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
Nucleation rate, or the number of crystals formed (per unittime per unit volume), for a given sugar is dependent on bothinternal and external factors. As noted above, each sweetener hasa 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 ofa supersaturated state to nucleate. In some sugars, a fairly widezone of supersaturation exists where nucleation is limited; in thismetastable zone, sweetener molecules do not attain the criticalcluster size for conversion to a stable nucleus. The width of themetastable zone of sucrose, mannitol, maltitol, and xylitol correlateswith the propensity of these sweeteners to crystallize (Bensouissiand others 2010). That is, systems with a lower metastablezone are faster nucleating than those with a large metastablezone.Measuring nucleation rate has generally proven difficult—nucleiare defined as the initial crystal forms, before the crystals grow to asize where they can be observed, and counting the number of nucleiformed over time is difficult. Because of this difficulty, manystudies have investigated the induction time for nucleation andthen assumed an inverse relationship between induction time andnucleation rate; however, this relationship does not work underall circumstances, especially when near the glass transition region(Levenson and Hartel 2005). Furthermore, measurement of inductiontime is also difficult since the time required for nuclei toreach a detectable size is often longer than the true induction timerequired for initial onset of formation of nuclei.Although numerous methods have been used over the years tomeasure nucleation rate or induction time, most of these methodsmake assumptions and introduce errors that limit their accuracy.One of the simplest methods of characterizing nucleation rateis to count the number of crystals that form as a function oftime. However, the time required for nuclei to grow to detectablesize may introduce significant errors depending on the sensingmeasurement. Besides visual and microscopic observations, toolssuch as calorimetry, turbidity, x-ray, and other spectroscopic toolshave been used. Sensing methods that get closest to the actualnucleus formation give the best results. Recently, Stapley andothers (2009) used an image analysis method to extract nucleationrate for samples nucleating on a microscope stage.To further compound the difficulties of studying nucleation,the natural variability inherent in formation of the crystal latticegenerally results in hugely variable results. A classical study on sucrosenucleation by Van Hook and Bruno (1949) documented thisvariability. Under carefully controlled conditions, a supersaturatedsucrose solution poured into 4 different vials varied in inductiontime from as short as a few hours to as long as 24 h. Only slightdifferences in the nucleating capability of heterogeneous nucleisites are sufficient to give such variable nucleation results. Experimentalmeasurement of induction time for nucleation of a sucroseand corn syrup mixture (based on microscopic evaluation of thepresence of crystals) showed that the variability in time for onsetof nuclei formation was greatest when induction times were attheir highest (Figure 8). That is, at the optimal temperature fornucleation, induction time was shortest and so was the variabilityin nucleation rate.Because of the variability in nucleation, seed crystals are oftenadded to bypass the nucleation step. For example, seeding ofnougat, fudge, or marshmallow with a small amount of fondantor powdered sugar circumvents the need for controlling nucleiFigure 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 withagitation initiated once syrup had reached the desired temperature (datafrom E. Wesner, unpublished).formation (Minifie 1999). Rather than carefully cooling and agitatingthe mass to induce graining, the fudge maker can electsimply to add fondant to the mass after cooking. The seed crystalsthat remain after adding fondant simply dissolve or grow until thesaturation concentration has been reached. However, the trade-offwith seeding is that the crystal size in the finished product is onlyas small as the size of the seed crystals added; thus, slightly coarserproduct is generally obtained from seeding
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