Crystallization in Foods

CRYSTALLIZATION IN FOODS!
Dr Abd Karim Alias, 2005
PRESENTED BY: Prof. Abd Karim Alias
What do chocolate, butter, margarine, ice cream, sugar, and hard candy have in common?
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CRYSTALLIZATION IN FOODS !!Bagaimana hablur terbentuk dalam sistem makanan? !!Apakah faktor-faktor yang mempengaruhi proses penghabluran? !!Apakah signifikan proses penghabluran semula terhadap kualiti makanan dan bagaimana cara untuk mengawalnya? !!Bagaimana pembentukan hablur (dan proses penghabluran semula) dapat mempengaruhi kualiti dan kestabilan makanan?
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CRYSTALLIZATION
REFERENCES !!R.W. Hartel (Editor) (2001). Crystallization in Foods. Aspen Publishers,Gaithersburg, Maryland. [TP370.5 H328] !!Hartel, R.W. & Shastry, A.V. (1991). Sugar crystallization in food products. Critical Reviews in Food Science and Nutrition 1(1), 49-112.
CRYSTALLIZATION
!!The structural elements in foods (air cells, crystals, fat globules) play an important role in determining quality & shelf stability. It is the structure that provides the desired rheological properties of the food (hardness, stiffness, snap, etc) & contributes to organoleptic properties (melt-down rate, cooling effect, etc.) !!Crystalline phase is one of the most important structural elements in many foods " it has impact on quality, texture, and shelf life.
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CRYSTALLIZATION
!! For example, the crystalline microstructure of cocoa butter in chocolate provide the desired snap when a molded bar is broken !! The main components that form crystalline phase are water (ice), sugars (and sugar alcohol), lipids, and starches !! Other components may crystallize: salts, organic acids (eg. citric acid), proteins, and emulsifiers
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CRYSTALLIZATION
!!Crystallization is a term that describes several different phenomena related to the formation of a crystalline lattice structure. !!When a crystal forms, the molecules orient themselves in a regular pattern, or lattice structure. In contrast, molecules in amorphous material are more randomly oriented & move about freely
CRYSTALLIZATION
!! Crystal lattices are composed of an ordered layering of molecules, with the ordering dependent on the nature of the forces & the interactions between individual molecules freedom of motion is greatly restricted in a crystal lattice.
CRYSTALLIZATION
!!Control of crystallization in foods is an important aspect of food quality. !!Separation process (eg. sugar refining, fat fractionation) or !!To provide a certain texture within the food itself (eg. ice cream, fondant, chocolate)
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Crystallization may be employed as:
CRYSTALLIZATION
Unit Cell
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Arrangement of atoms in a simple cubic unit cell. The rest of this crystal can be built by stacking identical unit cells next to one another along the x, y and z axes to form a crystal lattice.
CRYSTAL FORMATION
Arrangement of sucrose molecules within crystal lattice structure
Shape of lactose crystals grown at different supersaturation

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CRYSTAL FORMATION Four steps in crystallization typically include: !! generation of supersaturated state !! nucleationthe formation of crystalline lattice structure from solution or melt !! growthsubsequent growth of nuclei until equilibrium is attained !! recrystallization a reorganization of the crystalline structure to a lower energy state, generally without any further change in the amount of crystalline phase volume
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CRYSTAL FORMATION
!! Any solutes (eg. sugar) will have its own solubility value (Cs) in solution; solutions with solute contents below this concentration are undersaturated & will allow further dissolution of solute crystals. !! Supersaturation can be expressed as the difference between the concentration of a saturated solution (Css) and the equilibrium solubility (Ceq): !C = Css Ceq
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CRYSTAL FORMATION
Metastable !B! (supersaturated)!
!A!
Solubility curve Stable " (Under saturated solution)!
Temperature
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Labile (supersaturated unstable)!

Sugar concentration
!C!
CRYSTAL FORMATION
!! When solute contents > solubility concentration (Cs), ! supersaturated solutions.

