The Statistical Associating Fluid Theory (SAFT) equation of state is a statistical mechanics based equation of state based on Wertheim's theory of associating fluids. Since SAFT is a statistical mechanics based equation of state, it is possible to include more physics in the model to make it more predictive. In this work we show the versatility of SAFT by applying it to monomers and polymers and include dipolar interactions in SAFT. SAFT is used to model phase equilibria in long chain-short chain alkane mixtures. It is shown that SAFT accurately models phase equilibria in these systems even when there is a large disparity between the chain lengths of the two alkanes. We then use the statistical associating fluid theory (SAFT) to model liquid-liquid phase equilibria in solutions of linear low density polyethylene (LLDPE) with hexane, heptane and octane. The effect of temperature, pressure, polymer concentration and polymer molecular weight on phase separation is studied. Finally, the effect of polydispersity on cloud point is also considered. SAFT results are compared with experimental data by de Loos et al. [1]. It is shown that SAFT can model the phase behavior of the polymer in different solvents at various state conditions with a single adjustable parameter. The applicability of SAFT to these monomers and polymers shows that it is a versatile thermodynamic model. We propose an algorithm for calculating phase equilibria of polydisperse polymer systems using the SAFT equation of state. The algorithm is formally exact and the computation time is independent of the number of pseudo-components used to represent the polymer molecular weight distribution. The algorithm makes use of the form of the SAFT equation of state and simplifications resulting from it to simplify the flash calculations. Distinctive features of the phase diagrams of polydisperse systems are illustrated by calculating the cloud point and shadow point curves of polyethylene solutions in ethylene using the algorithm proposed in this work. We present results from molecular simulation and statistical mechanics based theory for dipolar hard sphere chains and dipolar Lennard-Jones (LJ) chains. We consider the chains with dipoles on alternate segments. The equation of state is obtained by applying Wertheim's associating fluid theory in the total bonding limit to a mixture of non-polar and dipolar segments. It is shown that the theory developed here is in very good agreement with computer simulation. This theory simultaneously accounts for chain and dipolar effects and can handle multiple dipolar sites in a molecule. This is demonstrated by generalizing the theory to mixtures and applying it to dipolar monomers and copolymers. The theory accurately predicts the phase behavior of real dipolar fluids.

Using perfluoropolyether as the solvent, cutting of pristine SWNT has been achieved by extensive ozonolysis with 80% carbon yield at room temperature. The intense disorder mode in the Raman spectra of ozonated SWNT indicates that extensive reaction with the sidewalls of SWNT occurs during ozonolysis. AFM provided a measure of the extent of the cutting effects. Monitoring of the evolved gases indicates CO2 was produced during the ozonolysis process with a dependence on both system pressure and temperature. During heating, FTIR analysis of gases released indicates carbon oxygen groups on the sidewalls of SWNT are released as CO2. Room temperature ozonolysis of fluorinated SWNT and phenol-sulfonated SWNT have also been studied in PFPE. For fluorinated SWNT, etching at the end caps has been demonstrated to be the dominating effect during this process. The improved suspension in 96% sulfuric acid after ozonolysis enables the cutting by ammonia peroxydisulfate without defluorination with a hydrazine treatment. PS-SWNT was found to be effectively cut by ozonolysis in a water suspension with preserved water solubility. Controlled by the electron dosage, a high energy electron beam (3MeV) has been demonstrated to cut ozonated SWNT. Besides ozonolysis, 700°C has been shown an optimal temperature to cut F-SWNT by pyrolysis in an argon atmosphere.

The ability of an artificial surface to resist the non-specific adsorption of proteins in biological solutions greatly improves its biocompatibility---a desirable property to overcome many problems across the biomedical and biochemical processing areas. This thesis demonstrates the effectiveness of surface-initiated atom transfer radical polymerization for the synthesis of hydrophilic, protein resistant coatings with controlled thicknesses in the nanoscale regime (1--100 nm). The strategy uses the surface initiated atom transfer radical polymerization of commercially available oligo(ethylene glycol) methacrylate monomers with different chain lengths and either hydroxyl or methoxy group terminations. This thesis evaluated the effects of chain length and end group of the monomers on the kinetics of their polymerization and the protein resistance of the resulting films. Protein adsorption for plasma proteins (lysozyme, fibrinogen, and albumin) as measured by XPS shows that, these coatings show remarkable resistance against protein adsorption that depends on the attributes of the monomer.

