In this work, the ability of several solvents to induce gel formation from amylomaize starch solubilized in dimethyl sulfoxide (DMSO) was investigated. The formed gels were subjected to solvent exchange using ethanol and dried with supercritical carbon dioxide (sc-CO2) to obtain the aerogels. The influence of starch concentration (3–15 wt%) and solvent content (20–80 wt%) on gel formation was also studied. It was demonstrated that the gelation of starch in binary mixtures of solvents can be rationalized by Hansen Solubility Parameters (HSP) revealing a crucial hole of hydrogen bonding for the gel’s strength, which is in agreement with rheological measurements. Only the addition of water or propylene glycol to starch/DMSO solutions resulted in strong gels at a minimum starch and solvent content of 7.5 wt% and 50 wt%, respectively. The resulting aerogels showed comparably high specific surface areas (78–144 m2 g−1) and low envelope densities (0.097–0.203 g cm−3). The results of this work indicate that the HSP parameters could be used as a tool to guide the rational selection of water-free gelation in starch/DMSO systems. In addition, it opens up an attractive opportunity to perform starch gelation in those solvents that are miscible with sc-CO2, avoiding the time-consuming step of solvent exchange.
