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ANNUAL
REVIEWS Further Advances in Food
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Richard W. Hartel
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Annu. Rev. Food Sci. Technol. 2013. 4:27792 Keywords


The Annual Review of Food Science and Technology is ice, sugars, lipids, nucleation, growth, recrystallization
online at food.annualreviews.org

This articles doi: Abstract


10.1146/annurev-food-030212-182530
Crystals often play an important role in food product quality and shelf life.
Copyright  c 2013 by Annual Reviews. Controlling crystallization to obtain the desired crystal content, size distri-
All rights reserved
bution, shape, and polymorph is key to manufacturing products with desired
functionality and shelf life. Technical developments in the eld have im-
proved the tools with which we study and characterize crystals in foods.
These developments also help our understanding of the physico-chemical
phenomena that govern crystallization and improve our ability to control
it during processing and storage. In this review, some of the more impor-
tant recent developments in measuring and controlling crystallization are
discussed.

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INTRODUCTION
Imagine ice cream without ice crystals and you have the chalky sweet taste of freeze-dried astro-
Crystallization: naut ice cream; there would be nothing to provide a cooling effect on a hot summer day. Imagine
the overall process of chocolate without cocoa butter crystals to provide snap, gloss, and avor release. Clearly, crys-
creating solid particles tals play an important role in the functionality, quality, and consumer enjoyment of many food
out of liquids
products. In these products, getting the right crystalline phase (phase volume, size distribution,
Nucleation: morphology, polymorph, etc.) is crucial to product quality (Hartel et al. 2011). In other products,
formation of crystals
including hard candy, certain types of caramel, and cheddar cheese, the formation of crystals dur-
from liquid state
ing storage signals the end of shelf life because of a change in the desirable attributes. For example,
Growth: increase in
when lactose crystallizes out of ice cream, the sandy texture is a defect that makes it unacceptable
crystal size, usually
due to molecular (no matter how well the ice crystals are controlled).
incorporation into the Of the components in foods, the most important in terms of crystallization are water (ice),
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lattice sugars and polyols, fats, salts, and starch. Other components, including emulsiers and certain
Supersaturation: proteins, can also exhibit crystalline structures but are not as widely pertinent compared with
the thermodynamic the others. For the most part, these components crystallize within the matrix of the food, and as
driving force for structural attributes, contribute to functionality, consumer perception, and shelf life. However,
crystallization
at times certain compounds are crystallized in rening operations to produce puried ingredients
Recrystallization: (e.g., sugar, organic acids, and salt).
the process of crystal
Controlling crystallization, whether for prevention or to achieve the desired crystalline at-
rearrangements due to
minimization of tributes, is critical to producing products with the highest quality and with an extended shelf life.
internal energy Understanding the principles that underpin crystallization phenomena is necessary to achieve
that control, but further, enhanced methods of characterizing crystalline structures are needed to
ensure proper food functionality.
In this review, a brief overview of the principles of crystallization is provided before delving
into recent advances in the eld. The reader is referred to Crystallization in Foods (Hartel 2001) for
more details on crystallization principles and applications. Although there are numerous possibil-
ities for recent advances to choose from, the following areas are the focus of this review: methods
of measuring and characterizing crystalline structure in foods, new ideas for controlling crystal-
lization, and methods for optimization. Because of the scope of this review, only select articles
have been included.

PRINCIPLES OF CRYSTALLIZATION
Crystallization is often broken into four different stages. First, in order to get crystals to form
from the liquid state, the system has to reach the supersaturated zone in which there is a driving
force for crystallization. Once there is a driving force suitable to overcome the energy barrier
for crystallization, nucleation takes place, and liquid-state molecules come together in some form
to create a stable nucleus. After nuclei become stable, they quickly transition to the next stage
of crystallization, namely crystal growth, during which additional molecules (or growth units)
incorporate into the crystal lattice, decreasing the supersaturation driving force. Unless checked
by some kinetic constraint, growth continues until the system equilibrates, at which time the
driving force for crystallization goes to zero and the maximum phase volume of crystals has been
obtained. The nal stage of crystallization in foods occurs during storage, and population of
crystals goes through a recrystallization step to reach a more global state of equilibrium.
Although a thermodynamic driving force is required to initiate crystallization, this is often
not sufcient for crystals to form. The energy barrier for crystallization needs to be overcome
in a system to initiate nuclei formation. This leads to a metastable zone width that describes the

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supersaturation point above which nucleation occurs. Other kinetic constraints, whether specic
molecular interactions or limited molecular mobility, may also prevent crystallization even if
a considerable thermodynamic driving force exists. An example of this is seen in glass-forming
systems, which are metastable. There is a thermodynamic driving force for crystallization, but
kinetic limitations (decreased molecular mobility) prevent crystallization. Hartel et al. (2011)
discuss this balance between equilibrium (thermodynamics) and kinetics in terms of phase
transitions of sugars in confections.

