Solution and interfacial behavior of modified silicone polymers and their interactions with solid substrates

Surface treatment is very important step in many applications such as fabric finishing, coatings, cosmetics and personal care. Silicone polymers are a class of organic/inorganic materials that show unique properties such as weak intermolecular forces and high flexibility enabling even a very high molecular weight chain to achieve optimal orientation on surfaces. Material properties such as softness, repellency, bounciness and friction can therefore be tailored by using appropriately modified silicone polymers. Despite wide applications, the underlying mechanisms of material modification are unknown and tailoring silicones for applications remains mostly empirical. Thus the objective of this research is to understand the solution and interfacial behavior of functionalized silicone polymers, which govern their performance in material modification.;Modified silicones are simultaneously hydrophobic and oleophobic in nature and due to this nearly universal non-compatibility, the studies of these polymers present unusual challenges. Due to this incompatible nature, the functionalized silicone polymers were emulsified into O/W emulsions to study their solution and interfacial properties. The colloidal properties such as electrokinetic and droplet distribution of these emulsions are assumed to play an important role in the observed surface and physical properties of solid substrates (in present study, cellulosic substrates) as well the stability of emulsions itself. To understand the effects of modified silicones on cellulosic substrates a variety of techniques such as frictional analysis, scanning electron microscopy and atomic force microscopy that can probe from macro to nano level were used.;It is hypothesized that the size distribution and charge of silicone emulsions as well as the physiochemical conditions such as pH, control silicone conformation which in turn affect the modification of the substrate properties. With bimodal droplet distribution of silicone emulsions, the nano-sized droplets can penetrate deeper into the substrate to provide bounciness, whereas macro-sized droplets can coat the top layer leading to friction reduction. It was observed that at pH 5.5 the silicone treatment resulted in charge reversal of fibers as opposed to treatment at pH 9.5. On a macroscopic scale 20% reduction in frictional coefficient of the fabric was observed after treatment with quaternized (cationically modified) silicones as compared to untreated fibers. It was also observed using AFM that the fibrils treated with quaternized silicones are uniform, well stacked and smoother than the untreated fibers. Spectroscopic analysis of treated fibers using Raman spectroscopy indicated a decrease in fiber stress as a function of modification of silicone polymer and the interaction pH. It is concluded that the protonated amine functional silicone (below pH 7) as well as the quaternized silicone interacts with the negatively charged cellulose fibers primarily through electrostatic interactions. It is proposed that this initial surface coating is a uniform thin film which allows further deposition of polymer from the emulsion.;It was observed that at high pH the zetapotential of silicone emulsions decreases drastically and the nano emulsions turn turbid. It is proposed that the observed electrophoretic and nephelometric behavior at high pH is due to flocculation of nanosized droplets to micron size, which eventually leads to droplets coalescing and emulsion destabilization. It is also postulated that the nano emulsion possess a critical dilution concentration (CDC), above which dilution leads to rapid coalescence. This critical dilution phase was further confirmed through polarity parameter and excimer formation studies which show significantly different polymer and surfactant microstructures near the CDC. Hence it is concluded that the observed surface properties of the substrate obtained above the CDC are significantly different than those below the CDC. The results reveal the vital role of physiochemical parameters such as pH, droplet size, and concentration on the emulsion stability as well as the observed physical/chemical properties of the substrates.