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