High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Aerodynamic Load Characteristics Evaluation and Tri-Axial Performance Testing on Fiber Reinforced Polymer Connections and Metal Fasteners to Promote Hurricane Damage Mitigation

Damages during extreme wind events highlight the weaknesses of mechanical fasteners at the roof-to-wall connections in residential timber frame buildings. The allowable capacity of the metal fasteners is based on results of unidirectional component testing that do not simulate realistic tri-axial aerodynamic loading effects. The first objective of this research was to simulate hurricane effects and study hurricane-structure interaction at full-scale, facilitating better understanding of the combined impacts of wind, rain, and debris on inter-component connections at spatial and temporal scales. The second objective was to evaluate the performance of a non-intrusive roof-to-wall connection system using fiber reinforced polymer (FRP) materials and compare its load capacity to the capacity of an existing metal fastener under simulated aerodynamic loads. The Wall of Wind (WoW) testing performed using FRP connections on a one-story gable-roof timber structure instrumented with a variety of sensors, was used to create a database on aerodynamic and aero-hydrodynamic loading on roof-to-wall connections tested under several parameters: angles of attack, wind-turbulence content, internal pressure conditions, with and without effects of rain. Based on the aerodynamic loading results obtained from WoW tests, sets of three force components (tri-axial mean loads) were combined into a series of resultant mean forces, which were used to test the FRP and metal connections in the structures laboratory up to failure. A new component testing system and test protocol were developed for testing fasteners under simulated tri-axial loading as opposed to uni-axial loading. The tri-axial and uni-axial test results were compared for hurricane clips. Also, comparison was made between tri-axial load capacity of FRP and metal connections. The research findings demonstrate that the FRP connection is a viable option for use in timber roof-to-wall connection system. Findings also confirm that current testing methods of mechanical fasteners tend to overestimate the actual load capacities of a connector. Additionally, the research also contributes to the development a new testing protocol for fasteners using tri-axial simultaneous loads based on the aerodynamic database obtained from the WoW testing.