The increasing use of polymer-based materials (PBMs) across all types of industry has not been matched by sufficient improvements in understanding of polymer tribology: friction, wear, and lubrication. Further, viscoelasticity of PBMs complicates characterization of their behavior. Using data from micro-scratch testing, it was determined that viscoelastic recovery (healing) in sliding wear is independent of the indenter force within a defined range of load values. Strain hardening in sliding wear was observed for all materials-including polymers and composites with a wide variety of chemical structures-with the exception of polystyrene (PS). The healing in sliding wear was connected to free volume in polymers by using pressure-volume-temperature (P-V-T) results and the Hartmann equation of state. A linear relationship was found for all polymers studied with again the exception of PS. The exceptional behavior of PS has been attributed qualitatively to brittleness. In pursuit of a precise description of such, a quantitative definition of brittleness has been defined in terms of the elongation at break and storage modulus-a combination of parameters derived from both static and dynamic mechanical testing. Furthermore, a relationship between sliding wear recovery and brittleness for all PBMs including PS is demonstrated. The definition of brittleness may be used as a design criterion in selecting PBMs for specific applications, while the connection to free volume improves also predictability of wear behavior.

Wear is an important phenomenon that occurs in all the polymer applications in one form or the other. However, important links between materials properties and wear remain illusive. Thus optimization of material properties requires proper understanding of polymer properties. Studies to date have typically lacked systematic approach to all polymers and wear test developed are specific to some polymer classes. In this thesis, different classes of polymers are selected and an attempt is made to use multiple scratch test to define wear and to create a universal test procedure that can be employed to most of the polymers. In each of the materials studied, the scratch penetration depth s reaches a constant value after certain number of scratches depending upon the polymer and its properties. Variations in test parameters like load and speed are also studied in detail to understand the behavior of polymers and under different conditions. Apart from polystyrene, all the other polymers studied under multiple scratch test reached asymptotes at different scratch numbers.

The abrasive mechanism of polymer wear is dominant in the startup, or "breakin", stage of polymer/steel sliding systems. This mechanism controls the polymer wear rate until the voids in the hard metal surface are filled, much like the filling observed with a file when used on soft metals. This regime of polymer wear is modeled on an event-by-event basis. The model utilizes a digitized profile of the metal surface, bulk polymer properties such as flow pressure and elongation at break, and a few system parameters such as load and slider geometry. The predictions of the model are compared with experimental data. The predicted wear rates are within a factor of 3 of the measured wear rates for polymers with glass transition temperatures, Tg, above the interfacial temperature (rigid PVC and PCTFE). The validity of the model is shown to be related to the ductile or brittle behavior of the sliding polymer. / Ph. D. / Bibliography: leaves 78-80

A fundamental study was conducted to investigate the ability of thin polymeric coatings to prevent metallic contact and fretting corrosion in steel-on-steel systems. Ten polymer types were chosen for study: polymethylmethacrylate (PMMA), polytetrafluoroethylene (PTFE), polyimide (PI), polyvinylidene fluoride (PVDF), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), low-density polyethylene (LOPE), high-density polyethylene (HDPE), polysulfone (PSO) and polystyrene (PS). These polymers were applied as thin films to a steel disk which was in turn fretted by a normally-loaded steel sphere. The experimental investigation consisted of two phases. In the first phase, the lives of the ten polymer types were evaluated over a range of normal loads from 11.1 to 44.5 N. In the second phase, optical and electron microscopy were used to document the fretting process at the sphere-film interface as a function of time. / Master of Science

Chemically identical but topologically different cyclic and linear polymers not only result in marked differences in dynamics, but also lead to unique transport properties of their blends, where cyclic polymers have chances to be threaded onto the linear polymers. This dissertation addresses the effect of ring architecture on dynamics using different time/length scale techniques: self-diffusion coefficients, NMR spin-spin relaxation time (T2) and bulk viscosity. In deuterated water, synthesized cyclic poly(oxyethylene) (CPOE) (400-1500 g/mol) diffused faster than corresponding linear POE (LPOE) and linear POE dimethyl ether (LPOEDE). However, the self-diffusion coefficients in melts were arranged in the following manner: LPOEDE > CPOE > LPOE, in excellent agreement with T2 and viscosity data, showing topological and chain end effects. Compared to LPOEDE, both CPOE and LPOE had higher activation energies for viscosity with less dependence on the molecular weight. In the blends of CPOE and LPOE for 900 and 1500 g/mol, the diffusion coefficient and viscosity in melts were higher and lower than the values predicted by a binary mixing rule, respectively. These deviations were attributed to the threading conformation, and the weight fraction of the threaded chains for 1500 g/mol was estimated by a three-term mixing rule. This threading conformation also appeared to influence such important bulk properties as the glass transition and spherulitic growth rate of the blends.