The preparation of layered double hydroxides via titration with sodium hydroxide was thoroughly investigated for a number of M(II)/M(III) combinations. These titration curves were examined and used to calculate nominal solubility product constants and other thermodynamic quantities for the various LDH chloride systems.

Sulfur adsorbed on metallic and oxide surfaces, whether originating from gaseous environments or segregating as an impurity to metallic interfaces, is linked to the deterioration of alloy performance. This research dealt with investigations on the interactions between sulfur and iron or iron alloy metallic and oxide surfaces under ultrahigh vacuum conditions. Sulfur was either intentionally dosed from a H2S source on an atomically clean metal surface, or segregated out as an impurity from the bulk to the metal surface by annealing at elevated temperatures.

The thermocyclic fatigue behavior of the low-melting solder 43Sn/43Pb/14Bi has been investigated and compared to that of standard 60Sn/4OPb solder via metallographic analysis (using scanning electron microscopy) and evaluation of the degree of fatigue development (using a fatigue scale as a function of thermocycles). Specimens were subjected to shearing strains imposed by several hundred fatigue thermocycles. Both solder types fatigue by the same microstructural failure mechanism as described by other workers. The mechanism is characterized by a preferential coarsening of the solder joint microstructure at the region of maximum stress concentration where cracks originate.

The microstructural, mechanical and thermal properties of various composite solder formulations were investigated. Special interest was given in observing the processing properties, microstructural characteristics, fatigue behavior, tensile strength, and the effect of environmental ageing on the composite solder formulations. The solderability parameters wetting and speed of soldering, reflow temperature, and the thermal stability of the resulting composite solder were also examined.

Tungsten metal is used as an electrical conductor in many modern microelectronic devices. One of the primary motivations for its use is that it can be deposited in thin films by chemical vapor deposition (CVD). CVD is a process whereby a thin film is deposited on a solid substrate by the reaction of a gas-phase molecular precursor. In the case of tungsten chemical vapor deposition (W-CVD) this precursor is commonly tungsten hexafluoride (WF6) which reacts with an appropriate reductant to yield metallic tungsten. A useful characteristic of the W-CVD chemical reactions is that while they proceed rapidly on silicon or metal substrates, they are inhibited on insulating substrates, such as silicon dioxide (Si02). This selectivity may be exploited in the manufacture of microelectronic devices, resulting in the formation of horizontal contacts and vertical vias by a self-aligning process. However, reaction parameters must be rigorously controlled, and even then tungsten nuclei may form on neighboring oxide surfaces after a short incubation time. Such nuclei can easily cause a short circuit or other defect and thereby render the device inoperable. If this loss of selectivity could be controlled in the practical applications of W-CVD, thereby allowing the incorporation of this technique into …

The Semiconductor Industry Association (SIA) has identified the integration of copper (Cu) with low-dielectric-constant (low-k) materials as a critical goal for future interconnect architectures. A fundamental understanding of the chemical interaction of Cu with various substrates, including diffusion barriers and adhesion promoters, is essential to achieve this goal. The objective of this research is to develop novel organic polymers as Cu/low-k interfacial layers and to investigate popular barrier candidates, such as clean and modified tantalum (Ta) substrates. Carbon-silicon (C-Si) polymeric films have been formed by electron beam bombardment or ultraviolet (UV) radiation of molecularly adsorbed vinyl silane precursors on metal substrates under ultra-high vacuum (UHV) conditions. Temperature programmed desorption (TPD) studies show that polymerization is via the vinyl groups, while Auger electron spectroscopy (AES) results show that the polymerized films have compositions similar to the precursors. Films derived from vinyltrimethyl silane (VTMS) are adherent and stable on Ta substrates until 1100 K. Diffusion of deposited Cu overlayers is not observed below 800 K, with dewetting occurred only above 400 K. Hexafluorobenzene moieties can also be incorporated into the growing film with good thermal stability. Studies on the Ta substrates demonstrate that even sub-monolayer coverages of oxygen or carbide on polycrystalline …

