Although phase/state behavior is important, the second piece
to understanding and controlling phase transitions of sweeteners
is kinetics, or the rate at which crystallization (nucleation and
growth) takes place. Primarily, the rate of formation of nuclei is
the most important aspect for controlling crystallization since nucleation
rate determines the total number of crystals present in the
final product. However, the rate of crystal growth can influence
final properties as well. The rate of crystallization is governed by
a supersaturation driving force, but is also influenced by external
conditions such as heating or cooling rates, evaporation rates, and
shear or agitation rates. Furthermore, a supersaturated state may
exist but not lead to formation of crystals due to other constraints.
The effects of doctoring agents to moderate crystallization in confections
and the inability of the highly supersaturated glassy state
to grain are 2 examples where kinetic constraints act to retard or
completely inhibit crystallization.
The rate of crystallization is an important factor since it determines
the nature of the crystalline phase, whether there are
numerous small crystals or fewer larger crystals (Hartel 2001). The
nature of the crystalline dispersion influences numerous properties
of the food, including texture and appearance. For example, improper
crystallization in fondant leads to the occurrence of large
crystals that impart an undesirable coarse texture (Lees 1965).
Crystallization mechanisms
The general principles of crystallization have been covered in
great detail elsewhere (Dirksen and Ring 1991; Mullin 2001).
Crystallization in foods and sweeteners has also been reviewed in
detail (Hartel and Shastry 1991; Hartel 2001). In this section, we
briefly review the general principles and add recent citations on
mechanisms of sweetener crystallization.
Nucleation. Nucleation is the first and the most important step
of crystallization. Since the number and extent of nuclei determine
the amount and size of crystals in the finished product, controlling
crystallization starts with controlling nucleation (Hartel 2001).
Crystals can form only from a supersaturated solution, in which
the sweetener concentration exceeds the solubility concentration.
At a molecular level, nucleation occurs when enough sugar
molecules come together in an arrangement that minimizes their
free energy, leading eventually to formation of a crystal lattice.
While in the liquid state, sugar molecules associate with water
molecules through hydrogen bonds, with the number of molecules
of solvation water depending on the chemical structure of the
sugar and concentration of the dissolved sugar. For nucleation to
occur, these water molecules (the hydration layer) must de-solvate
from the sugar molecules to allow sugar-sugar molecular interactions,
which happen with increasing frequency as concentration
increases above the solubility concentration. A stable nucleus is
formed when a cluster of sugar molecules reaches the critical size,
which decreases with increasing supersaturation (Mullin 2001).
The propensity of different sugars to nucleate can be quite different;
for example, mannitol and maltitol nucleate readily compared
to sucrose and xylitol (Bensouissi and others 2010). How easily
nucleation occurs depends on the physicochemical properties of
the sweetener, such as solubility, viscosity (diffusivity), surface tension,
and hydration number (number of water molecules associated
with the sweetener molecule) (Bensouissi and others 2010).
Nucleation can occur by either homogeneous or heterogeneous
mechanisms. Homogeneous nucleation occurs when a sufficient
number of molecules come together to form a 3-dimensional, stable
nucleus, whereas in heterogeneous nucleation, a solid substrate
replaces a portion of the molecules needed to form a stable cluster.
Due to the natural presence of nucleating sites (such as dust
particles, other impurities, and so on), heterogeneous nucleation
is generally the predominant form of nucleation in foods. The
energy required for the formation of crystal volume and surface
(Dirksen and Ring 1991; Mullin 2001) needs to be overcome
by the driving force, or supersaturation. In heterogeneous nucleation,
foreign nucleation sites (dust and so on) decrease the energy
needed and the degree of supersaturation required for nucleation
(Mullin 2001).
Nucleation rate, or the number of crystals formed (per unit
time per unit volume), for a given sugar is dependent on both
internal and external factors. As noted above, each sweetener has
a propensity for nucleation based on its physicochemical nature,
but external heat and mass transport conditions (such as temperature,
cooling rate, and agitation) can also influence the ability of
a supersaturated state to nucleate. In some sugars, a fairly wide
zone of supersaturation exists where nucleation is limited; in this
metastable zone, sweetener molecules do not attain the critical
cluster size for conversion to a stable nucleus. The width of the
metastable zone of sucrose, mannitol, maltitol, and xylitol correlates
with the propensity of these sweeteners to crystallize (Bensouissi
and others 2010). That is, systems with a lower metastable
zone are faster nucleating than those with a large metastable
zone.
Measuring nucleation rate has generally proven difficult—nuclei
are defined as the initial crystal forms, before the crystals grow to a
size where they can be observed, and counting the number of nuclei
formed over time is difficult. Because of this difficulty, many
studies have investigated the induction time for nucleation and
then assumed an inverse relationship between induction time and
nucleation rate; however, this relationship does not work under
all circumstances, especially when near the glass transition region
(Levenson and Hartel 2005). Furthermore, measurement of induction
time is also difficult since the time required for nuclei to
reach a detectable size is often longer than the true induction time
required for initial onset of formation of nuclei.
Although numerous methods have been used over the years to
measure nucleation rate or induction time, most of these methods
make assumptions and introduce errors that limit their accuracy.
One of the simplest methods of characterizing nucleation rate
is to count the number of crystals that form as a function of
time. However, the time required for nuclei to grow to detectable
size may introduce significant errors depending on the sensing
measurement. Besides visual and microscopic observations, tools
such as calorimetry, turbidity, x-ray, and other spectroscopic tools
have been used. Sensing methods that get closest to the actual
nucleus formation give the best results. Recently, Stapley and
others (2009) used an image analysis method to extract nucleation
rate for samples nucleating on a microscope stage.
To further compound the difficulties of studying nucleation,
the natural variability inherent in formation of the crystal lattice
generally results in hugely variable results. A classical study on sucrose
nucleation by Van Hook and Bruno (1949) documented this
variability. Under carefully controlled conditions, a supersaturated
sucrose solution poured into 4 different vials varied in induction
time from as short as a few hours to as long as 24 h. Only slight
differences in the nucleating capability of heterogeneous nuclei
sites are sufficient to give such variable nucleation results. Experimental
measurement of induction time for nucleation of a sucrose
and corn syrup mixture (based on microscopic evaluation of the
presence of crystals) showed that the variability in time for onset
of nuclei formation was greatest when induction times were at
their highest (Figure 8). That is, at the optimal temperature for
nucleation, induction time was shortest and so was the variability
in nucleation rate.
Because of the variability in nucleation, seed crystals are often
added to bypass the nucleation step. For example, seeding of
nougat, fudge, or marshmallow with a small amount of fondant
or powdered sugar circumvents the need for controlling nuclei
Figure 8–Time required for onset of sucrose nucleation for sugar syrup
(80:20 sucrose to 42 DE corn syrup; 20% water content). Syrups (n = 3)
were cooled quickly from 80 ◦C to observation temperature with
agitation initiated once syrup had reached the desired temperature (data
from E. Wesner, unpublished).
formation (Minifie 1999). Rather than carefully cooling and agitating
the mass to induce graining, the fudge maker can elect
simply to add fondant to the mass after cooking. The seed crystals
that remain after adding fondant simply dissolve or grow until the
saturation concentration has been reached. However, the trade-off
with seeding is that the crystal size in the finished product is only
as small as the size of the seed crystals added; thus, slightly coarser
product is generally obtained from seeding.