An investigation of the mechanisms of degradation of a branched polymer in extrusion was performed using starch as substrate. Starch has the advantage that the distribution of degree of polymerization of individual branches can be readily obtained using a debranching enzyme and also that it does not undergo any reaction except scission during extrusion, thereby aiding mechanistic interpretation. Various starches, containing a range of the highly branched amylopectin component and the much less branched amylose component, were extruded in the presence of water and glycerol as plasticizers with extruder barrel temperatures ranging from 50 °C at the hopper zone through to 140 °C near the die exit. Analysis by size-exclusion chromatography of both whole and debranched samples subject to various levels of extrusion showed that the extrusion degradation process involved preferential cleaving of larger molecules, while causing the size distribution to narrow and converge toward a maximum stable size. This is analogous to a similar effect of shear degradation of droplets in emulsions. It was also found that the susceptibility of polymer molecules to shear degradation is not only dependent on the size of the molecule but also extensively influenced by the branching structure. High branching density and short branch length were associated with higher susceptibility to shear degradation. This is explained by the hypothesis that a short-chain hyperbranched polymer has a relatively inflexible structure, leading to a higher susceptibility to shear scission. The degradation process is not significantly selective toward the length of individual branches when the polymer is in a molten state but it preferentially breaks longer branches when the starch polymer is in a semicrystalline granular form. These inferences are generally applicable and use the additional information from the branch length distribution and absence of side reactions, which is generally not available for synthetic polymers.
The gelatinisation process of waxy starch was studied using both differential scanning calorimetry (DSC) and modulated temperature DSC (MTDSC). It was revealed that the results from the two techniques, especially the onset gelatinisation temperature, were slightly different, which may be due to the MTDSC principle and the mechanism of starch gelatinisation. Thus, it is suggested to avoid using MTDSC alone in the characterisation of starch thermal transitions especially in a quantitative way. However, MTDSC has the advantage in understanding the gelatinisation mechanism since it can separate the capacity change (reversible thermal event) from kinetic components (irreversible event). The stepwise change on reversible heat flow measured by MTDSC during gelatinisation was considered due to the phase transition of highly constrained starch polymer chains in granular packing. On the other hand, the glass transition of gelatinised starch (also thermoplastic starch) could not necessarily be detected by conventional DSC or MTDSC. However, by using a high‐speed DSC method, the extremely weak glass transition of the gelatinised starch with low moisture content could be enlarged and detected, which confirms the existence of glass transition of the gelatinised starch with low moisture content. This knowledge is helpful in the processing of starch‐based foods and polymeric materials.
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