Generating a Driving Force for Crystallization


In foods, there are two types of crystallizing systems: melt systems and solution systems. Solution
systems are the classic solute-solvent system, in which the solvent is nearly always water. Melt
systems are those that simply need to be cooled below a certain temperature, the melting point,
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in order to generate a driving force for crystallization. Water is the primary example, although
lipids exhibit similar behavior to some extent. Single triacylglycerols (TAGs) are true melt systems
because they exhibit a melting point above which the TAG is liquid and below which it solidies.
Some food systems exhibit a combination of the two behaviors. Natural fats and oils, for
example, exhibit both melt and solution behavior. Although individual TAGs exhibit melting
behavior, high-melting TAGs also dissolve in a low-melting TAG as a solute in a solvent (Zhou
& Hartel 2006). As a natural fat is cooled, the TAGs with the highest melting point crystallize
rst, but depending on the nature of liquid oil, they may actually crystallize from the solvent.
As temperature is cooled, additional TAGs crystallize, in part because the temperature has gone
below their melting point but also because their solubility in the liquid oil has decreased with
temperature. This combination of effects makes the lipid crystallization process quite complex. In
fact, it is this solubility effect on fats that has led some to consider fat bloom during storage to be
governed by the solubility of high-melting TAGs in low-melting oil (Matsuda et al. 2001).
During food manufacture, process conditions must be controlled to achieve the desired level
of control of supersaturation. In solution systems, this requires control of water content (or solute
concentration) and temperature, which places the food system at a specic point on a phase/state
diagram (Roos 2010). These diagrams can be used to ascertain process conditions appropriate
for either solvent or solute crystallization. Appropriate process conditions depend on whether
crystallization is desired or not (Hartel et al. 2011).

Nucleation
Nucleation, the process by which molecules in the liquid state transform into a crystal lattice, can
take place in several different ways through primary and secondary mechanisms (Hartel 2001,
Mullin 2001). Classical nucleation theory describes homogeneous primary nucleation on the
basis of molecular organization, with no external assistance, into a crystal lattice. In heterogeneous
primary nucleation, a solid foreign substance provides a portion of the energy for nucleation, mean-
ing that it occurs much faster than homogeneous nucleation. Finally, secondary nucleation occurs
when existing crystals of the crystallizing material spawn new nuclei through contact mechanisms.
Signicant changes in our understanding of nucleation have occurred in recent decades. Clas-
sical nucleation theory, developed in the late 1800s by Gibbs, is based on the condensation of
vapor molecules to a liquid. Over the years, the shortcomings and inconsistencies of the classical
theory have been pointed out (Erdemir et al. 2009). Recent work suggests that a modied view of
the nucleation step is warranted (Kawasaki & Tanaka 2010, Meldrum & Sear 2008, Vekilov 2010).
Current thinking suggests that most, if not all, nucleation occurs through a two-step process
(Erdemir et al. 2009). Molecular uctuations in the liquid phase lead to local organization of

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molecules into amorphous clusters (rather than as crystal embryos, as postulated by classical
nucleation theory), which then aggregate to form an amorphous cluster of critical size. This
formation of amorphous clusters is the rst step in nucleation. At some point, the molecules
in the cluster transform into a crystal lattice, the second step for making a stable nucleus. The
combination of these two events gives an induction time prior to onset of visual nucleation.
Heterogeneous nucleation has also come under study in recent years, with research docu-
menting the nature of the surface required for a solid surface to catalyze formation of nuclei.
As noted by Diao et al. (2011b), control of industrial crystallization is generally limited because
the mechanisms of heterogeneous nucleation have been poorly understood. Recent research has
begun to characterize surface chemistry and the presence of nanoscale pores on heterogeneous
nucleation (Diao et al. 2011a,b; Holbrough et al. 2011). Future work on designing surfaces specif-
ically for heterogeneous nucleation has the potential to signicantly improve control of industrial
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crystallization.

Crystal Growth
Once nuclei have formed, crystals quickly begin to grow in size based on the driving force for
crystallization (Hartel 2001, Mullin 2001). Although crystals can also grow larger through ag-
gregation (as in lipid crystalline spherulites), the main mechanism for growth is deposition of
molecules and growth units onto the existing crystal lattice. For this to happen, molecules of the
crystallizing species diffuse to the crystal interface while other molecules (including water) diffuse
away. Molecules of the crystallizing species, which may have to release waters of hydration prior
to crystal growth, diffuse along the crystal surface until they nd a lattice site and are incorporated
into the crystal structure. With the phase change comes the release of latent heat, which must be
transferred from the crystal surface.
Each system exhibits unique growth dependence based on the nature of the crystallizing
molecules. For example, ice crystal growth is known to depend primarily on the combination
of counter-diffusion of solute molecules away from the interface and heat removal. That is, the
two main rate-limiting steps for growth of ice crystals are how fast solute molecules diffuse away
from the growing surface and how fast the heat generated can be transferred away from the sur-
face. It is for these reasons that rapidly growing ice crystals favor the dendritic shape as the tip of
a dendrite allows rapid mass and heat transport. Sucrose crystal growth depends on two different
steps, namely, bulk diffusion of sucrose molecules to the crystal surface and surface incorporation.
That is, the rate-limiting steps for sucrose crystal growth are the speed at which sucrose molecules
can get to the surface of the growing crystal and the ease with which they can become incorporated
into the lattice (surface incorporation).

