Kumar Nanjundiah

Understanding rubber friction in the presence of water using sum-frequency generation spectroscopy

Infrared-visible sum-frequency-generation spectroscopy (SFG) was used to study the molecular structure of water between a poly(dimethylsiloxane) (PDMS) and a sapphire substrate. The observation of SFG peaks associated with the dangling surface hydroxyl groups (3690 cm(-1)) and water bands (3000-3400 cm(-1)) indicates that the contact spot between the PDMS lens and the sapphire substrate is heterogeneous. Within the contact spot there are regions where the methyl groups of the PDMS chains are in direct contact with the surface hydroxyl groups on the sapphire substrate. In the other regions, a thin water layer is trapped between the two surfaces with spectral features that are different from that of the unconfined water next to the sapphire or the PDMS surface. The higher adhesion and friction values observed in these experiments, compared to those expected for a uniform thin layer of water trapped between the PDMS and the sapphire substrate, are consistent with the hypothesis that the contact spot is heterogeneous. These results have important implications in understanding the sliding behavior of wet, deformable hydrophobic materials on hydrophilic substrates.

Holographic Polymer-Dispersed Liquid Crystals and Polymeric Photonic Crystals Formed by Holographic Photolithography

The present article describes the experimental and theoretical observations on the formation of holographic, polymer-dispersed, liquid crystals and electrically switchable, photonic crystals. A phase diagram of the starting mixture of nematic liquid crystal and photo-reactive triacrylate monomer was established by means of differential scanning calorimetry (DSC) and cloud point measurement. Photolithographic patterns were imprinted on the starting mixture of LC/triacrylate via multi-beam interference. A similar study was extended to a dendrimer/ photocurative mixture as well as to a single component system (tetra-acrylate). Theoretical modeling and numerical simulation were carried out based on the combination of Flory-Huggins free energy of mixing and Maier-Saupe free energy of nematic ordering. The combined free energy densities were incorporated into the time-dependent Ginzburg-Landau (Model C) equations coupled with the photopolymerization rate equation to elucidate the spatio-temporal structure growth. The 2-D photonic structures thus simulated were consistent with the experimental observations. Furthermore, 3-D simulation was performed to guide the fabrication of assorted photonic crystals under various beam-geometries. Electro-optical performance such as diffraction efficiency was evaluated during the pattern photopolymerization process and also as a function of driving voltage.

Melting of Linear Alkanes between Swollen Elastomers and Solid Substrates

We have measured the melting and freezing behavior of linear alkanes confined between cross-linked poly(dimethylsiloxane) (PDMS) elastomers and solid sapphire substrates. Small molecules are often used as lubricants to reduce friction or as plasticizers, but very little is directly known about the migration or changes in physical properties of these small molecules at interfaces, particularly the changes in transition temperatures upon confinement. Our previous studies highlighted striking differences between the crystal structure of confined and unconfined pentadecane crystals in contact with sapphire substrates. Here, we have used surface-sensitive infrared-visible sum-frequency-generation spectroscopy (SFG) to study the melting temperatures (Tm) of alkanes in nanometer thick interfacial regions between swollen PDMS elastomers in contact with sapphire substrate. We find that confined alkanes show depression in Tm compared to the melting temperature of unconfined bulk alkanes. The depression in Tm is a function of chain length, and these differences were smallest for shorter alkanes and largest for 19 unit long alkanes. In comparison, the DSC results for swollen PDMS elastomer show a broad distribution of melting points corresponding to different sizes of crystals formed within the network. The Tm for confined alkanes has been modeled using the combination of Flory-Rehner and Gibbs-Thomson models, and the depression in Tm is related to the thickness of the confined alkanes. These findings have important implications in understanding friction and adhesion of soft elastomeric materials and also the effects of confinement between two solid materials.