The technique of infrared kinetic spectroscopy has been used to study the reaction of the propargyl radical (C3H3) with nitric oxide (NO). The overall rate constant at the high pressure limit for the reaction was determined to be 1.09 +/- .28 * 10-11 cc molec-1 s -1 at 296 K. The reaction has an apparent negative activation energy for temperatures between 195--473 K and its rate constant is pressure dependent at 195 K and 296 K. At these temperatures the mechanism is believed to involve adduct formation. The establishment of an adduct equilibrium is not observed at higher temperatures, however. Instead the reaction is thought to form final stable products. A search was carried out for several possible reaction products including HCN, HCCN, HCNO, HCCH, HNC and H2CN. Several of these species were observed and their yields determined. These species were at most produced in 5% yield and are therefore not a major product channel. An alternative sources of these species are reactions between NO and other photolysis products. A possible explanation for the failure to observe any smaller molecular products is that the adduct does not dissociate at high temperatures and instead, rearranges to a stable isomer of C3H 3NO. Transient IR laser spectroscopy near 3100 cm-1 was used to observe the nu1 and nu13 transitions of the allyl radical, with their band origins found to lie at 3113.9779(3) cm -1 and near 3110.5 cm-1, respectively. Detailed assignment and analysis of the nu1 transition identified over 1100 transitions, and yielded improved values for DeltaK and phiK ground state centrifugal distortion constants, as well as a new set of excited state (nu1 = 1) rotational and centrifugal distortion constants, in addition to determining the band origin. Transitions involving states with quantum number up to Ka = 11 and N = 27 were identified. Strong perturbations were found in the excited state, included global perturbations of the Ka' = 3 branch, extensive perturbations in the Ka' = 2 and 4 branches, and very localized perturbations in the Ka' = 6 branch. The K a' = 9 and 10 branches appear to be the most perturbed. Possible sources for these perturbations are discussed.

An unique linear aliphatic trisazoalkane was synthesized. Its thermolysis proceeded stepwise to yield seven fragments, with an overall reaction enthalpy of -93.6 kcal/mol, 66.6 kcal/mol lower than that for azo-t-butane. Due to the stepwise feature, the difference in overall reaction enthalpy resulted in only an 8.6 fold rate increase for the trisazoalkane relative to azo-t-butane at 153.46°C. Photolysis of a novel cyclic azimine obtained during the synthesis of the trisazoalkane yielded a highly strained triaziridine and an unusual triazane. The triaziridine rapidly reverted to the azimine with a rate constant of 2.05 x 10-4 s-1 at 24.4°C. Arylmethylenecyclopropanes with para azo, azoxy and other related N-containing substituents were synthesized to study radical stabilizing effects. The order of increasing radical stabilizing ability was determined to be -N(O)=NBu-t, -N3, CH=NBu-t, -N=NBu-t, -NH2, -CH=NOMe, -CH=NNMe 2, -N=N(O)Bu-t, -N=NPh and -CH=N(O)Bu-t. The last three groups, azoxy, nitrone and phenylazo, were the best non-ionic radical stabilizers ever studied. The large rate enhancements in the thermal rearrangement resulted from radical stabilization through spin delocalization by the para-substituents in the transition state. A cumyl type 1,3,5-trisazoalkane and its monoazo, para-bisazo and meta-bisazo analogs were synthesized. Thermolysis of C3 and C4 followed a stepwise mechanism; that is, the two azo groups decomposed sequentially. Mathematical models were developed for analyzing the kinetics data. The rate constants for these azoalkanes increased statistically with the number of -N=N-groups. In addition to the stepwise mechanism, the para-bisazo compound also decomposed concertedly to a quinodimethane. To demonstrate that the 1,3,5-triazoalkane could serve as a radical initiator, different trapping products were made by thermolysis of the 1,3,5-trisazoalkane in the presence of PhSH and nitroxyl radicals. In the binary system of C4 and TEMPO, low polydispersity (1.13) was obtained for polystyrene.

The principal aims of the thesis were to carry out a systematic analytical study to determine the solution properties of narrow-distribution and broad-distribution linear poly(ethylene oxide) (PEO) polymer samples in aqueous and organic solution and to study the adsorption properties of these polymer samples onto glass interfaces and spherical latex particles. The deposition characteristics of various types of bare and PEO coated latex particles onto collector surfaces were also studied. / These studies allowed to ascertain the presence of PEO clusters in aqueous solution. The cluster size was found to be time dependent and to vary between 0.45 $ mu$m and 0.90 $ mu$m. The clusters were found to be in a thermodynamic equilibrium with the free polymer in solution and were found to reform spontaneously after a 30 minute period following filtration. / Adsorption studies indicated that the adsorption of PEO onto latex particles is kinetically controlled and that increased surface roughness and polarity of the latex particles decreases PEO adsorption. PEO clusters in solution were found to increase the value of the effective diffusion constant, D$ rm sb{eff}$ and thus decrease the calculated hydrodynamic layer thickness. / Evanescent wave light scattering was used in conjunction with a hydrodynamic impinging jet method for the study of depositing and non-depositing colloidal systems near interfaces. For non-depositing systems a comparison of the measured particle concentration profiles to the theoretically expected particle concentration profiles, calculated from DLVO theory, was made. The agreement was found to be very good. / The deposition of bare and PEO-coated latex particles onto glass interfaces was also investigated. From the data it was found that bare and smooth latex particles adsorb much more strongly onto collector surfaces than "hairy" latex particles which have long copolymer chains, such as itachonic acid, grafted onto their surfaces. The results indicated that the thicker the adsorbed polymer layer, the stronger the steric force preventing deposition of the polymer coated colloidal particles onto the collector surface. When the combined ellipsometric layer thickness of the particles and the collector surface exceeded a critical value, found to be about 15 nm, no particle deposition onto the collector surface was possible.