Precipitates of a series of alkaline earth metal (barium and strontium) carbonates, chromates, phosphates, and sulfates were formed at high supersaturation by diffusion through silica hydrogel, agarose hydrogel, and the freshly developed agarosesilica mixed gels. The reaction vessels could be a small test tube, a recently designed standard micro slide cassette and a enlarged supercassette. Homogeneous nucleation is thought to have taken place, and particle development led to the formation of an unusual category of materials, known as Induced Morphology Crystal Aggregates [IMCA], at high pH under far-from-equilibrium conditions. Standard procedures were developed in order to produce homogeneous gels. Particle development led to characteristic style of pattern formation, which I have called monster, spiral, and flake. Among these IMCA, barium carbonate, chromate, and sulfate were moderately easy to grow. Barium phosphate was very difficult to grow as IMCA due to formation of poorly crystalline spherulites. IMCA of strontium carbonate, chromate and sulfate could be developed at high basic pH in the presence of silicate. Strontium carbonate sheet morphology displays a unique property, double internal layer structure, which was identified by backscattering electron imaging (BEI). Selected electron diffraction (SAD) revealed a new crystal phase which was called "Dentonite". Precipitate particles were …

As the miniaturization keeps decreasing in semiconductor device fabrication, metal contamination on silicon surfaces becomes critical. An investigation of the fundamental mechanism of metal contamination process on silicon surface is therefore important. Kinetics and thermodynamics of the copper out-plating process on silicon surfaces in diluted HF solutions are both evaluated by several analytical methods.

A variety of novel cage-functionalized pyridyl containing crown ethers have been prepared for use in selective alkali metal complexation studies. A highly preorganized, cage-functionalized cryptand also has been designed and has been synthesized for use as a selective Li+ complexant. The alkali metal picrate extraction profiles of these cage-functionalized crown ethers also have been studied. Novel cage-functionalized diazacrown ethers have been prepared for selective alkali metal complexation studies. Alkali metal picrate extraction experiments have been performed by using this new class of synthetic ionophores to investigate the effects of cage-annulation and the influence of N-pivot lariat sidearms upon their resulting complexation properties. Novel pyridyl containing calix[4]arene receptors were prepared. Analysis of their respective 1H NMR and 13C NMR spectra suggests that calix[4]arene moieties in the ligand occupy the cone conformation. The complexation properties of these host molecules were estimated by performing a series of alkali metal picrate extraction experiments. An optically active cage-functionalized crown ether which contains a binaphthyl moiety as the chiral unit was prepared. The ability of the resulting optically active crown ether to distinguish between enantiomers of guest ammonium ions (i.e., phenylethylamonium and phenylglycinate salts) in transport experiments was investigated. Hexacyclo[11.2.1.02,12.05,10.05,15.010,14]hexadeca-6,8-diene-4,11-dione was prepared from hexacyclo[7.4.2.01,9.03,7.04,14.06,15] pentadeca-10,12-diene-2,8-dione. Unanticipated …

Part I: In the first study of pyrethroids, twenty-one novel pyrethroid esters bearing strong electron-withdrawing groups (e.g., halomethylketo and nitro groups) in the double bond side chain of the cyclopropane acid moiety have been synthesized and evaluated for insect toxicity. Rather than the usually employed Wittig reaction for these syntheses, the novel pyrethroid acid moieties were prepared by amino acidcatalyzed Knoevenagel condensations under mild conditions. In the second study of pyrethroids, fourteen pyrethroid-like carbonates were synthesized by condensation of a variety of alcohols and the chloroformates of the corresponding known pyrethroid alcohols.

New one- and two-dimensional NMR techniques were used to elucidate the solution structures of these complex mixtures. The system, lithium tert-butoxide/tert-butyllithium, was studied as a model system with O/Li ratios varying from 0/1 to 1/1. It was found that at low O/Li ratios, a single mixed tetrameric aggregate was formed. At higher O/Li ratios, mixed hexameric species were formed. Two other systems, lithium isopropoxide/iso-propyllithium and lithium n-propoxide/n-propyllithium were also studied at low O/Li ratios.

The purpose of this dissertation is to investigate the thermodynamic properties of nonelectrolyte solutes dissolved in ternary solvent mixtures, and to develop mathematical expressions for predicting and describing that behavior in the solvent mixtures. Thirty-four ternary solvent systems were studied containing either alcohol (1-propanol, 2-propanol, 1-butanol, and 2-butanol), alkane (cyclohexane, heptane, and 2,2,4-trimethylpentane) or alkoxyalcohol (2-ethoxyethanol and 2-butoxyethanol) cosolvents. Approximately 2500 experimental measurements were performed. Expressions were derived from the Combined Nearly Ideal Multiple Solvent (NIMS)/Redlich-Kister, the Combined Nearly Ideal Multiple Solvent (NIMS)/Bertrand, Acree and Burchfield (BAB) and the Modified Wilson models for predicting solute solubility in ternary solvent (or even higher multicomponent) mixtures based upon the model constants calculated from solubility data in sub-binary solvents. Average percent deviation between predicted and observed values were less than 2%, documenting that these models provide a fairly accurate description of the thermodynamic properties of nonelectrolyte solutions. Moreover, the models can be used for solubility prediction in solvent mixtures in order to find the optimum solvent composition for solubilization or desolubilization of a solute. From a computational standpoint, the Combined Nearly Ideal Multiple Solvent/Redlich-Kister equation is preferred because the needed model constants can be calculated with a simple linear regressional analysis. Model constants …

