Improved volatile cargo retention and mechanical properties of capsules via sediment-free in situ polymerization with cross-linked poly(vinyl alcohol) as an emulsifier

Hypothesis: It is hypothesized that poly(vinyl alcohol) (PVOH) as an emulsifier destabilizes the insoluble molecular aggregates by increasing interparticle interactions and their tendency toward agglomeration into large particle aggregates during the encapsulation process of one-step in situ polymerization. Porosity of capsule shells is expected to decrease with reducing agglomeration tendency to allow dense packing of smaller insoluble aggregates. Cross-linking the polymer network further reduces shell permeability to improve the retention of volatile cargos. PVOH also modifies the short-range order of polymer network to bestow improved mechanical properties in addition to the shell thickening effect at appropriate synthesis conditions.

Experiments: PVOH was used to stabilize a heptane-in-water emulsion as a template for producing capsules via one-step in situ polymerization. Shell morphologies at different PVOH concentrations were compared. Physical freeze-thawing and chemical cross-linking were adopted separately to synthesize capsules with a volatile cargo, and its retention was characterized qualitatively by a solvatochromism-based fluorescent method and quantitative payload calculation. Mechanical properties of capsules were tested with micromanipulation. The effect of graphene oxide (GO) impregnation into capsules was studied with various co-emulsifiers.

Findings: When PVOH alone was used as the emulsifier for capsule synthesis, the higher its concentration, the more porous the shell structure was. At very low concentrations, visible pores were eliminated. Freeze-thaw cycles reduced the permeability of capsule shells when visible pores were absent. Chemical cross-linking with poly(acrylic acid) (PAA) significantly improved the retention of volatile cargo heptane. PVOH substantially reduced polymer sediment during capsule synthesis, which eliminated the tedious centrifugation procedure that normally would have followed. Superior mechanical strength of capsules was achieved with PAA cross-linked PVOH at appropriate conditions. The impregnation of aqueously dispersed GO into capsules was also promoted by using PVOH but not hydrocolloid emulsifiers.