Recrystallization
Recrystallization has been dened as any change in the number, size, shape, orientation or per-
fection of crystals following completion of initial solidication (Fennema et al. 1973). Of primary
concern during food storage, recrystallization is responsible for ice-crystal coarsening in ice cream
and fat bloom in chocolates and coatings. Certain highly crystallized sugar products, such as fon-
dant and creams, also experience crystal coarsening through recrystallization (more details can be
found in Hartel 2001).
The basic mechanism that underlies recrystallization of sugars and ice is the size-dependent
equilibrium (melting temperature or solubility) documented by the Gibbs-Thomson effect. Small
crystals, owing to the low radius of curvature of the surface, are slightly more soluble or have a

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slightly lower melting point than larger crystals (approximating at surfaces). Over time, these
differences promote the disappearance of small crystals and the growth of large ones. These
changes generally occur without a change in crystalline phase volume and are driven by the
thermodynamic difference in equilibrium behavior based on crystal size. They occur slowly at
constant temperature but are greatly enhanced with uctuating temperature as the phenomenon
called melt-refreeze becomes dominant. When temperature goes up in a temperature cycle, crystals
either melt or dissolve to maintain phase equilibrium. Small crystals, because they are slightly less
stable, disappear rst. When the temperature goes back down in the thermal cycle, crystal phase
volume increases, but only through growth; no new nuclei are formed. Any small crystals that
have disappeared are gone for good, with their mass being redispersed among the remaining
larger crystals. As the mean size increases, the number of crystals decreases because of these
thermodynamic effects. In this way, a dispersion of numerous small crystals tends to minimize
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surface energy (and surface area) through recrystallization (Hartel 1998). Interestingly, similar
recrystallization phenomena occur in magma systems (Mills et al. 2011).
In lipid systems, a similar process occurs, but along with the surface effect, there is also a change
in internal perfection through polymorphic transformation. Although numerous factors inuence
bloom formation on chocolates and coatings, the primary mechanisms involve recrystallization
and the polymorphic transformation (Lonchampt & Hartel 2004).

RECENT ADVANCES

Measurement and Quantification


As science and technology evolve, new methods of characterizing crystallization are continually
being developed. These developments generally serve two purposes: to help improve our un-
derstanding of the principles that govern crystallization in foods and to help guide processing
operations to better control crystallization.

Online measurements. Measuring crystals and crystallization progress in situ during process-
ing has always been a challenge in any crystallization operation (Braatz et al. 2002). Sensors have
typically included online measurement of either solution concentration as an indirect measure of
crystallization or as a direct measurement of the crystal population. Traditionally, solution concen-
tration as an indirect measure of crystallization progress is determined with probes that measure
some physical attribute that correlates with concentration, such as refractive index, density, or
conductivity. Braatz et al. (2002) recommended attenuated total reection Fourier transform in-
frared spectroscopy as an advanced technique with the potential to measure solution concentration
with an accuracy of 0.1%.
Online crystal detectors, based on either laser backscattering or particle imaging, have also
become more common, although their use in the food industry is still limited. These measurements
are often coupled with uid dynamics and population balance models to better understand process
operations (see below). Inline particle size sensing of ice crystal formation in a scraped-surface
freezer has been the topic of several recent publications. For example, Haddad Amamou et al.
(2010) and Arellano et al. (2012) used the focused-beam reectance measurement (FBRM) tool
to follow ice formation in continuous freezing of sorbet. The FBRM is a laser backscattering
detector that provides a chord distribution (rather than a true size distribution). By characterizing
the changes in chord length distribution, researchers documented the effects of changes in process
and formulation parameters. Such online crystal measurement methods have potential to provide
advanced control over crystallization operations. To study nucleation and metastable zone width,

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FBRM was coupled with a particle video monitoring (PVM) device (Simon et al. 2009). Proof of
concept was demonstrated for both caffeine and palm oil crystallization.
Ultrasonic methods, measured by velocity and/or attenuation, have been used recently for a
variety of applications in foods (Coupland 2004), including following crystal formation. Chaleepa
et al. (2010) compared an ultrasonic velocity method with a laser backscattering method based
on chord length measurement for determining the metastable zone width for natural fats. In this
system, the ultrasonic measurements gave more accurate and reproducible results compared with
light backscattering. Also, ultrasonic velocity was used to follow lard crystallization during storage
and gave better results than light-scattering methods (Santacatalina et al. 2011). However, the
main limitation to ultrasound methods for characterizing crystallization is that, as an indirect
measurement of crystal formation, other factors (e.g., viscosity) also affect the ultrasound signal.
To that effect, Birkhofer et al. (2008) combined a pulsed ultrasound Doppler-based velocity prole
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measure with a pressure drop in a pipe section during ow to measure crystallization of cocoa
butter in a shear cell. This combination of technologies allowed inline monitoring of cocoa butter
during crystallization and conrmed that the cocoa butter crystal slurry was shear thinning, with
the power law index decreasing as slurry density increased.