The temperature dependence of the reactions of halogen atoms Cl and Br with SiH4 and (CH3)3SiH have been investigated with the flash photolysis-resonance fluorescence technique. CCI4 and CH2Br2 were used as precursors to produce Cl and Br atoms, respectively. Experiments gave {k(Cl + SiH4) (295 - 472 K)} = (1.56 +0.11) x 10-1 exp[(2.0 + 0.2) kJ mol'/RT] cm3 s4, {k(Br + SiH4)(295 - 575 K)} = (9.0 + 1.5) x 10-" exp[-(17.0 + 0.6) Id mol'/RT] cm3 s', {k(Cl + (CH3)3SiH)(295 - 468 K)} = (1.24 0.35) x 104 exp[(1.3 + 0.8) Id mol4/RT] cm3 s', and {k(Br + (CH3)3SiH)(295 - 456 K)} = (7.6 + 3.3) x 1010 exp[-(28.4 + 1.3) Id mol'/RT] cm3 s'. The results were compared with values from earlier work.

The kinetics of ligand substitution for CO in Co4(CO)10(mu4-PPh2) , 1, have been investigated for the ligands P(OMe)3, P(OEt)3, PPh2H, P(0-i-Pr)3, P(n-Bu)3, PPh3, P(i-Pr)3, and PCy3 over a wide temperature range.

I. Diels-Alder reactions of 1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-metha- nonaphthalene (16) and 1,2,3,4,9,9-hexachloro-1,4,6,7-tetrahydro-1,4-methanonaphthalene (17) toward dienophiles N-methyl-1,2,4-triazoline-3,5-dione (MTAD), N-phenyl-1,2,4-triazoline-3,5-dione (PTAD) and/or N-methylmaleimide (NMM) have been examined. II. Epoxides derived from functionalized 1,4,4a,9a-tetrahydro-9,10-dioxo-1,4-methanoanthracenes (1a and 1b) undergo acid- and base-promoted intramolecular nucleophilic ring-opening to form new polycyclic alcohols. III. The title cycloalkylidenecarbene has been generated via reaction of 8-methylenepentacyclo[5.4.0.0^{2,6}.0^{3,10}. 0^{5.9}]undecan-11-one (44) with diethyl diazomethyl-phosphonate (DAMP). This species could be trapped in situ by cyclohexene, thereby affording the corresponding cycloadduct 46a and 46b.

Chain conformations and the presence of chain overlaps and entanglements in dilute polymer solutions have been analyzed. The fundamental problem of existence of chain overlaps in dilute solutions is related to the drag reduction phenomenon (DR). Even though DR occurs in solutions with the concentration of only few parts per million (ppm), some theories suggest that entanglements may play an important role in DR mechanism. Brownian dynamics technique have been used to perform simulations of dilute polymer solutions at rest and under shear flow. A measure of interchain contacts and two different measures of entanglements have been devised to evaluate the structure of polymer chains in solution. Simulation results have shown that overlaps and entanglements do exist in static dilute solutions as well as in solutions under shear flow. The effect of solution concentration, shear rate and molecular mass have been examined. In agreement with the solvation theory of DR mechanism, simulation results have demonstrated the importance of polymer + polymer interactions in dilute solutions.

With the values of 6Li T1 measured and the literature values of J(13C-6Li) for these compounds, three new 13C NMR techniques are developed for the analysis of organolithium compounds. Modifications to the spectrometer are discussed, as well as calibrations of the 6Li decoupler channel needed to set up these new experiments. The theoretical development of each technique is presented, as well as data from their verification, using organolithium compounds of known structure. Once qualified, the new experimental techniques are used to analyze a series of alkyllithium / lithium alkoxide mixed aggregates in solution, where structures and values of J(13C-6Li) may not be known. The combination of Ti relaxation measurements and 13C{1H, 6Li} triple resonance techniques serves as a means of determining the structure of organolithium aggregates in solution.