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!! Any crystals present in a supersaturated solution will not dissolve, but, rather, will grow larger as the solution attempts to approach its equilibrium condition. !! Supersaturated solutions are necessary for the crystallization processes of nucleation & growth.
CRYSTAL FORMATION How to achieve supersaturation? !!(1) for melt, cooling below the melting point of a compound (eg. water, fats) or !!(2) for solution, producing a concentration in solution greater than some solubility concentration, Cs, (sugars, salt, etc)can be achieved by:
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!! heating the solvent prior to dissolving the solute so

that high concentration solutions can be made; cooling this solution below the saturation temperature results in supersaturated solution (A ! B)
CRYSTAL FORMATION
!! adding a second solvent in which a solute is

insoluble (shift the solubility curve down).
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How to achieve supersaturation?.... !! evaporate solvent from a solution until the saturation concentration has been exceeded, and (A # C)
CRYSTAL FORMATION! Solubility-Supersolubility Diagram!

Labile (supersaturated unstable)!
Sugar concentration Dr Abd Karim Alias, 2005
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C Metastable (supersaturated)! B
Stable " (Under saturated solution)!

Temperature
CRYSTAL FORMATION
!! BUT not every supersaturated solution will crystallise during the time available for observation (metastable solution)
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!! Once the solution/melt has been supersaturated, there is a thermodynamic driving force for crystallization, i.e., the molecules tend toward the crystalline state to lower the energy level of the system.
CRYSTAL FORMATION !! METASTABILITY a region/zone where nucleation does not occur within the time scale of the process !! In metastable zone, crystal may grow (by adding seed crystal heterogeneous nucleation) but nucleation is negligible. !! In labile zone, nucleation occurs spontaneously. !! In the stable zone, nucleation will not occur any crystals put in this solution will dissolve.
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CRYSTAL FORMATION
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!! NUCLEATION molecules in the liquid state rearrange & eventually form into a stable cluster that organizes into a crystalline lattice. !! The ordered arrangement of molecules in the lattice involves a release of latent heat as the phase change occurs.
CRYSTAL FORMATION
NUCLEATION PRIMARY Homogeneous Heterogeneous SECONDARY

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CRYSTAL FORMATION !! PRIMARY NUCLEATION formation of crystal nuclei from a solution that contained no preexisting crystals ! !!Homogeneous nucleation is the formation of nuclei within a homogeneous uid rarely occurs in practical food processing conditions. ! !!Heterogeneous nucleation is initiated by contact with foreign particles and surfaces. ! !! SECONDARY NUCLEATION refers to the formation of crystal nuclei due to the presence of existing crystals !
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CRYSTAL FORMATION Secondary Nucleation

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Crystal
- Wall Crystal - Crystal

Fluid shear
New nuclei
Crystal - Stirrer
CRYSTAL FORMATION Rate of Nucleation
Homogeneous
Heterogeneous
Solubility Melting point
B Driving force
Glass transition
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Nucleation rate
CRYSTAL FORMATION !! CRSYTAL GROWTH nuclei that form can grow to larger size based on the available supersaturation in the solution. The extent of this growth depends on the magnitude of supersaturation remaining (DC) in solution after nucleation has occurred.! !! Growth continues until all of the available supersaturation has been depleted & the system approaches an equilibrium in phase volume, which depends on temperature & composition of the system.!
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CRYSTAL FORMATION !! For example, if a highly concentrated sugar syrup is allowed to crystallize, the concentration of the remaining solution phase decreases until it reaches the equilibrium concentration (solubility) for that temperature & system.! !! Once this solubility concentration is attained, crystallization ceases; the system has attained a stable phase volume of crystalline material.!
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CRYSTAL FORMATION Kinetics of Growth Rate

