Understanding the Grafting of Telechelic Polymers on a Solid Substrate to Form Loops

Recent experimental and theoretical studies have demonstrated that relative to singly tethered chains, the presence of polymer loops at interfaces significantly improves interfacial properties such as adhesion, friction, and wettability. In the present study, a simple system was studied to examine the formation of polymeric loops on a solid surface, where the grafting of carboxylic acid terminated telechelic polystyrene from the melt to an epoxy functionalized silicon is chosen. The impact of telechelic molecular weight, grafting temperature, and surface functionality on the telechelic attachment process is studied. It was found that grafting of the telechelic to the surface at both ends to form loops is the primary product of this grafting process. Moreover, examination of the kinetics of the grafting process indicates that it is reaction controlled. Fluorescence tagging of the dangling ends of singly bound chains provides a mechanism to monitor their time evolution during grafting, and these results indicate that the grafting process is accurately described by recent Monte Carlo simulation work. The results also provide a method to control the extent of loop formation at interfaces and therefore provide an opportunity to further understand the role of the loops in the interfacial properties in multicomponent polymer systems.

Impact of Solvent Quality on the Density Profiles of Looped Triblock Copolymer Brushes by Neutron Reflectivity Measurements

Preferential adsorption of poly(2-vinylpyridine)-deuterated polystyrene-poly(2-vinylpyridine) (PVP-dPS-PVP) triblock copolymers from toluene onto silicon leads to the formation of dPS loops tethered by the PVP end blocks. Using neutron reflectometry, we have determined the segment density profiles of these looped polymer brushes in toluene, a good solvent for the dPS block, and in cyclohexane at 20 °C (poor solvent), 32 °C, (near-Θ solvent), and 50 °C (marginal solvent). While the swelling behavior qualitatively agrees with that observed for singly grafted brushes, there are interesting differences in the local structural details: In a good solvent, the segment density profiles are composed of an inner parabolic region and a long, extended tail. In cyclohexane, the profiles are described by exponential decays. We ascribe these features to a novel polydispersity effect that arises due to tethering the PS loops by both ends. The results also show that the less dense layers undergo more significant changes in swollen height as solvent quality is changed and that the looped brushes of different molecular weight, asymmetry, and tethering density adhere to scaling relationships derived for lightly cross-linked polymer gels.

Study of Micro Rotary Ultrasonic Machining

Product miniaturization for applications in fields such as biotechnology, medical devices, aerospace, optics and communications has made the advancement of micromachining techniques essential. Machining of hard and brittle materials such as ceramics, glass and silicon is a formidable task. Rotary ultrasonic machining (RUM) is capable of machining these materials. RUM is a hybrid machining process which combines the mechanism of material removal of conventional grinding and ultrasonic machining. Downscaling of RUM for micro scale machining is essential to generate miniature features or parts from hard and brittle materials. The goal of this thesis is to conduct a feasibility study and to develop a knowledge base for micro rotary ultrasonic machining (MRUM). Positive outcome of the feasibility study led to a comprehensive investigation on the effect of process parameters. The effect of spindle speed, grit size, vibration amplitude, tool geometry, static load and coolant on the material removal rate (MRR) of MRUM was studied. In general, MRR was found to increase with increase in spindle speed, vibration amplitude and static load. MRR was also noted to depend upon the abrasive grit size and tool geometry. The behavior of the cutting forces was modeled using time series analysis. Being a vibration assisted machining process, heat generation in MRUM is low which is essential for bone machining. Capability of MRUM process for machining bone tissue was investigated. Finally, to estimate the MRR a predictive model was proposed. The experimental and the theoretical results exhibited a matching trend.