Abstract
This study applies differential scanning calorimetry (DSC) to probe the effect of nanoconfinement on gelation of mineral oil (MO), soybean oil (SO), ethylene glycol (EG), polyethylene glycol (PEG), and polypropylene glycol (PPG) by low molecular weight gelators, stearic and 12-hydroxystearic acids. Nanoconfinement is accomplished by embedding the gels into silica nanopores. In agreement with our previous work on high molecular weight polymeric gelators, nanoconfinement invariably causes a decrease in the heat of gelation. The effect is linked to restricted molecular mobility, which hampers integration of the gelator molecules into the network as well as spatially limits its growth. A new effect discovered in this work is a decrease in the gelation temperature of the nanoconfined MO and SO systems. By combining an advanced isoconversional method with the Turnbull-Fisher nucleation model it has been possible to link this effect to deceleration of gelation that originates from an increase in the nucleation energy barrier. It has been proposed that whether nanoconfinement causes a decrease or an increase in the gelation temperature can depend on polarity of liquid. The proposal is upheld by measurements on the systems involving polar liquids (EG, PEG, PPG) that have demonstrated an increase in the gelation temperature under nanoconfinement.
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