Solid-State Compatibilization of Immiscible Polymer Blends: Cryogenic Milling and Solid-State Shear Pulverization

The blending of common polymers allows for the rapid and facile synthesis of new materials with highly tunable properties at a fraction of the costs of new monomer development and synthesis. Most blends of polymers, however, are completely immiscible and separate into distinct phases with minimal phase interaction, severelydegrading the performance of the material. Cross-phase interactions and property enhancement can be achieved with these blends through reactive processing or compatibilizer addition. A new class of blend compatibilization relies on the mechanochemical reactions between polymer chains via solid-state, high energy processing. Two contrasting mechanochemical processing techniques are explored in this thesis: cryogenic milling and solid-state shear pulverization (SSSP). Cryogenic milling is a batch process where a milling rod rapidly impacts the blend sample while submerged within a bath of liquid nitrogen. In contrast, SSSP is a continuous process where blend components are subjected to high shear and compressive forces while progressing down a chilled twin-screw barrel. In the cryogenic milling study, through the application of a synthesized labeledpolymer, in situ formation of copolymers was observed for the first time. The microstructures of polystyrene/high-density polyethylene (PS/HDPE) blends fabricated via cryomilling followed by intimate melt-state mixing and static annealing were found to be morphologically stable over time. PS/HDPE blends fabricated via SSSP also showed compatibilization by way of ideal blend morphology through growth mechanisms with slightly different behavior compared to the cryomilled blends. The new Bucknell University SSSP instrument was carefully analyzed and optimized to produce compatibilized polymer blends through a full-factorial experiment. Finally, blends of varying levels of compatibilization were subjected to common material tests to determine alternative means of measuring and quantifying compatibilization,

Second-Generation Orthopaedic Measurement Device for in-vivo Assessment of Bone Quality

There are two main types of bone in the human body, trabecular and cortical bone. Cortical bone is primarily found on the outer surface of most bones in the body while trabecular bone is found in vertebrae and at the end of long bones (Ross 2007). Osteoporosis is a condition that compromises the structural integrity of trabecular bone, greatly reducing the ability of the bone to absorb energy from falls. The current method for diagnosing osteoporosis and predicting fracture risk is measurement of bone mineral density. Limitations of this method include dependence on the bone density measurement device and dependence on type of test and measurement location (Rubin 2005). Each year there are approximately 250,000 hip fractures in the United States due to osteoporosis (Kleerekoper 2006). Currently, the most common method for repairing a hip fracture is a hip fixation surgery. During surgery, a temporary guide wire is inserted to guide the permanent screw into place and then removed. It is believed that directly measuring this screw pullout force may result in a better assessment of bone quality than current indirect measurement techniques (T. Bowen 2008-2010, pers. comm.). The objective of this project is to design a device that can measure the force required to extract this guide wire. It is believed that this would give the surgeon a direct, quantitative measurement of bone quality at the site of the fixation. A first generation device was designed by a Bucknell Biomedical Engineering Senior Design team during the 2008- 2009 Academic Year. The first step of this project was to examine the device, conduct a thorough design analysis, and brainstorm new concepts. The concept selected uses a translational screw to extract the guide wire. The device was fabricated and underwent validation testing to ensure that the device was functional and met the required engineering specifications. Two tests were conducted, one to test the functionality of the device by testing if the device gave repeatable results, and the other to test the sensitivity of the device to misalignment. Guide wires were extracted from 3 materials, low density polyethylene, ultra high molecular weight polyethylene, and polypropylene and the force of extraction was measured. During testing, it was discovered that the spring in the device did not have a high enough spring constant to reach the high forces necessary for extracting the wires without excessive deflection of the spring. The test procedure was modified slightly so the wires were not fully threaded into the material. The testing results indicate that there is significant variation in the screw pullout force, up to 30% of the average value. This significant variation was attributed to problems in the testing and data collection, and a revised set of tests was proposed to better evaluate the performance of the device. The fabricated device is a fully-functioning prototype and further refinements and testing of the device may lead to a 3rd generation version capable of measuring the screw pullout force during hip fixation surgery.