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Crystallisation
Nucleation, Growth and Supercooling Post growth events, crystal ripening
Polymorphism
Fats and triglycerides have different forms with different melting points Each form is called a polymorph and the phenomenon is called polymorphism: Greek many forms Fats & triglycerides occur in any one of three basic types: (alpha), ' (beta prime) and (beta) All fats have an polymorph; some are ' stable; some are stable Transitions go from to ' to , in that order, which is the order of increasing stability.
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'
Tilted chains Tilted chains with adjacent with all zigzags zigzags in in same plane different planes
64C (147F) 73C (163F)
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Triple-Spacing Double-Spacing
-2
-3
Chain sorting
3X 2X
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22C
Liquid
37C
Solid '1-2
-15C
5 to 7C
Solid '2(sub-)
-5 to -10C
Solid -2 + -2
from Persmark & Stahl, 1976
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Polymorph Comment
-3 -2 -2 -2 -2 -2 -2 -3
Simple TAG mixture, mainly SOS type Simple TAG mixture, mainly SSS type. Except hydrogenated PO is -2. Complex TAG mixture Complex TAG mixture Complex TAG mixture Complex TAG mixture Moderately simple TAG mixture, diacylglycerols important Moderately simple TAG mixture, mainly SSO type
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Normal ()
Sandy ()
1 scale unit = 100
(Danisco TP 1504-2e)
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Crystallisation
Nucleation, Growth and Supercooling Post growth events, crystal ripening
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Temperature
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Crystallisation: Nucleation - 1
A crystal nucleus is the smallest crystal that can exist in a triglyceride mixture of a certain concentration and temperature Aggregates of molecules smaller than a nucleus are called embryos and will redissolve if formed A stable crystal will form only when the energy gain due to the heat of crystallisation exceeds that required to overcome the surface energy required to increase the surface
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Crystallisation: Nucleation - 2
Homogeneous Nucleation takes place spontaneously in the bulk of the liquid, but does not occur in fats in practice Instead, Heterogeneous Nucleation takes place and is initiated by solid particles such as dust, container wall or seed crystals This is why emulsions are difficult to crystallise - each droplet is isolated from the others so that seeds cannot propagate Secondary Nucleation occurs when small pieces break from existing crystals and act as nuclei for further crystallisation
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Crystallisation: Nucleation - 3
The least stable, , polymorph has the lowest surface energy, as well as the lowest heat of crystallisation Small differences in surface energy produce large differences in nucleation rate Thus nucleation rates are in the order:
> >
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Crystallisation: Nucleation - 4
108
'
No. of nuclei / second / m3 106
Nucleation rate is greater for the less stable polymorph and is exponentially dependent on temperature
104
102
24
32 36 28 40 Temperature (C)
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Crystallisation: Growth
Once a nucleus has formed, it starts to grow The growth rate is proportional to the degree of supercooling, i.e. lower temperature, and inversely proportional to the viscosity Like the nucleation rate, the growth rate depends on the polymorph crystallised The more stable the polymorph the less soluble it is and therefore the higher the growth rate, i.e.:
> >
But, rapid cooling of a fat always leads to the initial formation of unstable (or ) crystals because nucleation is exponentially related to temperature
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Crystallisation: Summary
Liquid Nucleation
. . . . . . . . . . . . . . .
Crystallisation
Separation
Agglomeration
Ripening
Stearin
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Olein
Adapted from: desmet ballestra
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Heater
Sample
Reference
Cooling/crystallisation
Sample Block
(held at -90 C) Resistance Thermometer Difference in heat required
Heating/melting
Computer
Temperature
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32
T 30 e m p e r a 28 t u r e / 26 C
Temp. Rise
24
10
20
30
40
50
Vacuum
Oil
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70 60 50 40 30 20 10 0 0 10 20 30 40
Minutes
This fat mixture crystallises more slowly than the other two fats
50 60 70 80
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Crystallisation
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