Nondestructive in situ methods. In situ methods for characterizing crystals in foods have also
been developed. Two that are discussed here are magnetic resonance imaging (MRI) and X-ray
microtomography. X-ray microcomputed tomography combines X-ray microscopy with tomog-
raphy, or imaging in sections, to reconstruct a two- or three-dimensional image of a material.
Mousavi et al. (2005) utilized X-ray microcomputed tomography to characterize ice crystal struc-
tures in a model food system (mycoprotein). By comparing the ice crystal results with those of
scanning electron microscopy (SEM), they showed that X-ray microcomputed tomography was
capable of distinguishing ice crystals. The same group then applied the method to characteriz-
ing ice crystal formation in various foods during freezing (Mousavi et al. 2007). On the basis of
the tomographic images, they showed the effect of freezing on ice crystal size distribution. As
expected, ice crystals were smaller near the cold surface of the food and got increasingly larger
at distances from the surface. Mousavi et al. (2007) also showed the effect of food structure on
freezing, with ice crystal size distributions that were quite different in different foods for the same
freezing conditions. Carrots, for example, had a signicantly larger ice crystal size distribution
than potato or cheese. Another example of using a three-dimensional X-ray tomography system
involved following changes in ice crystal size distribution during storage (Pinzer et al. 2012). This
system allowed for the rst time direct observation of the in situ changes that occur during ice
recrystallization and veried that the melt-refreeze mechanism was the dominant mode of ice
crystal evolution. Further advancements in this technology should improve the resolution and
allow visualization of smaller structures.
MRI has been used to characterize crystallization in foods, particularly of ice during food
freezing (Hindmarsh et al. 2004, Kerr et al. 1998) and of lipids during storage (Deka et al. 2006,
Maleky et al. 2012). Kerr et al. (1998) used MRI to characterize the changing state of water
during freezing of various foods. Clearly observed were the effects of freezing conditions on ice
formation in the different regions of nonhomogeneous foods (e.g., carrot cylinder and chicken
leg). Of particular interest were the observed differences in induction time for freezing of distinct
food units within the same plant (ear of corn) or package (peas). Using nuclear magnetic resonance
(NMR) imaging, the temperature of onset of nucleation in these compartments was determined.
Interestingly, peas in a package nucleated at higher temperatures (6 to 17 C, with a median of
9 C) than individual corn kernels on the cob (7 to 19 C, with a median of 16 C). This effect
was attributed to differences in heterogeneous nucleation sites in the products. Corn kernels must

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contain particulates or structures that more readily nucleate ice compared with the structures in
peas. One issue with MRI imaging is resolution. Hindmarsh et al. (2004) studied freezing of a
2 mm diameter sugar droplet with MRI. Although they could follow the general trends during
Polymorphism: the
freezing, resolution was limited to approximately 30 m, meaning that a lot of the detail was ability of a molecule to
missed. Cryo-SEM images of the frozen droplets showed the dendritic growth expected at the take on several
high rates of freezing, but these details were not visible with MRI. different crystal
structures
Synchrotron X-ray technologies. Following crystallization as it occurs in real time has always
been a challenge. Advances in X-ray technologies have opened avenues for characterizing real-
time changes during crystallization. Specically, the development of synchrotron X-ray sources,
with more than 1,000 times the intensity of regular X-ray sources, has signicantly enhanced the
capability of investigating the time dependence of crystal formation and has signicantly improved
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the resolution at which crystals can be probed (Merrield et al. 2011). Synchrotron X-ray analysis
has been used, for example, to study fat crystallization and polymorphism during fat crystallization
and ice formation during freezing.
Varshney et al. (2009) used synchrotron X-ray diffraction to follow the freezing of water. With
the higher intensity of synchrotron X-rays, they observed unique phenomena during freezing that
have not been seen before. Splitting of the X-ray peaks was attributed to local stresses on the
lattice as the ice formed. The authors suggested that further studies on this system might provide
better understanding of the destabilization of proteins and biological systems during freezing.
Another interesting recent study used synchrotron X-ray visualization of ice formation in insects
to better understand when freezing is lethal and when it is not (Sinclair et al. 2009). The method
was shown to qualitatively demonstrate the onset of freezing. Interestingly, the results suggested
that although freeze-tolerant larvae had some control over ice nucleation, the process of forming
ice was not different between freeze-tolerant larvae and those that were not freeze-tolerant. Of
greatest importance, though, is that these methods now allow study of crystallization processes
that have not before lent themselves to study.
One area in which synchrotron X-ray studies have been applied recently is in understanding
lipid crystallization and polymorphism. Numerous publications have appeared in the past decade
or so in which synchrotron X-ray analysis has been used to quantify lipid crystallization and poly-
morphism. Sato & Ueno (2011) summarize much of that recent work. By way of example, Ueno
et al. (2008) used synchrotron X-ray analysis to study crystallization and polymorphic transforma-
tion of trilaurin. With this method, they determined that the spherulite crystals typically formed
from the  polymorph of trilaurin were actually composed of nanometer-sized crystals that stacked
together to form the arms of the spherulites. Details of the polymorphic transformation were also
discussed. As another example, Arima et al. (2009) used two-dimensional microbeam small-angle
X-ray diffraction to observe nucleation of fats at the interface of an oil-in-water emulsion droplet.
They found the ordering expected for surface-induced nucleation, but a subsequent study ex-
plored these effects in greater detail through the use of a synchrotron source (Wassell et al. 2012).
Although surfactant surface-induced nucleation of oil droplets had been previously suspected, the
actual observation of the phenomenon was not possible until these new developments in X-ray
technology.
Synchrotron X-ray diffraction technology has been applied to provide a better understanding
of the effects of shear on fat crystallization and polymorphism. As expected from previous research,
shear was shown to accelerate the polymorph transformation in milk fat, although there was no ef-
fect on the induction time for crystallization (Mazzanti et al. 2009). Further study used synchrotron
X-ray analysis to show that shear also inuenced the nature (thickness) of the nanoplatelets that
formed during crystallization (Mazzanti et al. 2011).

