Relationship between size and cellulose content of cellulose microgels (CMGs) and their water-in-oil emulsifying capacity

Soluble polysaccharides have been used extensively as gelling/thickening agents in emulsions, but they generally display weak surface activity. Insoluble polysaccharides such as cellulose can be converted to thickening agents and even emulsifiers, but generally only after considerable chemical modification. Here we use the ionic liquid (IL) 1-butyl-3-methyl imidazolium acetate (BmimAc) to dissolve and reprecipitate cellulose in the presence of oil, i.e., a physical process, to tune the cellulose properties. ILs have previously been used in this way to form hydrophobic (‘oily’) cellulose microgels (CMGs), potentially capable of stabilizing water-in-oil (W/O) emulsions. However, these previous CMGs were made via a ‘top-down’ method and were relatively large and polydisperse, giving limited stability to the W/O emulsions formed. Here we demonstrate how the CMG size can be drastically reduced via a ‘bottom-up’ approach and employing high-pressure homogenization (HPH), thus achieving sub-micron CMG particle sizes. This has previously been impossible with other reported IL-cellulose coagulation methods and the corresponding W/O emulsions were more stable. In addition, confocal and cryo-scanning electron microscopy (SEM) revealed that the surface coverage of these CMGs on droplets increased over time, which led to the formation of even thicker interfacial layers and further enhanced emulsion stability (at least 2 months). We also demonstrate unequivocally that the stability of the W/O emulsions is indeed due to the CMGs adsorbing via the Pickering mechanism, rather than forming a stabilizing cellulosic network in the continuous phase, thus providing a novel route to ‘green’ Pickering emulsions.