Experimental mole fraction solubilities of benzil, thianthrene, trans-stilbene, thioxanthen-9-one, diphenyl sulfone and dibenzothiophene sulfone are determined in pure noncomplexing and complexing solvents. Predicted solubility values are calculated for benzil, thianthrene, trans-stilbene and thioxanthen-9-one using expressions derived from Mobile Order theory. Large deviations between experimental and predicted solubilities in alcohol solvents exist, therefore optimized solute - solvent association constants are determined. Previously measured thianthrene solubilities in five binary alkane + cyclohexane solvent mixtures are compared with values predicted from Mobile Order theory using the measured solubility in each of the pure solvents as input parameters. The experimental mole fraction solubility of benzil in eight binary alcohol + 1-octanol solvent mixtures are also measured and compared with predicted values.

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.

Nitroglycerin and isoamyl nitrate have been used as nitrovasodilators since the nineteeth century. However, not until recently has it been known that these compounds were useful since they promoted the release of NO in the body. More recently, a new class of drugs, NO donors, has been developed. These include S-nitrosothiols (RSNO), sydnonimines, and nucleophilic NO adducts.

Five different complexes of aluminum and amino acids have been synthesized and characterized. Reaction between aluminum halides and amino acids that do not contain either a carboxylate or a hydroxy group in the side chain produce complexes of the general formula, [Al(amino acid)_n(halide)_3-n]_m. The most prevalent form of this form of complex is where n = 2, and an example of this in which the halide is replaced by hydroxide ligand has been structurally characterized. The complex for which n = 3 may be obtained by employing a large excess of acid, and that for which n = 1 may be obtained by employing either equimolar conditions or an excess of aluminum halide. Reactions of aluminum halides with amino acids that contain either a carboxylate or hydroxy-containing side chain may result in complexes in which the side-chain is also bound. These proved impossible to characterize fully in the case of aspartic acid. For serine, however, a complex in which the amino acid binds in a chelating fashion through both the carboxylate and hydroxy groups was isolated. It was possible to form complexes when utilizing aluminum alkyls as the metal source. However, these complexes could only be isolated when the reactivity …

Semiconductor devices are built using hyperpure silicon and very controlled levels of doping to create desired electrical properties. Contamination can alter these precisely controlled electrical properties that can render the device non-functional or unreliable. It is desirable to determine what impurities impact the device and control them. This study consists of four parts: a) determination of acceptable SCI (Standard Clean 1) bath contamination levels using VPD-DSE-GFAAS (Vapor Phase Decomposition Droplet Surface Etching Graphite Furnace Atomic Absorption Spectroscopy), b) copper deposition from various aqueous HF solutions, c) anion contamination from fluoropolymers used in chemical handling and d) metallic contamination from fluoropolymers and polyethylene used in chemical handling. A technique was developed for the determination of metals on a silicon wafer source at low levels. These levels were then correlated to contamination levels in a SCI bath. This correlation permits the determination of maximum permissible solution contaminant levels. Copper contamination is a concern for depositing on the wafer surface from hydrofluoric acid solutions. The relationship between copper concentration on the wafer surface and hydrofluoric acid concentration was determined. An inverse relationship exists and was explained by differences in diffusion rates between the differing copper species existing in aqueous hydrofluoric acid solutions. Finally, …

This research was designed to investigate the hydration reaction of fly ash when exposed to water. The effects that calcium nitrate and calcium formate have on the hydration reactions were also examined.

The purpose of this study was to determine the factors affecting the acid degradation of chrysotile asbestos (Mg_3Si_2O_5(OH_4)) . Millions of tons of asbestos have found use in this country as insulative or ablative material. More than 95 percent of the asbestos in use is of the chrysotile variety. The remaining 5 percent is composed of various types of fibrous amphiboles. The inhalation of asbestos can lead to several diseases in humans. Asbestosis, lung cancer and mesothelioma are the most common afflictions associated with asbestos inhalation, and they may occur up to 40 years after the initial exposure. It has previously been reported that if more than 50 percent of the magnesium is removed from a chrysotile sample its carcinogenicity is reduced to nil. Several inorganic acids were studied to determine their ability to leach magnesium from chrysotile. It was found that the ability to leach magnesium was dependent upon the acidic anion in addition to the concentration of the acid. The ordering of the efficiency of the acids in their ability to remove magnesium from chrysotile was found to be HCl > H_2SO_4 > H_3PO_4 > HNO_3. Predictive equations were developed to allow the calculation of the amount of …