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SOLID CARBOHYDRATE ST RUCTURE TRANSITION AND I T S

RELATIONSHIP TO FOOD PRODUCTS AND PROCESSES


Solid Carbohydrate Structure Transition
The properties of solid carbohydrates will dpend on the method of preparation, paricularly regarding
its structure (crystalline or amorphous). The largest effect on solid carbohydrates properties result
from sorption of water, especially for the recrystallization of amorphous carbohydrate.

N iss an (1976A, B; 1977A, B) investigated how the change in mechan ical


properties for H-bond-dominated solids ( mechan ical properties that are
determined by H bonds) is related to the destruction of , the H bonds. Two modes of
action for the addition of , water are defined, one at water contents below the BET
monolayer, where each added water dissociates one H bond, and the second at water
contents above the BET monolayer where H-bond cooperativity is active and one
water acts to dissociate one H bond, but where that breakage disrupts more H
bonds in th e structure.

Effect of Water Sorption. There have been inane invest igations of the effect of
water sorption on the properties of dried car bohydrate in particular, the
recrystalliza tion of amorphous carbohydrates.

K a r g i n ( 1957) noted that glucose glass sorbs water only on the surface due to
t h e low diffusivity of water in the glass. As the surface hydrates, a saturated
solution forms and the glass softens, giving higher water diffusion.

Collapse Temperature of freeze-dried sugar.


T s o u r o u f l i s (1976) investigated collapse temperatures of freeze-dried sugars
and s u g a r mixtures as a function of moisture content and blend composition. It
was shown that by addition of high molecular weight materials . The collapse
temperature of sensitive low molecular weigh materials can be effectively raised.

To and Flink (1978A, B, C) expanded the earlier studies on collapse of freeze-dried


carhohydrate. The influence of moisture, molecular weight, and various additives on
secon-order transitions in sugar was determined . Freeze-dried sucrose was
shown to have a glass transition at 52 o C, a devitrification at 112 o C, and a
melting of crystals formede at 192 o C. Freeze-dried maltose, on the other hand
demonstrated only a glass transition at 100oC (Fig.17). Since maltose forms a
monohydrate crystal, it. is possible that the lack of a recrystallization peak in the
DTA is due to the fact that only heating was used to cause collapse. In this case,
the anhydrous state of the sucrose crystal allows the formation of the crystal
under the action of heat alone, while formation of a maltose crystal would also
require the presence of adequate water to develop the monohydrate.

The collapse behaviour of blended systems of two components shown two types of
behaviour. When the freeze-dried system contained components thats could form a
crystalline phase, then total collapse was associated with the melting of the crystalline
phase. Though partial collapse of the amorphous component could occur prior to
crystallite melting. For blends that freeze dry as amorphous solids, collapse
temperature showed a nonlinear relationship with composition. Freiser and Tummala
(1975) indicated that the glass transition temperatures for mixture generally showed
nonlinear behaviour when the mixture composition is expressed on a weight %
basis. when volume % or mole %, is used to quantify the mixture composito n,
a linear relationship is obtained, which supports the concept that volume
change is the critical factor in the glass transition.

The collapse temperature was shown to be inversely proportional to the


molecular weight for a homologous series of' malto-oligosaccharides.

In all the above conditions, collapse behavior could be calculated using


equations similar to those developed in the literature for glass transitions. It
s eems likely, therefore, that collapse and glass trans i tions are closely
related. While it is tempting to think of collapse as the macroscopic
manifestation of a glass tr ansition in the freeze-dried ma terial where the
subsequent viscous flo w occurs over a time frame so that it is visible, it is
valuable to remember tha t the glass transition is reversible (if no
recrystallization has occur ed) while collapse has not been shown to be reversible.

White and Cakebread (1966; 1969) have described conditions for formation
of glassy carbohydrates in foods, the relationship of the glassy state in food
products to their properties, and the changes that can occur if the glassy
state is allowed to become unstable. They describe changes that can occur in
boiled sweets (distortion, stickiness, or graining), milk powders (caking, and
lumpiness), ice cream (sandiness), and freeze drying (liquification and
caking). The primary change in all these cases is the viscous flow of the
carbohydrate, which in many cases will be followed by its recrysatllization.

Collapse in Freeze Drying. A review of the status of information on collapse phenomena


during freeze drying was presented by Mac Kenzie (1975).
Collapse during freeze drying results from a CAS, viscosity, which is inadequate
to support the weight of the CAS and withstand surface forces present. This loss of structure
can occur at either the interface or in the “dry” layer.

Bellows and King ( 1973) indicated that both drying rate and aroma retention during
freeze drying were dependent on collapse bahavior. While drying rate would increase
with increase with incrace in ice layer temperature, due to higher heat transfer rates,
the onset of collapse resulted in no further improvements in drying rate. Ettrup
Pedersen et al.( (1973) examined the influence of chamber pressure on retention
of flavor for freeze-dried coffee and were able to show that when the chamber
pressure corresponded to an ice front temperature above coffee's collapse
temperature, there was o f significant loss of volatile compounds. It was also noted
that the color of the coffee darkened significantly a t this point, due to the changed
light reflectance properties of the collapsed surface. In that study, overall particle
geometry was maintained, collapse bang limited to the surfaces of the CAS.

Swinnen el al. (1974) and Tobback et al.(1979) studied the effect of mixed
systems of glucose and salt on collapse behavior during freeze drying. Tobback et
al. (1979) also demonstrated that aroma retention was dependent on the stability
of the CAS, though in this case, conditions which lead to recrystallization does not
occur under freeze drying, aroma retention is height.

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