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For many years, numerous studies on the effects of minor lipid components (phospholipids and
other emulsiers) on lipid crystallization have been conducted in an attempt to understand how
these components, whether found naturally or added specically to provide some functional ad-
vantage, affect nucleation, growth, and polymorphism. Recently, Huck-Iriart et al. (2009) applied
synchrotron X-ray scattering to study the effects of a palmitic sucrose ester on the crystallization
of mixtures of a high-melting milk-fat fraction in sunower oil. Synchrotron X-ray scattering
allowed them to follow the initial stages of crystal formation and polymorphic transformations.
The sucrose ester inuenced both nucleation and the polymorphic transformation, with the effects
dependent to some extent on crystallization temperature. In general, the sucrose ester delayed the
transformation from to  forms.
By coupling synchrotron X-ray technology with other analytical methods (calorimetry, Raman
spectroscopy, tomography, etc.), even greater understanding of crystallization and polymorphism
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has been forthcoming. For example, Klimakow et al. (2010) coupled synchrotron X-ray analysis
with Raman spectroscopy (employing acoustic levitation of droplets to minimize heterogeneous
nucleation) to identify polymorphic transformation of a pharmaceutical compound in different
solvents. The combination of methods allowed simultaneous monitoring of crystallization with
polymorphic identication.
One combined technology that has been widely used in lipid crystallization studies involves
synchrotron X-ray analysis coupled with differential scanning calorimetry (DSC), as described by
Ollivon et al. (2006). Ollivons group in Paris used this system to characterize crystallization of a
variety of fats, including cocoa butter (Loisel et al. 1998) and milk fat (Lopez et al. 2001a,b, 2005).
With this combined method, the peaks observed on the DSC were easily explained as crystallization
and/or transformation of different polymorphs or crystal structures. One particularly interesting
and unique application was the study of crystallization and polymorphism of dromedary (camel)
milk fat (Karray et al. 2004, 2005). Their results showed that high-melting TAGs in camel milk
fat, due to heat adaptation to a desert climate, caused signicant differences in crystallization
compared with bovine milk fat.
Synchrotron X-ray microtomography and X-ray diffraction were used to study both surface
structure and crystal/phase orientation (Merrield et al. 2011). They attained imaging resolution
at a scale of 20 to 50 m during crystallization of aspirin in a batch cooling crystallizer while
also obtaining crystallographic data on the unit cells of the lattice. Combined systems of this type
hold promise to open new avenues of research that will rapidly advance the understanding of
crystallization phenomena.

Microscopy. Microscopy has been a long-standing mainstay for studying food structures, includ-
ing crystals (Kalab et al. 1995, Hartel 2001). In addition to conventional microscopy techniques,
including polarized light microscopy, SEM, and transmission electron microscopy (TEM), sev-
eral more recent applications of microscopy for studying crystals in food include confocal laser
scanning microscopy (CLSM) and atomic force microscopy (AFM). Maleky et al. (2011) provide a
recent example of using electron microscopy to understand the nanostructure of fat crystals. Com-
bined use of cryo-SEM and cryo-TEM clearly documented the effects of shear and orientation on
the structure of the nanoparticles that make up the crystalline matrix. Of particular interest here is
the clarity of images obtained from cryo-TEM, which documented the structures that were only
hinted at with cryo-SEM and optical microscopy.
The primary benet of CLSM over conventional microscopy is that it can be used, at least to
some extent, to probe the three-dimensional structure below the surface of a food, depending on
the opacity of the sample. CLSM allows focusing the image at a specic plane, which can be inside
the surface of the food. Imaging depth is highly dependent on opacity, but for certain samples,

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such as dilute dispersions of lipid crystals, a three-dimensional image can be obtained by taking
sequential images at focal planes deeper and deeper into the product. Because CLSM depends on
uorescent imaging, a dye is typically needed to enhance imaging. Evans et al. (1996) used CLSM
to study the effects of freeze-thaw cycles on characteristics of various protein-based solutions.
Using CLSM, ice crystal size was shown to be a function of the type of protein, with all proteins
causing a reduction in ice crystal width. Another example of using CLSM to study ice crystallization
is the study by Baier-Schenk et al. (2005) on dough freezing. Here, CLSM was used to show that
ice nucleation began at the gas pore interface in the dough and that the freeze concentration effect
of ice formation did not reversibly change gluten microstructure. In lipid systems, Marangoni &
Hartel (1998) documented the effects of minor lipids on the crystalline microstructure of milk
fat by using CLSM. Native milk fat, with its inherent minor lipids, crystallized into spherulites,
whereas puried milk-fat TAG crystallized into more disordered structures. Also, Herrera &
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Hartel (2000) used CLSM to study two-stage crystallization of a milk-fat model system. Crystals
from the rst stage (25 C to 30 C) could be imaged by a polarized light microscope, but once that
slurry had been cooled to refrigerator temperatures to promote secondary crystallization, CLSM
was needed to image the different crystalline microstructures.
Although AFM has wide application in foods (Shimoni 2008), the primary application of AFM
for crystals in foods has been studying bloom in chocolates (Hodge & Rousseau 2002, Smith &
Dahlman 2005, Rousseau & Smith 2008). AFM operates at the nanometer level at the surface
of a material. The AFM probe interacts with the surface structure to provide a topographical
representation of the surface. As such, AFM allows visualization of the changes in the chocolate
surface over time. For example, Sonwai & Rousseau (2006) tracked the increasing roughness of
a chocolate surface over time using AFM. When combined with NMR (solid fat content), X-ray
powder diffraction (polymorph determination), and whiteness index, AFM provided a deeper
understanding of the role of the polymorphic transformation on the development of bloom in
chocolates. The surface changes documented by AFM have been shown to depend on the type of
bloom and whether the chocolate was lled (fat migration) or not. In either mechanism, however,
AFM allowed the changes in shape of surface fat crystals to be documented.

