The purpose of this investigation is threefold: (1) to examine in detail the cycloaddition of halogenated ketenes and carbonyl compounds, (2) to study the decarboxylation of the resulting halogenated 2-oxetanones,and (3) to investigate the effect of halogens in the halogenated 2-oxetanones on the nucleophilic addition reaction.

The purpose of the present work is to study the bonding interactions between the substituents and the ring π system for a series of ortho and para MeₙH₃₋ₙM (M = C or Si, n = 0-3) substituted N,N-dimethylaniline . Both ground and excited-state interactions were studied and their magnitudes determined. The experimental data were then used in conjunction with molecular orbital calculations to differentiate among inductive, hyperconjugative, and d-pπ interactions on the ground and excited states. Overall, the study indicates that d orbital involvement in the interactions of organosilicon substituents with unsaturated systems is much less significant than is generally held. The importance of pₛᵢ⁻π and pₛᵢ⁻π* hyperconjugative interactions between silicon σ* orbitals and π system in producing the effects of silicon substitution on unsaturated systems has become more apparent.

Methylglyoxal synthetase, which catalyzes the formation of methylglyoxal and inorganic phosphate from dihydroxyacetone phosphate, was found in extracts of Proteus vulgaris. An efficient purification procedure utilizing ion exchange column chromatography and isoelectric focusing has been developed. Homogeneity of the enzyme preparation was confirmed by polyacrylamide gel electrophoresis and rechromatography.Two components of methylglyoxal synthetase were obtained upon isoelectric focusing. A comparison of the chemical and physical properties of the two components was carried out. The enzyme is a dimer. In the presence of inorganic phosphate, the hyperbolic saturation kinetics with dihydroxyacetone phosphate are shifted to sigmoidal.

This investigation deals with the preparations of cyclic organosilanes via two different types of organometallic precursors: borane adducts to chlorovinylsilanes and tertbutyllithium adducts to chlorovinylsilanes. The regiospecificity of the hydroboration of various types of boranes to chlorovinylsilanes was studied by three different methods. It was found that, by using bulky hydroborating agents, about 80% isomerically pure terminal borane adducts to chlorovinylsilanes could be obtained. While the adducts are potential precursors to silacyclopropanes, when these borane adducts were treated with bases such as sodium methoxide and methyl Grignard, no evidence for silacyclopropane formation was found.

A method has been developed for the rapid, quantitative separation of normal and abnormal phosphoglucose isoemrase allozymes from individuals heterozygous for genetic variant forms of the enzyme. The method utilizes a substrate gradient elution of the enzyme from carboxymethyl Biogel and is far superior in terms of resolution and recovery to methods based on electrophoresis and isoelectric focusing. Four different genetic variant forms of the enzyme were isolated and subjected to a systematic comparison of their physical, catalytic and stability properties. The physical and catalytic properties of the variants were similar; however, clear differences in the stability of the allozymes were apparent.

Two types of solder samples, pins and through-holes were tested by SERA™ (Sequential Electrochemical Reduction Analysis) and Wetting Balance after various length of steamaging treatment. It was shown that after steam-aging, both types of specimen gave a similar electrochemical reduction curve, and solderabilty predictions made from SERA™ test agree with results obtained from Wetting Balance test on a qualitative base. Wetting balance test of pin samples after SERA™ test confirmed that SERA™ is a non-destructive testing method -- it even restored solderability. Comparison of electrochemical reduction behavior of samples under different treatment indicates that steam-aging can not reproduce exactly the effect of naturally atmospheric aging, and may not be the best artificial accelerating environment adopted.

The Sn/Pb eutectic alloy system is the most widely used joining material in the electronics industry. In this application, the solder acts as both an electrical and mechanical connection within and among the different packaging levels in an electronic device. Recent advances in packaging technologies, however, driven by the desire for miniaturization and increased circuit speed, result in severe operating conditions for the solder connection. In an effort to improve its mechanical integrity, metallic or intermetallic particles have been added to eutectic Sn/Pb solder, and termed composite solders. It was the goal of this study to investigate the growth and morphology of the two intermetallic phases (Cu6Sn5 and Cu3Sn) that form between a Cu substrate and Sn/Pb solder under different aging and annealing conditions.

