitors). A full un-
derstanding of the effects of each of these pa-
rameters has not been developed as yet, although
some qualitative understanding exists. An ex-
ample of the above influences can be seen in
some data presented by Cakebread174 and Lees,176
as taken from a Russian source. The effects of
beating temperature on the crystal size distribu-
tion in fondant was determined. These results are
summarized in Table 3. In general, as the beating
temperature is increased, the percentage of larger
crystals (>20 |xm) is seen to increase. Desmarais
and Ganz179 show the same effect of increased
crystal size with increased beating temperature.
This is partially due to the lowered viscosities at
these elevated temperatures allowing more sub-
stantial growth of the nuclei that are formed and
partially due to the phenomena of nucleation being
inhibited by higher viscosities.176 In addition, the
intensity of beating influences the crystal size
distribution. Rapid beating generally results in
smaller crystals, while slow beating gives a
coarser fondant. Previous authors174-176 have at-
tributed this to the effects of depletion of the
syrup phase around a growing crystal, which re-
sults in cessation of growth. The effects of energy
input on nucleation may also play a direct role
in this as well, since the number of nuclei formed
is directly related to the amount of energy put
into the solution. If a great many nuclei are
formed, the overall extent of growth of any one
crystal will be less than if there were lower num-

103
 bers of crystals. This is the result, again, of com-
petition between nucleation and growth for
available supersaturation.
Another factor observed to affect the crystal
size distribution in fondants is the syrup formu-
lation. Previous work, as reported by Cake-
bread,174 Lees,176 and Mullineaux,177 shows that
the higher the level of corn syrup in the fondant
formulation, the smaller the crystals in the prod-
uct (see Table 3). This work also shows that
smaller crystals are formed when the total solids
content in the confection is higher. Additives,
such as corn syrup and invert sugar, will tend to
reduce both the rate of nucleation and the sub-
sequent rate of growth of these nuclei at condi-
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tions of identical supersaturation. Since these
components also reduce the solubility of sucrose
in solution, the supersaturation of various for-
mulations with varying compositions will also be
different, and exact comparison of the crystalli-
zation effects is not possible with the available
data. However, some general trends can be
understood from the basic information given in
the previous sections on crystallization phenom-
ena. When the total solids content is increased
for a given ratio of sucrose to corn syrup, the
supersaturation of the sucrose will increase due
to the additional sucrose in solution. Thus, higher
nucleation rates will occur at these higher total
solids levels, resulting in the formation of greater
numbers of particles. This is demonstrated by the
increase in the percentage of solids in the fon-
dant, which also increases with increasing total
solids in the formulation. The larger number of
particles formed will result in less growth onto
each crystal (although the total mass deposited
must be the same in order to reach equilibrium)
and, therefore, the average size of the crystals
will be lower. When the percentage of corn syrup
is increased in the formulation, the solubility of
sucrose is further decreased, but the total amount
of sucrose is also decreased. The net effect is
that the supersaturation of sucrose is lowered.
The rates of nucleation and growth are also low-
ered due to the inhibitive effect of the corn syrup.
Therefore, the number of crystals that are formed
is lower at high corn syrup additions; however,
these crystals do not grow very large due to the
lower supersaturations.
The effects of added fructose (0 to 10%) on
104
crystallization processes in fondants has been
studied in detail by Mullineaux.177 The average
size of the fondant sugar crystals and the per-
centage of solid in the product was seen to de-
crease as the fructose content was increased (for
a constant initial total solids level). These results
are similar to those described above. Addition of
cellulose gum (CMC) on the crystallization of
fondants has been studied by Desmarais and
Ganz.179 Addition of CMC resulted in smaller
sucrose crystals and slower growth since the CMC
acted as a crystallization inhibitor. DuRoss and
Knightly180 demonstrate the effects of added sor-
bitol on the average size of sucrose crystals in
fondants made with sucrose, corn syrup solids,
and sorbitol. Since these studies have varied com-
position of these ingredients, it is impossible to
determine, from a mechanistic standpoint, which
components have the greatest effect on the size
and exactly how this effect is accomplished. These
results clearly show, however, that varying the
ingredient composition can have a significant ef-
fect on the crystallization properties, as well as
on the overall textural characteristics of the fon-
dant, since sorbitol is an effective humectant.