Controlling Crystallization
Many recent advances in crystallization relate to better control over process operations to achieve
more uniform control of nished product and extended shelf life. Several recent examples are
noted here.
Lactose rening involves lling the crystallizer tank with warm, concentrated whey permeate
followed by a controlled cooling prole to promote crystallization and enhance yield. In lactose
rening, it is common to nd a wide range of crystal sizes that makes subsequent separation of
product crystals from the mother liquor extremely inefcient. It is primarily the formation of
secondary nuclei through contact mechanisms that introduces a substantial population of nes
(crystals smaller than approximately 10 m) that causes this problem. Through a better under-
standing of the dynamic metastable zone width pertinent in lactose-cooling crystallizers, Wong
et al. (2011) documented that secondary nucleation based on crystal contacts causes the nes prob-
lem. The effects of agitation rate on secondary nucleation were also clearly dened. This work
led to improved modeling and optimization of the lactose rening process (Wong et al. 2012), as
discussed further below.
Ultrasonic energy applied to crystallizing systems, or sonocrystallization, has long been seen as
a way to promote crystallization processes (Ruecroft et al. 2005). It is thought that the vibrational
energy input from the ultrasonic energy is sufcient to promote nucleation and growth through

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FO04CH14-Hartel ARI 1 February 2013 21:28

enhanced heat and mass transfer. Further, the ultrasonic energy may possibly promote heteroge-
neous nucleation by shaking nucleation sites loose from the walls of the vessel. Sonocrystallization
of foods has been recently promoted for sucrose rening (Stasiak & Dolatowski 2008), lactose
recovery from whey (Bund & Pandit 2007), fat crystallization (Martini et al. 2008), and ice crystal-
lization during freezing of foods (Zheng & Sun 2006). Through manipulation of nucleation and
growth, sonocrystallization can potentially provide enhanced control for either building crystal
structures in foods to control texture or for improved separation.
The application of shear during crystallization has also been recently studied in detail, with an
emphasis on controlling lipid crystallization and polymorphism. As noted above, shear can have
signicant effects on lipid crystallization and polymorphism (Maleky et al. 2011; Mazzanti et al.
2009, 2011). Maleky et al. (2012) utilized this concept to manipulate the cocoa butter structure
of chocolate to inuence oil migration. Shearing the system during crystallization resulted in
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reduced oil migration through the chocolate matrix, probably because of the formation of ner
nanoparticles (Maleky et al. 2011). This is a nice example of how fundamental research on crystal-
lization characteristics can lead to solutions to modern commercial problems (oil migration and
subsequent fat bloom in chocolate).
Crystallization of cocoa butter (tempering) is important to obtain the desired properties of
chocolate: good snap, contraction from the mold, and resistance to bloom. Recent research has
improved our understanding of the amount of seeds needed to obtain good temper. Kinta & Hartel
(2010) documented that a minimum amount of seeds in the stable polymorph was needed to allow
proper crystallization of the chocolate mass. When seed level was below this critical value, unstable
polymorphs formed that led to under-tempered bloom (Lonchampt & Hartel 2006). Svanberg
et al. (2011) also studied the effects of precrystallization and seeding on the microstructure of
chocolate. A clear decrease in structure density was observed when there were no cocoa butter
seed crystals, with the more open structure leading to higher local oil migration rates.
Another example of controlling crystallization in foods relates to the challenge of producing and
maintaining small ice crystals in frozen foods and desserts. Recent advances in both processing and
formulation additives have greatly improved the control of ice formation and recrystallization, par-
ticularly in frozen desserts. Pressure-shift freezing and low-temperature extrusion are recent exam-
ples of processing advances that produce small ice crystals in frozen desserts. In pressure-shift freez-
ing, nucleation is induced uniformly throughout a food through rapid depressurization at 15 C
to 20 C (Volkert et al. 2011). At high pressure, water is still liquid at these temperatures. Rapid
release of pressure causes the entire food mass to be subcooled uniformly (rather than from the
surface inwards through conventional freezing), and nucleation of small crystals occurs uniformly
throughout the food. These small crystals improve product quality and extend shelf life. Pressure-
shift freezing is still primarily a technology under study and has yet to be commercialized. In con-
trast, several commercial ice creams and frozen desserts based on the low-temperature extrusion
process are currently available (Windhab & Bolliger 1998, Wildmoser & Windhab 2001). Here,
the product of primary (dynamic) ice crystallization in a scraped-surface freezer is passed immedi-
ately into a low-temperature extruder, where the slow churning effect of the screws cools the mass
with minimal recrystallization. The small crystals that result from this process give a smoother tex-
ture, or as found commercially, the creaminess of these small ice crystals allows removal of some of
the fat to make a reduced-fat product with equivalent creaminess to the full-fat version. From a for-
mulation standpoint, ice-structuring proteins have been found to provide outstanding protection
against ice recrystallization (Crilly et al. 2008, Hassas-Roudsari & Goff 2012). These proteins, of-
ten called antifreeze proteins, adsorb strongly to the ice crystal surface and prevent further growth
or recrystallization. These proteins are responsible for the cold-tolerance of many sh, insects, and
plants. Another ingredient that has been found to signicantly reduce ice recrystallization is the