C Glass transition Nucleation Homogeneous
Growth rate
Heterogeneous
Growth
B Driving force
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CRYSTAL FORMATION !! RECRYSTALLIZATION Once equilibrium in phase volume has been attained, changes still may take place in the crystalline structure during longterm storage, especially where temperature & RH are likely to vary over time this changes within the crystalline structure is to minimize the energy of the system further (ie approach global equilibrium).! !! Two examples of recrsytallization: coarsening of ice crystals in frozen food during storage & formation of fat bloom in chocolate.!
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TYPES OF CRYSTAL LATTICE STRUCTURE
The complexity of the molecular structure may lead to differences in the crystal lattice structure. Such cases may be due to:! "! crystallization of different types of isomers of a molecule present in solution; example: enantiomers (D-glucose & L-glucose) and anomers (a-lactose & b-lactose);!
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"! polymorphism, where complex molecules crystallize in more than one molecular arrangement depending on conditions.!
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"! crystallization of hydrates, where one or more molecules of water are incorporated into the crystal lattice along with the molecule of the crystallizing species;!
!! If a lactose solution is concentrated & cooled rapidly, an amorphous lactose glass can be formed. In addition, an anhydrous a-lactose crystal can be formed, either by drying a-lactose monohydrate crystals or by direct crystallization from nonaqueous solvent.!
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!! Conversion between enantiomeric & hydrated forms may occur, depending on the conditions. Example: a lactose solution can crystallize into either a-lactose monohydrate at T <93.5 C or blactose (anhydrous) at T>93.5 C.!
Different anomeric forms of !- and "-lactose crystals
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Different forms of lactose crystals

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!! POLYMORPHISM some materials exhibit the ability to crystallize into multiple crystal structures, depending on the arrangement of the molecules, eg. Sorbitol forms 4 polymorphs (", #, $ and %). !! Polymorphism in lipids Lipids (triglycerides or fats in particular) forms 3 main polymorphs, ie. ", $ and $, although in some cases there may be additional polymorph (a very low stability % form) & subclasses within a main polymorphic type ($ $ $1 and $ 2).
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!!The arrangement of the lipid molecules (angle of orientation & packing arrangement) in the crystal lattice structure is different for each polymorph. !!Differences in physical properties between lipid polymorphs arise due to differences in molecular arrangement. The least stable forms have lower density, lower melting point, and lower heat of fusion than the more stable forms, since the molecules in the less stable forms are not arranged in their lowest energy conformation. 36
Free energy change during nucleation for different lipids polymorphs
Nucleation rate of lipid polymorphs

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Transformation of polymorphic form of lipid crystals

Fat heat Oil rapid cooling
LIQUID Temperature
Solidification
$'
"&
SOLID
Monotropic polymorphism of lipids
Stability, melting point
$&
38
Polymorphism in lipids .cont
!! Rapid cooling generally results in formation of less stable polymorphs since the more stable polymorphs require longer times to allow proper orientation of the molecules into the most stable lattice structure.
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!! Lipids exhibit monotropic polymorphism, where the less stable polymorphs form first and then transform to the more stable polymorphs
Polymorphism in lipids .cont
!! Some fats, eg milk fat & palm oil does not crystallize into the $ form (due to the molecular complexity of the fatty acids); the $-polymorph is the most stable form found in these fats.
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!! Therefore, the less stable polymorphs (%, ", $) generally crystallize before the most stable $polymorph. After crystallization has taken place, the less stable polymorphs then transform to the more stable forms. Eventually, the most stable polymorph will form, although this may take many months in food products.
CONTROLLING CRYSTALLIZATION Several circumstances for controlling crystallization in foods: (1) Control to produce desired crystalline structure !! control of the correct number, size (and distribution), shape, and polymorph of crsytals is required to provide the desired processing characteristics, quality (texture, flavor, etc), appearance, and shelf stability of the product
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CONTROLLING CRYSTALLIZATION
cont
(1) Control to produce desired crystalline structure !! A certain crystal size distribution is desired in sugar products (sugar-frosted cereals, fondants, panned candies, caramels, etc), frozen foods (ice cream, frozen desserts, etc), and lipid-based products (tempering of chocolate, butter, margerine, shortening, etc)in these products, numerous small crystals are desired to give the desired smooth texture.
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cont
(1) Control to produce desired crystalline structure !! In other processes, fewer but larger crystals are desired, eg, for efficient separation during refining of sugars, fractionation of fats & freeze concentration !! Controlling crystal size distribution (by controlling the kinetics of nucleation & growth) is vitally importantthrough proper choice of formulation & processing conditions
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Few nuclei formed at points A and C
Nucleation Homogeneous
0
0
0
0
Growth rate
Heterogeneous
Growth
0 0 0 0 0 0 0 0
0
0 0d 0 0 0
0
0 0d 0
0 0 0
00
0
0 0
0 0
0 0
000 0 0
00
0d 0
0 0 0 0
00 0
0 0 0
00 0
0d 0
0
0 0 0
0
0
0
0
0
0 0 0
B Driving force
Glass transition
Many nuclei formed at points B
Schematic diagram of nucleation and growth rate curve
Crystal size distributions generated at different points on the crystallization rate curves (at point A, B and C)
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CONTROLLING CRYSTALLIZATION (2) Control to prevent crystallization

