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10.3.3.2 AnnealingIf the water content is high enough for gelatinization but the temperature is toolow, the conditions might be suitable for annealing (i.e., a process that improvesAmust be below Tmor the crystallites will just melt and above Tgor the systemwill be too rigid for anything to happen. In this temperature range, the leastperfect crystallites melt and the molecules crystallize on the other, more nearlyperfect crystals. For starch, this means that the same type of crystallites will beobtained, but of better quality and perhaps with a higher degree of crystallinity.If gelatinization then occurs (i.e., see upward movement in Figure 10.2), it willbe apparent that the gelatinization temperature range has moved to highertemperatures and has become more narrow. [83,106,127–129].For large barley starch granules, the modal gelatinization temperature wasfound to increase from 61 to 74°C after annealing at 50°C for 6 weeks [116].Such long annealing times are not necessary for an effect. For steeping (i.e.,when cereal grains are soaked in water to facilitate the extraction of starch),changes in properties have been observed after 24 to 72 hours [86,87]. Whenstarch is treated, annealing times much less than 24 hours have been reported[83,129]. The important parameter is not time but the difference between Toand TA. If this difference is 20 to 25°C or more, no influence at all is evident,whereas a difference around 5°C has been observed to cause an increase inToof around 13°C for wheat and potato starches [129]. No subsequent leakingof amylose occurs during the annealing [83].Just as for heat treatment, annealing causes an increase in the onset ofgelatinization, but then some interesting differences occur. With annealing, thegelatinization temperature range narrows [83,127,129]. If the annealing iscarried out at water contents for which a biphasic DSC endotherm is obtainedfor the untreated starch, annealing will transform the biphasic endotherm intoa single one [129]. Changes in enthalpy (∆H) after annealing have beenreported, but these changes are difficult to interpret; for example, a decreasein ∆Hmight indicate that TAis too close to To(i.e., gelatinization has occurred).A change in the polymorphic form as a result of annealing has not beenreported, but a slight improvement of the x-ray diffraction lines and a decreasein the background have been [87,130]. For normal and high-amylose starches,an increase in the V-pattern due to annealing has been reported [87]. Swellingand solubility are both affected by annealing, and usually they are found todecrease [86,87]. An exception has been found in barley starch, for which theswelling was found to increase at 90°C.Commercial starches might undergo an annealing treatment during theproduction process. When laboratory-prepared samples of corn starch werecompared with commercially produced ones [131], the laboratory-preparedsamples showed a broad gelatinization temperature range, whereas the commercial samples showed a rather narrow range. Annealing, however, did not© 2006 by Taylor & Francis Group, LLCthe crystallinity; see Figure 10.2). The temperature for achieving annealing (T)
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