Potential uses for hydrogels span the full range of science, technology, and medicine. In this work two different hydrogel matrices were studied in the context of ion sensing and drug transport. In chapter one the fundamentals of sensing using a shear-mode acoustic device are described. In chapters two and three the experimental and theoretical work to understand sensor behavior are described. Chapter four treats the diffusion of a model drug through aged, physically gelled PVOH. In chapter five the change of gel structure with time is investigated and the relationship between aging and gel preparation is discussed.

Single Site Catalysts (SSCs) have been utilized for olefin polymerization. Altering the metal-ligand architecture in the SSCs, polyolefin properties can be enhanced in a rational manner. This influence of the ligands in the SSC on the property of polyolefins prepared can be referred to as the primary ligand influence. Extending this understanding and subsequent control of the metal-ligand framework to the interaction of SSCs within organic and inorganic supports is vital for the synthesis of polyolefins with tailored properties. The motivation behind this thesis was to explore the support influence on the reactivity of the SSC tethered to a support matrix during ethylene homo and copolymerization. In order to address this question of the support influence on the final polyolefin properties, synthetic routes to covalently bind SSCs on different matrices have been explored. Two distinct supported SSCs have been used to prepare branched polyethylenes. Branched polyethylenes can be prepared by either copolymerization (ethylene and α-olefin) or oligomerization/copolymerization processes (ethylene and in situ generated α-olefin). Synthetic routes to prepare precursor catalysts to Constrained Geometry Catalysts (CGCs) by silyl elimination chemistry have been developed (Chapter 2). Efficient synthetic protocols to assemble CGCs on aminomethylpolysytrene matrices (Chapter 3) and amine-functionalized mesoporous silica (Chapter 4) are also reported. These supported catalysts, with appropriate cocatalysts have been used to prepare ethylene homo and copolymers, the polymer thermal properties and microstructures were analyzed by various analytical techniques. Branched polyethylenes (LLDPE) can be prepared by copolymerization chemistry. It has been observed is that the influence of the support is seen in the production of lower crystalline forms of high density polyethylene (HDPE, 20–50% crystalline), while homogeneous polymerization of analogous soluble CGCs afford HDPE of higher percent crystallinity (greater than 60% crystalline). High-density polyethylene with crystallinity of 40–60% can be prepared by using cocatalysts tethered to AMPS or silica in conjunction with analogous soluble, homogeneous CGCs (Chapter 6). Preparative methods to assemble piano stool complexes on hydroxy polystyrenes have been designed. These supported catalysts in conjunction with cocatalysts act as both oligomerization and copolymerization catalysts and allow the preparation of branched polyethylenes from ethylene only feed (Chapter 7).

Currently, there is tremendous interest in using block copolymers to generate nanostructures where a critical issue is the control of long range order. This dissertation focuses on how molecular architecture of block copolymers influences the long range order. Using a series of AnBn star block copolymers with different numbers of arms (n = 1, 2, 4 and 16), the effect of molecular architecture on the grain growth kinetics is investigated by both thermal annealing and annealing in supercritical carbon dioxide (CO 2). Across this entire series of materials, all the A arms are polystyrene (PS) blocks from the same anionically synthesized batch, and all the B arms are polyisoprene (PI) blocks from the same anionically synthesized batch. Thus, all the star block copolymers employed in this study are composed of the same A and B arms linked together in symmetric numbers and the only difference within this series is the number of arms, n. The grain growth kinetics of these AnBn materials is then monitored in real space by transmission electron microscopy (TEM), followed by subsequent micrograph image analysis. It is found that the molecular architecture influences the grain growth kinetics of these An Bn star block copolymers significantly under both thermal and supercritical CO2 annealing. Their grain growth kinetics shows a strong dependence on the number of arms. Also, the grain coarsening kinetics followed a scaling law as V ∼ tβ, where V is the characteristic grain volume and t is annealing time. Under simple thermal annealing, the exponent, β, is found to be about 0.2 for the A1B1 diblock copolymer (AnBn with n = 1) and 0.4 for all three star block copolymers with n = 2, 4 and 16. Meanwhile, under supercritical CO2 annealing, the grain growth dynamics of these AnB n stars with n = 2, 4, and 16 is found to be the same as that of the same AnBn materials under thermal annealing. However, the grain growth kinetics of the A1B1 diblock is dramatically enhanced in supercritical CO2 relative to thermal annealing. Comparison of the scaling relationships strongly suggests that the difference in grain growth between the A1B1 diblock and the AnB n star block copolymers can be attributed to the difference in chain entanglements and to the thermodynamic barrier to diffusion perpendicular to the lamellar layers.

