| A new class of polymers known as "bioplastics" has emerged and is expanding rapidly. This class consists of polymers that are either bio-based or biodegradable, or both. Among these, polysaccharides, namely starch, are of great interest for several reasons. By gelatinizing starch via plasticizers, it can be processed in the same way as thermoplastic polymers with conventional processing equipment. Hence, these bio-based and biodegradable plastics, with their low source and refinery costs, as well as relatively easy processability, have made them ideal candidates for incorporation into various current plastic products.;Four different plasticizers have been chosen here for gelatinization of thermoplastic starch (TPS): glycerol, sorbitol, diglycerol and polyglycerol, with the latter two being used for the first time in such a process. Two methodological categories are used. The first involves a calorimetric method (Differential Scanning Calorimetry) as well as optical microscopy; these are "static" methods where no shear is applied A wide range of starch/water/plasticizer compositions were prepared to explore the gelatinization regime for each plasticizer. The onset and conclusion gelatinization temperatures for sorbitol and glycerol were found to be in the same vicinity, while diglycerol and polyglycerol showed significantly higher transition temperatures. The higher molecular weight and viscosity of polyglycerol allow this transition to occur at an even higher temperature than with diglycerol. This is due to the increase in molecular weight and viscosity of the two new plasticizers, as well as their significant decrease in water solubility. It is demonstrated that the water/plasticizer ratio has a pronounced effect on gelatinization temperatures. When plasticizer content was held constant and water content was increased, it was found that the gelatinization temperature decreased for all the plasticizers. Meanwhile, when the water content was held constant and the plasticizer content was increased, the gelatinization temperature increased for glycerol, sorbitol and diglycerol, but it moved in the opposite direction in the case of polyglycerol. The gelatinization temperature variation for glycerol, sorbitol and diglycerol caused by changing water and plasticizer content indicates that water is the primary agent causing granular swell and plasticization in the gelatinization process. Due to the high molecular weight and viscosity, as well as the low hydroxyl group density (~ one --OH per two carbon) and borderline solubility of polyglycerol in water, it is believed that water-aided penetration of the plasticizer among the crystalline structure of starch molecules is significantly decelerated. So it is proposed that in the case of low-water solubility of the plasticizers, gelatinization temperature is determined more by the total amount of the plasticizer and water, rather than the water/plasticizer ratio. Increasing the miscibility of polyglycerol in water by increasing the temperature of the initial slurry, results in a return of the system to the typical thermal dependence of gelatinization with plasticizer/water ratio.;Secondly, the gelatinization of starch under "dynamic conditions" was studied. In this case, a constant shear is applied to the slurry, along with a temperature ramp to induce gelatinization. This is, in fact, a rheological technique that heats up the slurry, while a mechanical shear is applied throughout. The reason for using this method is that in the plastic industry, thermoplastic starch is produced via processes involving shear such as extrusion, but, to date, there has not yet been a thorough study on the effect of pure shear on the gelatinization process. Glycerol, diglycerol and sorbitol were subjected to different dynamic gelatinization treatments in a couette flow system, and the results were compared with static gelatinization. Applying shear showed virtually no effect on the onset gelatinization temperature. However, the conclusion temperature was remarkably reduced with the presence of shear. So it can be stated that the conclusion temperature is more kinetically driven (i.e. by applying high shear), so that complete gelatinization can be achieved in a shorter time-frame. (Abstract shortened by UMI.). |
