Crystal growth. After the formation of nuclei, molecules start
to diffuse and attach to the surface of the crystal (Dirksen and
Ring 1991; Mullin 2001). At the same time, molecules of water
and any other dissolved molecules diffuse away from the growing
surface (Mathlouthi and Genotelle 1998). The molecules of the
crystallizing species are thought to migrate along the surface until
they find a suitable site to incorporate into the lattice structure. As
the crystal grows, the latent heat of crystallization must be removed
from the vicinity, either through the liquid phase and/or through
the growing crystal.
At the macroscopic level, heat and mass transfer are both important
in the crystal growth process. However, heat transfer is
relatively fast compared to mass transport phenomena and, consequently,
mass transport limitations generally control the crystal
growth rate while heat transport seldom has an effect on crystal
growth of sugars (Dirksen and Ring 1991). In general, growth of
sucrose crystals has been shown to be limited primarily by diffusion
of sucrose molecules to the growing surface and diffusion
of growth units along the surface to a lattice incorporation site
(Van Hook 1981). Depending on supersaturation, surface growth
is generally driven by self-propagation of spiral dislocations at the
surface of the growing surface (Mathlouthi and Genotelle 1998)
and/or by the birth-and-spread model, where 2-dimensional nucleation
of a stable nucleus on the surface is followed by growth,
or spread, of a step as more sugar molecules fill in the layer (Khaddour
and others 2010). Martins and Rocha (2007) characterized
sucrose crystal growth according to a spiral dislocation model,
which combined 2-dimensional nucleation and spiral growth.
In addition to these surface-controlled mechanisms, desolvation
of water molecules from the sugar molecules and counter diffusion
of this free water away from the growing surface have
also been found to play a major role in determining sucrose
crystal growth (Bensouissi and others 2010). The mechanism(s)
responsible for sucrose crystal growth remains an active area of
research.
Crystal growth continues as long as the solution is supersaturated
and molecules have enough mobility to organize into the crystal
lattice. As growth continues, the concentration of the remaining
liquid phase decreases, or desupersaturates, until phase equilibrium,
as defined by the solubility curve on the phase diagram, is
reached (Hartel 2001). In Figure 1, this is seen as a decrease in
liquid phase concentration as a supersaturated system, initially at
Point A, reaches the equilibrium state (assuming constant temperature)
on the solubility curve (at Point B).
Factors that affect growth. The same parameters that influence
nucleation generally influence growth rate in much the same way.
The specific effects of each parameter depend, to some extent, on
the mechanism(s) of growth.
Supersaturation. Sucrose crystal growth has been studied extensively,
as summarized by Hartel and Shastry (1991). For the most
part, sucrose crystal growth rate increases linearly with increasing
supersaturation at concentrations below the point where molecular
mobility becomes a limiting factor.
As with nucleation, crystal growth rate increases as supersaturation
increases, up to the point where decreased molecular mobility
limits diffusion and growth rate decreases. For example, at room
temperature, an increase in sweetener concentration above the saturation
concentration initially results in increased growth rate as
supersaturation increases. At some point, however, the increased
concentration leads to a decrease in the ability of molecules to
diffuse and growth rate begins to decrease. When the sweetener
concentration is high enough (water content low enough) so that
the glass transition temperature of the mixture reaches room temperature,
mobility is sufficiently decreased and growth of sugar
crystals is shut down completely.
Temperature. Growth rate in concentrated sugar solutions is influenced
by changes in temperature in much the same manner as
nucleation rate.When a sweetener solution with constant concentration
is cooled, there is a temperature where growth rate reaches
a maximum, with slower growth at temperatures both above and
below that optimal point. Initially, the growth rate increases as the
solution is cooled below the solubility point due to the increased
supersaturation. However, the increased driving force induced by
cooling is offset by the decreased molecular mobility of sweetener
molecules.
Molecular mobility/viscosity. As noted for nucleation, mobility is
governed primarily by temperature and solution concentration.
Diffusivity, or the ability for molecules to move in space, generally
correlates inversely with viscosity. Diffusivity decreases (reduced
molecular mobility) as concentration increases and temperature
decreases (Zhymria 1972).
When molecular mobility is near zero, as in the glassy state,
growth is effectively stopped. Any crystals that nucleate prior to
formation of the glassy state remain unchanged, without growing,
within the metastable glass matrix. Commercial hard candies can
potentially contain crystals since a portion of the manufacturing
process falls within the crystallization boundary (see Figure 7B).
One study estimated that hard candy contains, on average, 2%
to 3% crystals (Smidova and others 2004). Any crystals imbedded
within the hard candy glass matrix do not grow despite the highly
supersaturated condition because of the lack of mobility (Hartel
and others 2008).
Agitation. Agitation of the solution phase in the presence of
growing crystals generally enhances the crystal growth rate, particularly
in systems like sugars where growth is strongly influenced
by mass transfer (Hartel 2001). Increased agitation enhances mass
transfer by convection, bringing molecules more quickly to the
growing interface. However, once any mass transfer limitation has
been completely alleviated, further increases in agitation have little
effect on growth (Van Hook 1945).
Formulation factors. Many of the ingredients used in confections
influence the rate of molecular incorporation into the crystal lattice.
Additives may affect crystal growth either due to a change
in the thermodynamic driving force (effect on solubility concentration)
or due to specific growth inhibition effects of the
individual molecules (Mullin 2001). Growth inhibition from foreign
molecules may have 3 causes (Hartel 2001): (1) the foreign
molecules may impede diffusion of the sweetener to the crystal
surface and thereby slow growth, (2) the foreign molecules may
adsorb to the crystal surface (most likely due to hydrogen bonding)
and inhibit the ability of molecules to incorporate into the
lattice, and (3) the foreign molecules may adsorb so strongly that
they actually become incorporated into the lattice itself, thereby
preventing addition of new sweetener molecules to the lattice.
To properly study the effects of ingredient additives on crystal
growth, it is necessary to account for any changes in solubility induced
by the additive. As noted previously, many of the common
additives in confections (such as invert sugar and corn syrup) also
decrease solubility, causing a change in driving force for crystallization.
As shown in Table 3, replacement of sucrose with corn
syrup in a formulation changes both the amount of sucrose present
and its solubility in the remaining water, thus changing the supersaturation.
Unfortunately, not all studies have accounted for this
difference.