More controlled studies with ingredient addition
at levels appropriate for comparison at constant
supersaturation levels must be performed in order
to determine the crystallization mechanisms im-
portant for each individual ingredient.
Cakebread174 and Lees176 also discuss changes
in crystal size during storage of fondants. Lees176
references earlier data that show an increase in
the mean size of a fondant from 2.7 |xm after 1
h to 5.2 \xm after 22 d of storage. The results of
Desmarais and Ganz179 and Woodruff and Van
Gilder181 also demonstrate the increases in av-
erage crystal size in fondants of different for-
mulations during storage for up to 1 month. These
authors also suggest that the width of the distri-
bution (spread of crystal sizes) decreases during
this storage period. That is, the difference be-
tween the largest and smallest crystals gets rel-
atively smaller as the fondant matures. These
changes in storage have been related to the con-
tinued growth of the seeds present in the fondant
after manufacture, and the subsequent decrease
in the concentration of the liquid phase results in
softening of the fondant. Whether these changes
in crystal size are due to growth caused
 by normal depletion of the supersaturation or by
some other effect, particularly crystal ripening,
remains a subject for further study.
Cakebread174-175 considers the idea that the so-
lution around each growing crystal may become
depleted and thereby reduce any further imme-
diate crystal growth. On storage, however, suf-
ficient time is allowed for sucrose molecules in
the solution at further distances from the crystals
to diffuse or migrate to the crystal surface. Slow
growth, dependent on the rate of mass diffusivity
of sucrose molecules through the solution, will
result. Lees176 discusses the possibility of the ma-
turing of fondants being due to insufficient crys-
tallization time (insufficient beating, excessive
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beating, or high invert sugar content). That is,
only fondants that have not been properly crys-
tallized undergo further changes on storage. On
the other hand, these crystal size changes may
be due to Ostwald ripening effects due to the
small sizes of the sugar crystals.178 In the ther-
modynamic process of ripening, small crystals
dissolve due to their enhanced solubility, while
the larger crystals grow. In practice, the effects
of ripening appear to be the growth of larger
crystals along with the disappearance of smaller
ones. Further details of Ostwald ripening theory
may be found in Mullin.54 The exact mechanism
of crystal size changes in maturing fondants is
not clear from the data available in the literature.
Some combination of each of the above ideas
may actually occur within a maturing fondant.
Detailed investigations on the number and size
distribution of sucrose crystals during storage of
a fondant will be necessary to specify the exact
mechanism.
Heating of fondants after manufacture and
storage will also have a significant impact on the
final product crystal size distribution.174-175 If the
fondant is heated to a high enough temperature
(dependent on formulation), some of the small
crystals will begin to dissolve and eventually dis-
appear until the solid and liquid phases approach
the equilibrium condition for that temperature.
When the fondant is cooled again to storage tem-
perature, the solution returns to the supersatur-
ated state and the remaining crystals will grow
(no new crystals will form). Thus, the remaining
crystals will be larger and the fondant will be
coarser. Continued fluctuations in temperature
will cause the fondant to become more and more
coarse. Addition of a sugar syrup (bob-syrup) for
the processing of fondants or creams will result
in similar coarsening due to the elevated tem-
peratures required for mixing and blending of the
fondant with the syrup.
Moisture considerations also play an impor-
tant role in the stability of the sugar crystals in
a fondant, particularly on storage. If a fondant
is stored in a dry place, where the relative hu-
midity is lower than the equilibrium relative hu-
midity of the solution phase, the fondant will dry
out. This moisture loss will cause the concentra-
tion in the liquid phase to increase, resulting in
higher supersaturations. The crystals will then
grow to equilibrate with this new solution con-
dition. In practice, however, a crust of high crys-
talline content will be formed where the drying
takes place and further drying will be reduced.