286 Hartel
FO04CH14-Hartel ARI 1 February 2013 21:28

140

120 Boiling

Boiling point elevation Forming


100
Temperature (C)

80
Heating

60 Sucrose solubility

40
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Glass
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transition
20
Final
product
0
40 45 50 55 60 65 70 75 80 85 90 95 100

Total dissolved solids (wt%)

Figure 1
Phase/state diagram for preventing crystallization in hard candy [with permission from Hartel et al. (2011)].

emulsier propylene glycol monostearate (PGMS) (Aleong et al. 2008). Although the mechanism
by which PGMS inhibits ice crystal growth is uncertain, it has a signicant effect in reducing both
ice crystal size in a scraped-surface freezer and inhibiting further changes due to recrystallization.
No discussion on recent advances in controlling crystallization is complete without mention
of how the phase/state diagram is being used to guide manufacturing processes. Roos (2010), for
example, notes how the phase/state diagram for lactose can be used to better understand freezing
operations in ice cream as well as the problem of lactose crystallization during storage (sandiness
defect). In Hartel et al. (2011), the phase/state diagram for sucrose-corn syrup mixtures is used to
document the different manufacturing processes for hard candy and fondant (Figure 1). In hard
candy, crystallization should be avoided even though the manufacturing process passes through the
supersaturation zone. Processing conditions (e.g., minimal agitation) and formulation factors (e.g.,
sufcient corn syrup content) must be appropriate to slow crystallization kinetics until molecular
mobility is sufciently reduced to inhibit crystallization as the glassy state is attained. As long as
the system is maintained in the glassy state, no crystallization can occur. Only when the system
exits the glassy state, for example, by heating above the glass transition temperature (Tg ), can
crystallization occur (Levenson & Hartel 2005). For fondant, the manufacturing process follows a
different track on the phase/state diagram because a high level of crystallization is needed to give
the desired texture and quality attributes. In this case, the sugar mass is brought to a temperature
and composition that puts it squarely in the middle of the crystallization zone, at which point
severe agitation promotes rapid crystallization (Figure 2). This produces the numerous small
crystals that provide the smooth eating texture of fondant.

Modeling and Optimization


In recent years, tools such as computation uid dynamics (CFD) have been applied to food prob-
lems (Norton & Sun 2006), including crystallization. CFD, through solution of the governing
transport equations, allows prediction of heat, mass, and momentum transfer in food-processing

www.annualreviews.org Advances in Food Crystallization 287


FO04CH14-Hartel ARI 1 February 2013 21:28

140

120 Boil off water


Boiling point elevation
100

Temperature (C)
Heat to boiling point Sugar crystal,
Sucrose plus solution
80 solubility
Cool to
crystallization
temperature
60

Crystallize
40
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Glass
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transition Glass
20

0
50 55 60 65 70 75 80 85 90 95 100

Solution concentration (wt%)

Figure 2
Phase/state diagram for controlling crystallization in fondant [with permission from Hartel et al. (2011)].

operations. When coupled with population balance models, CFD allows prediction and even
optimization of crystallization problems.
For example, Wong (2011) applied CFD coupled with a population balance model to study
lactose rening operations. CFD explained the effects of mixer type on fouling through dead zones
in the mixing eld and the effects of agitation rate on secondary nucleation through shear forces.
Coupling CFD with population balance models allowed prediction of crystal size distributions
when appropriate crystallization kinetic parameters were inserted into the algorithm. Wong et al.
(2012) applied these principles to the optimization of the cooling prole in a commercial lactose
crystallizer to minimize formation of crystal nes and enhance operation efciency.
Another example in which CFD has been coupled with population balance modeling is ice
crystallization in a scraped-surface freezer. Lian et al. (2006) applied CFD to predict uid velocity
vectors and temperature proles within the scraped-surface freezer and then coupled heat- and
mass-transfer principles with crystallization kinetics to predict the ice crystal size distribution ex-
iting the freezer. Despite the estimates of crystallization kinetic parameters and simplication of
mechanisms, the experimental size distributions were reasonably well predicted. Benkhelifa et al.
(2008) also coupled CFD and population balance modeling for ice crystallization in a scraped-
surface freezer. They modeled the change in population density, temperature, ice fraction, and
mean ice crystal size along the length of the freezer, successfully coupling heat transfer, uid ow,
and crystallization. Although these two studies represent excellent starts to improved understand-
ing, the actual processes that occur during ice crystallization within a scraped-surface freezer are
extremely complex (Cook & Hartel 2011). Future efforts will need to rene the crystallization
input parameters to the model to more accurately predict product outputs.