The kinetic and mechanistic details involved in the morphological transitions occurring in aggregates prepared from the copolymer polystyrene-b-poly(acrylic acid) (PS-b-PAA) in dioxane-water mixtures and the ability of sodium dodecyl sulfate to induce architectural changes in these aggregates are described in this dissertation. The kinetics of the sphere-to-rod, rod-to-sphere, and vesicle-to-rod transitions were determined by following the change in the solution turbidity as a function of time after the transitions were induced by a sudden jump in one of the solvent components of the system. The kinetics of each transition was explored as a function of the initial solvent composition, the magnitude of the solvent content jump, and the initial polymer concentration. In another study, the amphiphile, sodium dodecyl sulfate (SDS), was found to induce morphological transitions in the copolymer aggregates at lower water contents than those required in the absence of surfactant. The effect was studied as a function of SDS concentration, solvent composition, and copolymer concentration.

The micellization of polystyrene based block copolymers was investigated in aqueous and in organic media. Micelles formed from polystyrene-b-poly(sodium acrylate) (PS-b-PANa) in sodium chloride solutions were investigated by static light scattering (SLS). The aggregation numbers (N$ rm sb{agg})$ were influenced by low salt concentrations ($<$0.10 M) and they were essentially independent of the soluble block lengths. The core radii ($ rm sb{e}$ agreed well with previous solid state results on similar samples studied by small-angle X-ray scattering (SAXS). It was thus concluded that no supermicellar aggregates were present and that the cores were solvent free. / A method to evaluate the critical micelle concentrations (cmc's) of block copolymer micelles by SLS was developed to account for the effects of polydispersity on the cmc. It was found that for block copolymers which have a significant dependence of the cmc on the insoluble block length and which are polydisperse only the present approach was able to evaluate the cmc. / The micellization of PS-b-PANa and PS-b-poly(acrylic acid) (PS-b-PAA) block copolymers were investigated in organic solvents. The cmc's were found to range from $1 times10 sp{-7} { rm to} 5 times10 sp{-9}$ M for insoluble block lengths ranging from 2.6 to 18 units. The N$ rm sb{agg}$ and R$ rm sb{e}$ values for four PS-b-PANa series in tetrahydrofuran, were found to be a function of the length of both blocks. The effect of the degree of neutralization of the PAA block on micellization was probed by SLS and SAXS; micelle formation was found to commence at 5% neutralization. The distribution of water between toluene and the polar cores of block ionomer and sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles was investigated by proton chemical shift measurements as a function of temperature. The amount of water solubilized and the thermodynamic parameters of transfer were found to be a function of the core nature.

Modified biphenols which contain 2,2$ sp prime$-disubstituents on the biphenyl groups and also hydroquinones containing multiple substituents were synthesized in order to prepare novel thermally stable polymers. The structure/properties relationship which were investigated using viscometry, DSC, TG/DTA, TMA, and GPC are discussed. / The prepared polymers (polysulfones and poly(ether ketone)s) exhibit considerably enhanced glass transition temperatures and are soluble in common organic solvents due to the noncoplanar biphenyl rings which increase the disorder along the polymer backbone thereby reducing interchain interactions. The polyesters prepared show poor solubility and their Tg's and Tm's increase considerably over the unhindered polyester analogs due to the chain stiffness. / Polyimides were prepared from the reaction of novel dianhydrides and m- and p-phenylene diamines. A series of bisanhydrides were prepared via the nitro-displacement reaction of hindered biphenols and N-methyl-4-nitrophthalimide. The polymers exhibit good solubility in common organic solvents and show high Tg's. Blends of polycarbonate and polyimides, prepared from m-phenylene diamine, show better miscibility compared to those of polyimides from p-phenylene diamine. / The 2,2$ sp prime$-substituted biphenols which can be oxidized to bisphenoxydiradicals are applicable as oxidizing agents for diphenylmethanes and primary alcohols, and also undergo C-O coupling reactions with activated methylene groups. An additional modified biphenol was synthesized for REDOX polymers applications and the properties of these polymers are discussed.

Thermolysis was investigated as a process to convert waste olefin-based polymers into value-added products at a moderate temperature. Virgin, linear low density polyethylene was used for the majority of the experiments. The thermolysis of virgin polystyrene, recycled polyethylene and 3:2 mixtures of polyethylene and polystyrene were also investigated. The final process that was developed employed the reactive distillation of polyolefins under an inert atmosphere and at moderate reaction temperatures, ranging from 375 to 450$ sp circ$C. The major products from thermolysis of polyethylene were a distribution of low-molecular-weight straight chain alkanes and $ alpha$-olefins ranging from C$ sb6$ to C$ sb{25}.$ Overall volatile product yields up to 90% were obtained from the starting polymer. The initial molecular structure of the polyethylene was found to have a large effect on the rate of molecular weight reduction. A significantly enhanced rate of thermolysis was also observed when polyethylene was processed as a mixture with polystyrene. The mechanisms of thermolysis of polyethylene, polystyrene and mixtures of the two polymers were elucidated. Furthermore, the mechanism of dimer production from polystyrene was found to be different than what has been reported previously.