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!! In some products, crystallization is undesired even though, thermodynamically, there is a driving force (supersaturation or subcooling) for crystallization to occur.
CONTROLLING CRYSTALLIZATION (2) Control to prevent crystallization Some examples: !!The unfrozen phase of ice cream, which is supersaturated in lactose, may crystallize during storage, causing a sandy defect in the ice cream !!In caramel, the aqueous phase contains sucrose & lactose, both of which may be supersaturated during storage at room temperature & develop crystalline structure " graining defect
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CONTROLLING CRYSTALLIZATION (2) Control to prevent crystallization Two ways to prevent crystallization: (i)! the system must have sufficiently low mobility (high viscosity), or (ii)! the crystallizing species must be inhibited by addition of other molecules, eg, by addition of corn syrup to prevent graining in caramels
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CONTROLLING CRYSTALLIZATION (3) Control of change in crystalline structure (recrystallization) Some examples: !!Ice crystals in ice cream & frozen foods gradually increase in size during storage, leading to coarse/ sandy texture & loss of structural integrity upon thawing !!Changes in lipid crystals (due to polymorphic transformation)bloom formation in chocolate, grainy texture in margerine)
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.Cont
!! The overall process is called recrystallization typically driven by reequilibrium to either a lower surface energy or lower internal energy without a change in the amount of crystalline mass
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(3) Control of change in crystalline structure (recrystallization)
Mechanisms of recrystallization !!Ostwald ripening conditions may exists where small crystals are in undersaturated conditions at the same time that large crystals are in supersaturated conditions # small crystals dissolve/melt & large crystals grow !!Accretion crystals that are very close to each other tend to grow together to form one large crystal; this mechanism is very important in some foods, particularly those with high numbers of very small crystals in close proximity (eg. ripening of ice crystals in ice cream)
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Mechanisms of recrystallization
.Cont
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!!Polymorphic transformation lipids undergo a polymorphic change as less stable crystal forms change to a more stable forms. The subsequent release of additional latent heat during the transformation may cause substantial problems in the product
.Cont
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!!Melt/refreeze A change in the phase volume of crystalline material occurs as temperatures fluctuate during storage, accompanied by a change in crystalline structure (size, number, shape, etc); the smallest crystals are most sensitive to temperature increases & may eventually disappear or dissolve/melt away.
N0
Mean crystal size Number of crystals
r0 Time
Crystal size
Increase in mean size and decrease in total crystal numbers with time of crystallization
Typical changes in crystal size distribution in ice cream during storage

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Storage time
Frequency (%)
Factors affecting control of crystallization (1) Heat & mass transfer rates !!The rates of heating, cooling, holding times & temperatures, evaporation of waters and agitation all can impact crystallization !!Example: In production of grained caramel and fudge, the rate of cooling to a desired crystallization temp determines the extent & type of nucleation. !!If crystallization is not desired,cooling must be sufficiently rapid that the material passes through the crystallization zone before nucleation 54 occurs.
Factors affecting control of crystallization

.Cont
!!If large crystals are desired for efficient separation, then nucleation must occur at a higher temperature (or lower supersaturation) so that fewer nuclei are formed.
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(1) Heat & mass transfer rates !!For lipids, suitable time-temperature protocol (tempering) must be chosen to maximize formation of the desired polymorphic form