SUMMARY
Numerous advances have been made in recent years relative to crystallization in foods. New
technologies continue to improve our understanding of the mechanisms of crystallization through

288 Hartel
FO04CH14-Hartel ARI 1 February 2013 21:28

improved capabilities of probing crystal structures during formation and storage. These tools
provide opportunities to better control crystallization and recrystallization to ensure the highest
quality foods.

SUMMARY POINTS
1. Numerous advances in technology and instrumentation for studying and characteriz-
ing crystals in foods have enhanced our understanding of crystallization principles and
improved our ability to control crystallization.
2. Recent advances in numerical modeling methods have also allowed better control of
crystallization.
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DISCLOSURE STATEMENT
The author is not aware of any afliations, memberships, funding, or nancial holdings that might
be perceived as affecting the objectivity of this review.

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292 Hartel
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Annual Review
of Food Science
and Technology

Contents Volume 4, 2013

Wine Matrix Compounds Affect Perception of Wine Aromas


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Remedios R. Villamor and Carolyn F. Ross p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 1


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Potential Application of Pectinase in Developing Functional Foods


Mahejibin Khan, Ekambaram Nakkeeran, and Sukumaran Umesh-Kumar p p p p p p p p p p p p21
Design of Foods with Bioactive Lipids for Improved Health
Bingcan Chen, David Julian McClements, and Eric Andrew Decker p p p p p p p p p p p p p p p p p p p p p35
Advances in the Control of Wine Spoilage by Zygosaccharomyces
and Dekkera/Brettanomyces
J.M. Zuehlke, B. Petrova, and C.G. Edwards p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p57
Myoglobin Chemistry and Meat Color
Surendranath P. Suman and Poulson Joseph p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p79
Impacts of Preharvest Factors During Kernel Development
on Rice Quality and Functionality
Terry J. Siebenmorgen, Brandon C. Grigg, and Sarah B. Lanning p p p p p p p p p p p p p p p p p p p p p 101
Methicillin-Resistant Staphylococcus aureus: A Food-Borne Pathogen?
Sarah Wendlandt, Stefan Schwarz, and Peter Silley p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 117
Microbial Interactions in Food Fermentations
Melissa Ivey, Mara Massel, and Trevor G. Phister p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 141
Naturally Occurring Antimicrobials for Minimally Processed Foods
P. Michael Davidson, Faith J. Critzer, and T. Matthew Taylor p p p p p p p p p p p p p p p p p p p p p p p p 163
Genetic and Phenotypic Characteristics of Bakers Yeast:
Relevance to Baking
Francisca Randez-Gil, Isaac Corcoles-Saez, and Jose A. Prieto p p p p p p p p p p p p p p p p p p p p p p p p p p 191
Breeding Research on Sake Yeasts in Japan: History, Recent
Technological Advances, and Future Perspectives
Hiroshi Kitagaki and Katsuhiko Kitamoto p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 215
Food Oral Processing: Conversion of Food Structure
to Textural Perception
H. Koc, C.J. Vinyard, G.K. Essick, and E.A. Foegeding p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 237

v
FO04-FrontMatter ARI 13 February 2013 20:19

The Secretion, Components, and Properties of Saliva


Guy H. Carpenter p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 267
Advances in Food Crystallization
Richard W. Hartel p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 277
Aatoxin Biosynthesis: Current Frontiers
Ludmila V. Roze, Sung-Yong Hong, and John E. Linz p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 293
A New Generation of Food-Borne Pathogen Detection Based
on Ribosomal RNA
Kristin Livezey, Shannon Kaplan, Michele Wisniewski, and Michael M. Becker p p p p p p 313
Access provided by ALI: Academic Libraries of Indiana on 06/04/15. For personal use only.

Off-Flavor Precursors in Soy Protein Isolate and Novel Strategies


Annu. Rev. Food Sci. Technol. 2013.4:277-292. Downloaded from www.annualreviews.org

for their Removal


Srinivasan Damodaran and Akshay Arora p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 327
Bacteriophages in Food Fermentations: New Frontiers in a
Continuous Arms Race
Julie E. Samson and Sylvain Moineau p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 347
Surface-Enhanced Raman Spectroscopy Applied to Food Safety
Ana Paula Craig, Adriana S. Franca, and Joseph Irudayaraj p p p p p p p p p p p p p p p p p p p p p p p p p p p 369
Nutrimetabonomics: Applications for Nutritional Sciences, with
Specic Reference to Gut Microbial Interactions
Sandrine P. Claus and Jonathan R. Swann p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 381
Parameter Estimation in Food Science
Kirk D. Dolan and Dharmendra K. Mishra p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 401

Errata

An online log of corrections to Annual Review of Food Science and Technology articles may
be found at http://food.annualreviews.org

vi Contents

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