Starch-based emulsion
microgel particles with different starch
(15 and 20 wt %) and oil contents (0–15 wt %) were synthesized,
and their lubrication performance under physiological conditions was
investigated. Emulsion microgels were subjected to skin mimicking
or oral cavity mimicking conditions, i.e., smooth
hydrophobic polydimethylsiloxane ball-on-disc tribological tests,
in the absence or presence of salivary enzyme (α-amylase). In
the absence of enzyme, emulsion microgel particles (30–60 vol
% particle content) conserved the lubricating properties of emulsion
droplets, providing considerably lower friction coefficients (μ
≤ 0.1) in the mixed lubrication regime compared to plain microgel
particles (0 wt % oil). Upon addition of enzyme, the lubrication performance
of emulsion microgel particles became strongly dependent on the particles’
oil content. Microgel particles encapsulating 5–10 wt % oil
showed a double plateau mixed lubrication regime having a lowest friction
coefficient μ ∼ 0.03 and highest μ ∼ 0.1,
the latter higher than with plain microgel particles. An oil content
of 15 wt % was necessary for the microgel particles to lubricate similarly
to the emulsion droplets, where both systems showed a normal mixed
lubrication regime with μ ≤ 0.03. The observed trends
in tribology, theoretical considerations, and the combined results
of rheology, light scattering, and confocal fluorescence microscopy
suggested that the mechanism behind the low friction coefficients
was a synergistic enzyme- and shear-triggered release of the emulsion
droplets, improving lubrication. The present work thus demonstrates
experimentally and theoretically a novel biolubricant additive with
stimuli-responsive properties capable of providing efficient boundary
lubrication between soft polymeric surfaces. At the same time, the
additive should provide an effective delivery vehicle for oil soluble
ingredients in aqueous media. These findings demonstrate that emulsion
microgel particles can be developed into multifunctional biolubricant
additives for future use in numerous soft matter applications where
both lubrication and controlled release of bioactives are essential.