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.

Tubular and sector heat pipes with interconnected branches for gas turbine and/or compressor cooling

Designing turbines for either aerospace or power production is a daunting task for any heat transfer scientist or engineer. Turbine designers are continuously pursuing better ways to convert the stored chemical energy in the fuel into useful work with maximum efficiency. Based on thermodynamic principles, one way to improve thermal efficiency is to increase the turbine inlet pressure and temperature. Generally, the inlet temperature may exceed the capabilities of standard materials for safe and long-life operation of the turbine. Next generation propulsion systems, whether for new supersonic transport or for improving existing aviation transport, will require more aggressive cooling system for many hot-gas-path components of the turbine. Heat pipe technology offers a possible cooling technique for the structures exposed to the high heat fluxes. Hence, the objective of this dissertation is to develop new radially rotating heat pipe systems that integrate multiple rotating miniature heat pipes with a common reservoir for a more effective and practical solution to turbine or compressor cooling. In this dissertation, two radially rotating miniature heat pipes and two sector heat pipes are analyzed and studied by utilizing suitable fluid flow and heat transfer modeling along with experimental tests. Analytical solutions for the film thickness and the lengthwise vapor temperature distribution for a single heat pipe are derived. Experimental tests on single radially rotating miniature heat pipes and sector heat pipes are undertaken with different important parameters and the manner in which these parameters affect heat pipe operation. Analytical and experimental studies have proven that the radially rotating miniature heat pipes have an incredibly high effective thermal conductance and an enormous heat transfer capability. Concurrently, the heat pipe has an uncomplicated structure and relatively low manufacturing costs. The heat pipe can also resist strong vibrations and is well suited for a high temperature environment. Hence, the heat pipes with a common reservoir make incorporation of heat pipes into turbo-machinery much more feasible and cost effective.

Tubular and Sector Heat Pipes with Interconnected Branches for Gas Turbine and/or Compressor Cooling

Designing turbines for either aerospace or power production is a daunting task for any heat transfer scientist or engineer. Turbine designers are continuously pursuing better ways to convert the stored chemical energy in the fuel into useful work with maximum efficiency. Based on thermodynamic principles, one way to improve thermal efficiency is to increase the turbine inlet pressure and temperature. Generally, the inlet temperature may exceed the capabilities of standard materials for safe and long-life operation of the turbine. Next generation propulsion systems, whether for new supersonic transport or for improving existing aviation transport, will require more aggressive cooling system for many hot-gas-path components of the turbine. Heat pipe technology offers a possible cooling technique for the structures exposed to the high heat fluxes. Hence, the objective of this dissertation is to develop new radially rotating heat pipe systems that integrate multiple rotating miniature heat pipes with a common reservoir for a more effective and practical solution to turbine or compressor cooling. In this dissertation, two radially rotating miniature heat pipes and two sector heat pipes are analyzed and studied by utilizing suitable fluid flow and heat transfer modeling along with experimental tests. Analytical solutions for the film thickness and the lengthwise vapor temperature distribution for a single heat pipe are derived. Experimental tests on single radially rotating miniature heat pipes and sector heat pipes are undertaken with different important parameters and the manner in which these parameters affect heat pipe operation. Analytical and experimental studies have proven that the radially rotating miniature heat pipes have an incredibly high effective thermal conductance and an enormous heat transfer capability. Concurrently, the heat pipe has an uncomplicated structure and relatively low manufacturing costs. The heat pipe can also resist strong vibrations and is well suited for a high temperature environment. Hence, the heat pipes with a common reservoir make incorporation of heat pipes into turbo-machinery much more feasible and cost effective.