The Abraham solvation model (ABSM) is an experimentally derived predictive model used to help predict various solute properties. This work covers various uses for the ABSM including predicting molar enthalpies of vaporization, predicting solvent coefficients for two new solvents (2,2,5,5-tetramethyloxolane and diethyl carbonate), predicting values for multiple new ionic liquids (ILs). This work also introduces a novel method for updating IL ABSM parameters by updating cation- and anion-specific values using linear algebra and binary matrices.

With the reliability requirements of automobile microelectronics pushing towards near 0 ppb levels of failure control, halide induced corrosion issues in wire bonded devices have to be tightly controlled to achieve such a high reliability goal. With real-time corrosion monitoring, for the first time we demonstrated that the explosive H2 evolution coupled with the oxygen reduction reaction, occurring at the critical Al/Cu interfaces, is the key driving force for the observed aggressive corrosion. Several types of passivation coating on Cu wire surfaces to effectively block the cathodic H2 evolution were explored with an aim to disrupt this explosive corrosion cycle. The properties of the protective coating were evaluated using various analytical techniques. The surface coating exhibited high thermal stability up to 260 °C (evaluated using TGA analysis). A uniform, highly hydrophobic coating (surface contact angle of >130° with water), was achieved by carefully controlling CVD parameters such as time of deposition, surface control of Cu metal, amount of inhibitor compound loading, temperature of coating process etc. FTIR spectroscopy combined with corrosion screening was used to optimize the CVD passivated coating with strong chemisorption. SEM and EDX, XPS were carried out on various coated surfaces to understand the composition and selectivity …

Graphene receives enormous attention owing to its distinctive physical and chemical prosperities. Growing and transferring graphene to different substrates have been investigated. The graphene growing on the copper substrate has an advantage of low solubility of carbon on the copper which allow us to grow mostly monolayer graphene. Graphene sheet of few centimeters can be transferred to 300nm silicon oxide and quartz crystal pre-deposited with metal like Cu and Ru. Characterization of the graphene has been done with Raman and contact angle measurement and recently quartz crystal microbalance (QCM) has been employed. The underpotential deposition (UPD) process of Bi on Ru metal surface is studied using electrochemical quartz crystal microbalance (EQCM) and XPS techniques. Both Bi UPD and Bi bulk deposition are clearly observed on Ru in 1mM Bi (NO3)3/0.5M H2SO4. Bi monolayer coverage calculated from mass (MLMass) and from charge (MLCharge) were compared with respect to the potential scanning rates, anions and ambient controls. EQCM results indicate that Bi UPD on Ru is mostly scan rate independent but exhibits interesting difference at the slower scan. Bi UPD monolayer coverage calculated from cathodic frequency change (ΔfCathodic) is significantly smaller than the monolayer coverage derived from integrated charge under the cathodic …

The development of the semi-empirical atomistic potential called the embedded atom method (EAM) has allowed for the efficient modeling of solid-state environments, at a lower computational cost than afforded by density functional theory (DFT). This offers the capability of EAM to model the energetics of solid-state phases of varying coordination, including defects, such as vacancies and self-interstitials. This dissertation highlights the development and application of two EAMs: a Ti potential constructed with the multi-state modified embedded atom method (MS-MEAM), and a Ni potential constructed with the fragment Hamiltonian (FH) method. Both potentials exhibit flexibility in the description of different solid-states phases and applications. This dissertation also outlines two applications of DFT. First, a study of structure and stability for solid-state forms of NixCy (in which x and y are integers) is investigated using plane-wave DFT. A ground state phase for Ni2C is elucidated and compared to known and hypothesized forms of NixCy. Also, a set of correlation consistent basis sets, previously constructed using the B3LYP and BLYP density functionals, are studied. They are compared to the well-known to the correlation consistent basis sets that were constructed with higher-level ab initio methodologies through computations of enthalpies of formation and combustion enthalpies. …