This thesis focuses primarily on the structure-property relationships of poly (styrene-ethylene-butylene-styrene) triblock copolymer TPEs. First evidence for strain-induced crystallization occurring in certain SEBS block copolymers has been established using unique techniques like deformation calorimetry, combined in-situ small angle X-ray and wide angle X-ray diffraction (SAXD/WAXD). Also the ramifications of such strain-induced crystallization on the mechanical properties like cyclic hysteresis, stress relaxation/creep retention of these SEBS systems have been studied. In addition, the structural changes in the morphology of these systems on deformation have been investigated using combined SAXD/WAXD setup. Small angle X-ray diffraction probed the changes at the nano-scale of polystyrene (PS) cylinders, while wide angle X-ray diffraction probed the changes at molecular length scales of the amorphous/crystalline domains of the elastomeric mid-block in these systems. New structural features at both these length scales have been observed and incorporated into the overall deformation mechanisms of the material. Continuous processing techniques like extrusion have been used to obtain ultra long-range order and orientation in these SEBS systems. Thus well ordered crystal like hexagonal packing of cylinders, where in each element in this hexagonal lattice can be individually addressed without any grain boundaries can be realized using these robust techniques. The effect of long-range order/orientation on the mechanical properties has been studied. In addition, these well ordered systems serve as model systems for evaluating deformation mechanisms of these SEBS systems, where the relative contributions of each of the phases can be estimated. EPDM/i-PP thermoplastic vulcanizates (TPVs) have micron size scale phase separated morphologies of EPDM rubber dispersed in a semicrystalline i-PP matrix as a result of the dynamic vulcanization process. Confocal microscopy studies, along with scanning electron microscopy (SEM) studies show that the morphology of these EPDM/i-PP systems resembles a microcellular "filled" foam in which i-PP occupies the strut regions and EPDM the inner core. Based on this, an analytical model has been developed that takes into account composition information, molecular weight, cure state and morphology into account.

In this dissertation, the cold-drawing response of a commercial high-density polyethylene (HDPE) resin has been studied using solid-state nuclear magnetic resonance (NMR) spectroscopy and variety of other complementary techniques. Melt-crystallized, isotropic samples of the HDPE have been drawn to various extensions at ambient temperature (21°C) and at a relatively slow strain rate (0.0013 s−1). Using solid-state NMR, the first unambiguous evidence for a major morphological component intermediate to the crystalline and amorphous domains in the cold-drawn HDPE microstructure has been found. Employing an ‘inverse 13 C T1 filter’ and other filtering techniques, signals from the various components have been selected and compared. The intermediate component comprises chains of all-trans conformation but with significant disorder in packing. The chains show fast, intermediate-amplitude motions about their axes and are generally aligned with the draw direction, but with a greater distribution of orientation angles relative to crystalline phase. A quantitative 13C NMR procedure has been utilized in the analysis of morphological component composition during cold drawing. In the undeformed material, the NMR-derived composition shows excellent agreement with other common techniques. The mass fraction of the intermediate component has been measured by NMR to be as high as 35% in the cold-drawn HDPE, greater than the contributions from the amorphous domains and monoclinic crystals. The intermediate component content dramatically increases by 240% just after necking, along with a doubling in the monoclinic crystals. At the same time, decreases of about 25% in the total crystalline and amorphous phases occur. A general re-ordering in the microstructure takes place during neck propagation and strain hardening. The total crystallinity rises by about 8%, with a corresponding decrease in the monoclinic crystals (50%) and amorphous material (30%). Based on 1H spin diffusion data, a microstructural model of cold-drawn HDPE is offered. The spin diffusion data identify the intermediate component with tie-molecule bundles that connect small ‘mosaic block’ crystallites (ca. 10–15 nm side dimension) along the draw direction. The bundles consist of about 30 chains and are estimated to be about 2.5 nm in diameter and 3 nm in length.

