To help address the growing need for more and better sensors, an attempt was made to produce an in-situ mass and spectroscopic analysis of liquid and solid samples, to characterize samples and sensors. Spectroscopic analysis consisted of Raman and FTIR where mass measurements were carried out. The sample or sensor’s holder would allow for spectroscopic analysis as well as expose the sample to high temperatures and various chemicals. While Raman and FTIR were successful in producing reliable and consistent data, the constructed watt balance was not. This failure was a result of eliminate vibrational noise.

Graduation date: 1998

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There has been a continuous effort to unveil the physics of hypersonic flows both experimentally and numerically, in order to achieve an efficient hypersonic vehicle design. With the advent of the high speed computers, a lot of focus has been given on research pertaining to numerical approach to understand this physics. The features of such flows are quite different from those of subsonic, transonic and supersonic ones and thus normal CFD methodologies fail to capture the high speed flows efficiently. Such calculations are made even more challenging by the presence of nonequilibrium thermodynamic and chemical effects. Thus further research in the field of nonequilibrium thermodynamics is required for the accurate prediction of such high enthalpy flows. The objective of this thesis is to develop improved computational tools for hypersonic aerodynamics accounting for non-equilibrium effects. A survey of the fundamental theory and mathematical modeling pertaining to modeling high temperature flow physics is presented. The computational approaches and numerical methods pertaining to high speed flows are discussed. In the first part of this work, the fundamental theory and mathematical modeling pertaining to modeling high temperature flow physics is presented. Continuum based approach (Navier Stokes) and Boltzmann equation based approach (Gas Kinetic) are discussed. It is shown mathematically that unlike the most popular continuum based methods, Gas Kinetic method presented in this work satisfies the entropy condition. In the second part of this work, the computational approaches and numerical methods pertaining to high speed flows is discussed. In the continuum methods, the Steger Warming schemes and Roe’s scheme are discussed. The kinetic approach discussed is the Boltzmann equation with Bhatnagar Gross Krook (BGK) collision operator. In the third part, the results from new computational fluid dynamics code developed are presented. A range of validation and verification test cases are presented. A comparison of the two common reconstruction techniques: Green Gauss gradient method and MUSCL scheme are discussed. Two of the most common failings of continuum based methods: excessive numerical dissipation and carbuncle phenomenon techniques, are investigated. It is found that for the blunt body problem, Boltzmann BGK method is free of these failings.

Vibrational sum frequency spectroscopy (VSFS) is a nonlinear optical process. The sum frequency signal is proportional to the square of second order nonlinear susceptibility, which is proportional to the average of polarizabilities of molecules, which is related to molecular orientation. Since the polarizabilities of molecules in bulk phase will be canceled out, a sum frequency signal can only be generated from interfaces where the inversion symmetry is broken. Because of its interfacial specificity, VSFS has been applied to study many interfacial phenomena. In this dissertation we investigated various biological interfaces with VSFS. Fibrinogen adsorption was studied at the protein/solid interface in combination with atomic force microscopy (AFM), immunoassay, and VSFS. Astonishing changes in the interfacial water orientation accompanied by the pH changes provided fibrinogen’s adsorption mechanism up to the amino acid level. Enzymatic fragmentation of fibrinogen revealed that the adsorption property of fibrinogen was mainly from the alpha C fragments of the protein. Mimicking of the fibrinogen binding site with polypeptides was successfully performed and showed very similar properties of fibrinogen adsorption. Protein stability is sensitive to the salts in solutions. The ability of ions to stabilize protein was ordered by Hofmeister in 1888 and the order is SO4 2- ≅ HPO4 2- > F- > Cl- > Br- > NO3 - > I- (≅ ClO4 -) > SCN-. Even though the phenomenon was observed in various biological systems, the origin of those ionic effects is still not well understood. We studied ion effects on alkyl chain ordering and interfacial water structure for octadecylamine, dimethyldidodecylammonium bromide, and dilauroylphosphotidyl choline monolayers. Because of its ability to probe a hydrophobic moiety and interfacial water at the same time, VSFS provided further information to understand the Hofmeister series. We found that the Hofmeister effect is a combinatorial effect of screening effects, ion binding, and dispersion forces.

Thesis (Ph. D.)--Lehigh University, 2000. / Includes bibliographical references and vita.

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