On the other hand, if the fondant is stored in high
relative humidity conditions, it will pick moisture
up from the air. This added moisture may cause
dissolution of some crystals if the solution con-
centration is decreased sufficiently. The presence
of other sugars in the fondant may play an im-
portant role in determining the effects of storage
moisture on the fondant characteristics.
Mullineaux177 investigated the effects of fructose
on the keeping properties of fondants. The results
showed that fructose has a stabilizing effect on
the fondant when stored under conditions that
would normally dry out the fondant. The fructose
acted as a humectant in this case to maintain
product moisture. However, very little effect on
storage stability under moist storage conditions
was observed.
Studies on other grained confections (fudge,
grained nougats, etc.) are summarized by Lees.176
Although there is very little quantitative data on
these products, behavior similar to fondants and
creams would be expected. The addition of other
additives, such as gelatin and pectin, will have
specific inhibiting activity on the nucleation and
growth of sucrose crystals. Due to the complexity
of these formulations, the effects of specific con-
stituents have generally not been delineated.
b. Panned Products
Although the development of panned sugar
105
 coatings, either hard coatings (as in jawbreakers)
or soft coatings (as in jellybeans), depends to a
great extent on the control of sugar crystalliza-
tion, very little work has gone into understanding
how sugar crystals form during the panning pro-
cess. This situation leaves the processor of panned
goods with a process that is more of an art than
a science. There is a definite need for developing
an understanding of the influences of product and
processing parameters on the rate of heat and
mass transfer during the coating and drying steps
of the panning process. The relative rates of these
transport processes when compared with the crys-
tallization kinetics is crucial in determining the
formation of the sugar shell during panning.
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2. Ungrained Confections
In the case of hard candies, nougat, toffee,
jellies, etc., the formation of sugar crystals is
considered a defect to be avoided. Here, infor-
mation pertinent to the prevention of sucrose
crystallization becomes important. In hard can-
dies and toffees, high-concentration syrups are
made by boiling to high temperatures to drive off
moisture. These syrups are then cooled rapidly
below the point where nucleation of the sucrose
will occur. Nucleation is further inhibited by ad-
dition of invert sugar or corn syrup to result in
a stable hard candy in the amorphous state (glass).
The critical parameters for forming this sugar
glass are moisture content (or total solids), rate
of cooling, temperature to which it is cooled, and
presence of nucleation-inhibiting additives. When
the proper conditions are met, a stable amorphous
solid can be formed.
Under certain conditions, particularly if these
products are stored improperly, the glassy struc-
ture may devitrify or crystallize. In the devitri-
fication process, sugar crystals form directly from
the amorphous phase. This may occur when the
product is stored at relatively high temperatures
and high relative humidities. The candy picks up
moisture from the environment, allowing the sugar
molecules to rearrange and form into a crystal
lattice.176178 Proper packaging has essentially
eliminated this problem in most commercial
applications.
106
B. Dairy Products
1. Spray-Dried Powders
Spray drying of fluid dairy products results
in the formation of amorphous lactose powders.
Upon storage or conditioning under moist air con-
ditions, the amorphous lactose will devitrify and
crystalline lactose will form. If a crystalline lac-
tose product is required in the final powder, the
lactose may be precrystallized in the liquid phase
prior to drying. Crystallization before and after
drying results in different properties of the pow-
ders since the course of lactose crystallization is
quite different. Roetman182 examined the micro-
scopic structure of spray-dried powders and dra-
matic differences in lactose crystal structure were
observed between "precrystallized" and "po-
stcrystallized" powders. Scanning electron mi-
crographs showed that the tomahawk-shaped a-
lactose monohydrate crystal was formed in the
powder when the lactose was allowed to crys-
tallize in the liquid prior to spray drying. In con-
trast, needle-shaped crystals of lactose were
formed when the amorphous powders were al-
lowed to crystallize after spray drying. These
differences may be attributed to the different su-
persaturation values at which crystallization takes
place. Exceedingly high supersaturations must
exist during the devitrification of the amorphous
structure due to the high lactose concentrations.