The reinforcement of polymers using additives of dimensions below one micrometer is presented: those acting at the molecular and nanometer scales. This thesis will describe new additives and morphologies exhibiting high levels of mechanical reinforcement. It is the focus of this work to chronicle the range of physical and material properties that are altered upon inclusion of these modifiers. Additionally, this thesis will establish how these physical-property changes affect the mechanical behavior of the resulting composite. In the area of molecular reinforcement, a new class of additive, the organophosphate, is shown here to enhance modulus and yield strength in epoxy polymers once cured. Initially, the effect on the physical and thermal properties of the polymer system is investigated as a function of additive molecular weight, solubility, and concentration. The altered properties include T g, density, thermal stability and initial epoxy viscosity. The mechanical properties of the modified epoxy are demonstrated to be a result of the physical changes made to the matrix polymer through the addition of the organophosphorous additive. By increasing the density of the polymer and reducing or eliminating sub-Tg relaxations, the modulus and yield strength of the polymer can be greatly enhanced. These property changes are investigated in a variety of epoxy polymer systems in order to elucidate the effects of both the additive and polymer chemical structure on final mechanical properties. Polymer modification using nanometer-scale additives and modifiers has been the focus of intense study recently. Heretofore, these studies have focused on the exfoliated, or delaminated, clay morphology to impart the property enhancements, effectively isolating the particulates within the matrix. This thesis focuses on polymer modification at the nanometer scale such that the added clays interact and positively change the composite fracture toughness. By introducing this clay-clay interaction, modulus and strength can be increased together with the toughness. Such a property combination is highly desirable, as most toughening agents reduce modulus and strength. Initially, the intercalated morphology is investigated in an epoxy system. Additionally, new routes to synthesizing intercalated morphologies of clay concentrations approaching 50% are developed.

This thesis focuses on the synthesis and characterization of polyolefin nanocomposites containing polyhedral oligomeric silsesquioxane (POSS) units. Two copolymerization methods were developed utilizing either ring-opening metathesis polymerization or metallocene-catalyzed reactions to incorporate cubic silsesquioxane into polyolefins. Ring-opening metathesis copolymerizations of cyclooctene and the POSS-norbornylene macromonomer have been performed using Grubbs' catalyst RuCl2(=CHPh)(PCy3)2. Random copolymers have been prepared and characterized with POSS loadings as high as 55 wt%. Diimide reduction of these copolymers affords polyethylene-POSS random copolymers. Polyethylene (PE) and isotactic polypropylene (PP) copolymers incorporating POSS have also been prepared using a metallocene/methylaluminoxane (MAO) cocatalyst system. A wide range of POSS concentrations was obtained in these polyolefin POSS copolymers under mild conditions; up to 56 wt% for PE-POSS copolymers and 73 wt% for PP-POSS copolymers were prepared. Copolymerizations of styrene and the POSS-styryl macromonomer have been performed using CpTiCl 3 in conjunction with MAO. Random copolymers of syndiotactic polystyrene and POSS copolymers have been formed and characterized. Novel nanocomposites of PE-POSS have been characterized using Wide Angle X-ray Scattering (WAXS). From both line broadening of the diffraction maxima and also the oriented diffraction in a drawn sample, we conclude that POSS forms anisotropically shaped crystallites. On the basis of this result, a novel approach to obtain nanocomposites containing inorganic nanolayers is proposed. Cubic silsesquioxane (POSS) nanoparticles are used to achieve the nanolayered “clay-like” structure through controlled self-assembly. The organic polymer, covalently connected to POSS, is intended to regulate the POSS crystallization into a two-dimensional lattice. The concept is demonstrated by random copolymers of polybutadiene and POSS. The data from WAXS and transmission electron microscopy clearly show the formation of lamellar nanostructure of POSS aggregates, which bares the similarity at low POSS loadings to the morphology of exfoliated polymer clay nanocomposites. By taking the advantage of controlled interactions between polymer chains, we open the door to the design of polymeric materials at important nanometer length scales beyond their primary sequence length. Ultimately, this may provide materials with properties bridging the performance gap between polymer and ceramics.