.Cont
(1) Heat & mass transfer rates

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!!In products where massive nucleation is desired, it is important to provide sufficient agitation to promote maximal nucleation. !!For example: during processing of fondant, the sugar mass is cooled to the desired crystallization temperature & then worked extensively in a beater to promote massive crystallization # results in production of many small crystals & produces a smooth fondant
Factors affecting control of crystallization (2) Product formulation !!Addition of various soluble components in a formulation typically inhibits crystallization, eg. The use of glucose syrups in hard candy inhibits graining of the sugar mass during processing & storage !!Addition of gums & proteins to ice cream reduce the rates of crystallization & the subsequent coarsening of the ice crystals
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Factors affecting control of crystallization (3) Post-processing effects Changes in crystalline structure may take place after processing or during storage. This could be due to: !! Incomplete crystallization has not been achieved during processing, ie, maximum phase volume of the crystalline phase may not be attained prior packaging !! Thermodynamic ripening effect (recrystallization) that can cause significant changes in crystalline structure & size distribution 58

.Cont
(3) Post-processing effects !! Equilibration in moisture content (during storage) due to moisture migration within different components of the same product (eg, between the sauce and crust of a frozen pizza) or through equilibration with the storage air conditions
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Control of crystallization during processing Example: Tempering of chocolate

!! Tempering process involves holding
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chocolate at the appropriate temperature for the proper time to form the desired crystalline structure. !! In commercial operations, the chocolate mass is pumped through a heat exchanger where the temperature is controlled in different sections to ensure proper crystallization.
Control of crystallization during processing Example: Tempering of chocolate !! Molten chocolate at about 50C is cooled rapidly in the first section to ~26C to initiate crystallization of the " polymorph. The rate of nuclei formation at these conditions is rapid so that many crystals are formed, which results in an increase in viscosity of chocolate mass. !! Since the "-polymorph is desired, the temperature of the chocolate mass is increase to cause melting of the unstable form & transformation on the more stable "-polymorph. 61
Typical time-temperature protocol during tempering of chocolate
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Chocolate bloom
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Crystallization in Foods

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CRYSTALLIZATION IN FOODS!

Dr Abd Karim Alias, 2005

PRESENTED BY: Prof. Abd Karim Alias

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

Crystallization may be employed as:

Arrangement of sucrose molecules within crystal lattice structure

Shape of lactose crystals grown at different supersaturation

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

Metastable !B! (supersaturated)!

Dr Abd Karim Alias, 2005

Labile (supersaturated unstable)!

!! When solute contents > solubility concentration (Cs), ! supersaturated solutions.

!! heating the solvent prior to dissolving the solute so

!! adding a second solvent in which a solute is

Dr Abd Karim Alias, 2005

CRYSTAL FORMATION! Solubility-Supersolubility Diagram!

Stable " (Under saturated solution)!

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

NUCLEATION PRIMARY Homogeneous Heterogeneous SECONDARY

Dr Abd Karim Alias, 2005

CRYSTAL FORMATION Secondary Nucleation

- Wall Crystal - Crystal

CRYSTAL FORMATION Rate of Nucleation

Solubility Melting point

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

Dr Abd Karim Alias, 2005

CRYSTAL FORMATION Kinetics of Growth Rate

Solubility Melting point

Dr Abd Karim Alias, 2005

TYPES OF CRYSTAL LATTICE STRUCTURE

Dr Abd Karim Alias, 2005

TYPES OF CRYSTAL LATTICE STRUCTURE

Dr Abd Karim Alias, 2005

TYPES OF CRYSTAL LATTICE STRUCTURE

Dr Abd Karim Alias, 2005

TYPES OF CRYSTAL LATTICE STRUCTURE

Different anomeric forms of !- and "-lactose crystals

Dr Abd Karim Alias, 2005

TYPES OF CRYSTAL LATTICE STRUCTURE

Different forms of lactose crystals

Dr Abd Karim Alias, 2005

TYPES OF CRYSTAL LATTICE STRUCTURE

Dr Abd Karim Alias, 2005

TYPES OF CRYSTAL LATTICE STRUCTURE

Dr Abd Karim Alias, 2005

TYPES OF CRYSTAL LATTICE STRUCTURE

Free energy change during nucleation for different lipids polymorphs

Nucleation rate of lipid polymorphs

Dr Abd Karim Alias, 2005

Transformation of polymorphic form of lipid crystals

Monotropic polymorphism of lipids

Stability, melting point

Dr Abd Karim Alias, 2005

Polymorphism in lipids .cont