From the pictures presented by Roetman,182 it
was not clear whether the needles were crystals
of a- or p-lactose. Herrington76 stated that lactose
glasses are supersaturated with respect to both a-
and p-lactose. Therefore, either crystal structure
may form from the devitrified powders, although
no experimental evidence was given for this state-
ment and no conditions were given that favor one
form over the other. Furthermore, work by Bush-
ill et al.183 using X-ray diffraction has demon-
strated that a crystal of combined forms may be
crystallized from spray- or freeze-dried milk
powders. These crystals had a molar ratio of a-
monohydrate to |3-anydride lactose of 5:3.
Further work on the crystallization of lactose
from dairy powders has been undertaken by
Saito184-185 and Wursch et al.186 Their results sug-
gest that p-lactose was crystallized from whole
 milk powders, but not from skim milk or whey
powders. This was attributed to the effect of the
fat on the movement of moisture within the pow-
der, although this has not been experimentally
verified. All crystals formed in these studies were
of the typical a-monohydrate or 3-anhydrous form
and no evidence for the 5:3 mixture of Bushill
et al.183 was observed. These studies are impor-
tant in that the state of lactose (amorphous or
crystalline) determines the flow and physical
properties of the powder,187 yet no clear under-
standing of the crystal formation process in dairy
powders has been presented to date.
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2. Ice Cream
The crystallization of lactose in ice cream
has been a problem in the past, since the growth
of large lactose crystals imparts a sandy texture
to the ice cream. Lactose crystallization in ice
cream should be avoided for the highest-quality
product. Yet, when ice cream is hardened, the
solubility of lactose in the fluid phase of the prod-
uct is exceeded by a large extent, resulting in
high supersaturations. Nickerson188'190 reviewed
the factors affecting lactose crystallization in ice
cream and the factors responsible for the reduced
incidence of sandiness in ice creams. Seeding of
ice cream with finely ground a-lactose crystals
was studied as a means of preventing the for-
mation of large lactose crystals responsible for
the sandy texture. The principle here was that
each of the many small nuclei would grow only
a small amount as the crystallization equilibrium
was approached and that these fine crystals would
remain below the threshold detection size. The
critical aspect of this seeding was that sufficient
lactose seeds were required so that the final crys-
tal size remained small. Nickerson190 stated that
the widespread use of gum stabilizers in the ice
cream mix formulation essentially prevents the
formation of large lactose crystals by inhibiting
the growth of these crystals. Thus, sandiness in
ice cream due to lactose crystallization is rarely
a problem under current manufacturing principles.
3. Sweetened Condensed Milk
A gritty or sandy texture can be found in
sweetened condensed milk due to the growth of
large (>25 p.m) lactose crystals if proper pro-
cessing conditions are not followed. The high
concentrations of lactose combined with the low
solubility level due to sucrose addition result in
high supersaturations for lactose. If careful ad-
dition of a large quantity of fine lactose seed
crystals is not accomplished during the process,
growth of large lactose crystals will occur. Under
normal conditions, sufficient seeds are added such
that the growth of any one crystal is small, yet
enough total mass deposition occurs to decrease
the supersaturation to safe levels.39
VI. SUMMARY
The crystallization of sugars plays an im-
portant role in determining overall product qual-
ity and textural characteristics. Control of the
crystallization process is critical to the formation
or prevention of sugar crystals. In many food
products, however, the complex interactions of
ingredients in terms of enhancing or preventing
crystal nucleation and growth result in a lack of
quantitative understanding of the specific effects.
In addition, the nucleation process is somewhat
spurious in nature due to the statistical variations
necessary to create nuclei centers. This results in
varying nucleation times that seem to depend on
no parameter in particular. Thus, control of crys-
tallization processes in foods in general is a dif-
ficult task at best. Many commercial processes
are still based on prior art tempered by a modicum
of quantitative information. Further studies re-
garding the basic mechanisms of crystal forma-
tion are necessary to fully understand the details
of textural development in crystallized food
products.
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