Polyhedral oligomeric silsesquioxanes (POSS) are molecularly precise isotropic particles with average diameters of 1-2 nm. A typical T 8 POSS nanoparticle has an inorganic Si8O12 core surrounded by eight aliphatic or aromatic groups attached to the silicon vertices of the polyhedron promoting solubility in conventional solvents. Previously, efficient synthetic methods have been developed whereby one of the aliphatic groups on the periphery is substituted by a functional group capable of undergoing either homo- or copolymerization. In the current investigations, preparative methods for the chemical incorporation of POSS macromonomers in a series elastomers have been developed. Analysis of the copolymers using WAXD reveals that pendant POSS groups off the polymer backbones aggregate, and can crystallize as nanocrystals. From both line-broadening of the diffraction maxima, and also the oriented diffraction in a drawn material, the individual POSS sub-units are crystallizing as anisotropically shaped crystallites. The formation of POSS particle aggregation is strongly dependent on the nature of the polymeric matrix and the POSS peripheral group. X-ray studies show aggregation of POSS in ethylene-propylene elastomers occurred only with a phenyl periphery, whereas POSS particles with isobutyl and ethyl peripheries disperse within the polymer matrix. By altering the polymer matrix to one containing chain repulsive fluorine units, aggregation is observed with both the phenyl and isobutyl peripheries. Altering the polymer chain to poly(dimethylcyclooctadiene), POSS aggregates with isobutyl, ethyl, cyclopentyl, and phenyl peripheries. The formation of POSS nanocrystals increases the mechanical properties of these novel thermoplastic elastomers, including an increase in the tensile storage modulus and formation of a rubbery plateau region. Tensile tests of these elastomers show an increase in elastic modulus with increasing POSS loading. The elongation at break was as high as 720%. Cyclic tensile test show some hysteresis of the elastomers. However, the curves show Mullins effect behavior, commonly seen in elastomers. Elastomers with POSS dispersion, however, show poor mechanical properties. These results demonstrate the novel material property gains by the incorporation and aggregation of POSS in thermoplastic elastomers, as well as the influence of the POSS periphery.

This thesis is focused in three areas: An investigation of a thermodynamic criterion for failure by environmental stress cracking using observations of the wetting behavior of stress-cracking liquids on glassy polymer substrates; Determination of the dominant chemical and physical degradation mechanisms associated with exposure of poly-p-phenylenebisbenzoxazole fiber to moisture moisture and UV-Vis spectrum light; And finally, the effect of constraint on fracture at a bi-material interface is investigated using a model epoxy-metallic adherend specimen. The wetting behavior of an ESC liquid on polycarbonate substrates has been evaluated as a function of substrate stress using a variation of Contact Adhesion Testing, a novel method of measuring small contact angles by refraction and conventional goniometry. The inelastic and elastic strain condition and time to the onset of crazing were also observed. A normalization of the time to onset of crazing using stress state, solubility difference and diffusion coefficients was shown to collapse the kinetic observations. A comprehensive study of the degradation mechanisms of PBO AS fiber exposed in a controlled manner to challenging chemical environments, moisture and UV-Visible spectrum light was undertaken. Fibers were characterized using a broad range of mechanical and physical tests including tensile testing, Elemental Analysis, scanning electron microscopy, small angle X-ray diffraction, wide angle X-ray diffraction and attenuated total reflectance infrared spectroscopy. Degradation by moisture is found to be primarily due to a loosening of the fiber's fibrillar structure. Degradation by UV-Visible spectrum light is found to be chemical in nature involving hydrolytic disruption of the oxazole ring and possible subsequent conversion to an amide bond. Approaches to alleviation of PBO AS fiber degradation were studied including super-critical carbon dioxide extraction of residual acid, the use of UV-Vis blocking coatings, compaction of the fiber microstructure and PBO AS/Siloxane composites prepared in super-critical carbon dioxide. Finally, the effect of constraint on fracture at the interface between a polymer and adherend having orders of magnitude larger stiffness was studied using a model epoxy/metallic adherend system. Fracture energy was measured using an Elastic Wedge Opened Double Cantilevered Beam test and the process zone imaged using photoelastic methods.

The ability to fundamentally understand how changes in the molecular architecture and reinforcement at the molecular and nano-scale effect the mechanical and thermal behavior of glassy thermosets is of considerable interest. A series of epoxy-based networks with controlled molecular weight between crosslinks and backbone stiffness are utilized to identify characteristics that govern yield behavior. Two parameters, the glass transition temperature, Tg, and cohesive energy density, Ec, are identified to describe changes in network stiffness and strength, respectively. The parameters are incorporated into a model that describes yielding over a range of stress states, strain rates, and temperatures. The same epoxy network is used to explore the effects of backbone stiffness and crosslink density on the strain hardening modulus and fracture. It is found the strain hardening modulus is directly related to the crosslink density of the network similar to a traditional rubber. The backbone stiffness appears to have no effect on several post-yield phenomena. A class of compounds labeled molecular fortifiers are then incorporated into the model epoxy network. Two phosphorus-based compounds, one that is included as a free additive and another that is covalently bound to the network, are shown to improve a range of mechanical, physical, and thermal properties. The covalently bound fortifier increases the crosslink density through specific physical bonding interactions and alters the characteristics of the network. In addition several sulfur and a carbon-based compound are investigated as possible molecular fortifiers. The phhysical interactions in the interphase region are found to be enhanced in nano-clay composites that contain fortifiers. These interactions lead to improved mechanical and thermal characteristics over composites utilizing commercially modified nano-clays.