Conjugated polymer based electronics, a type of flexible electronic devices, can be produced from solution by traditional printing and coating processes in a roll-to-roll format such as papers and graphic films. This shows great promise for the emerging energy generation and conversion. The device performance of polymer electronics is largely dependent of crystalline structures and morphology of photoactive layers. However, the solution crystallization kinetics of conjugated polymers in the presence of electron acceptor nanoparticles has not been fully understood yet. In this study, solution crystallization kinetics of poly (3-hexylthiophene) in the presence of carbon nanotubes and graphene oxide has been investigated by using UV-visible absorption spectroscopy and transmission electron microscope. Various kinetics parameters such as crystallization temperature, polymer solution concentration and nanoparticle loading will be discussed. The crystallization rate law and fold surface free energy will be addressed by using polymer crystallization theory of heterogeneous nucleation. This fundamental study will provide a foundation of fabricating high efficiency polymer based electronics.

Conjugated semi-conducting polymers have become well known for their potential applications in hybrid electronic devices like solar cells, LEDs, and organic displays. These hybrid devices also contain inorganic nanoparticles, which complement the polymer when they are combined into the same layer. Control over the conformation and crystallinity of the polymer is critical for device performance, yet not much is known about the effect that these nanoparticles have on the polymer. Here, zinc oxide nanowire was surface modified with mono-substituted-carboxylic acid tetraphenylporphyrin and dodecanethiol, and introduced to poly(3-hexyl thiophene) in solution. The electron transfer, kinetics, and thermodynamics of this system were investigated through spectroscopic methods. Chemical reaction rate laws and Lauritzen-Hoffman Growth Theory were employed to substantiate the mechanism and rate of polymer crystallization. Surface-modification of the ZnO nanowire suggested an improvement in polymer nucleation by as much as 43.8%. A synthetic procedure was also developed to modify the inorganic nanowire with quantum dots in order to improve electron transport into the nanowire. Development of these theories and exploration of these surface effects can help lead the way for a new generation of flexible, high efficiency, hybrid electronic devices.

Water-borne latex coatings represent a safer, more user-friendly, and environmentally responsible alternative to solvent-borne coatings, and are growing in popularity each year. However, these coatings often exhibit unfavorable performance when exposed to water for extended periods of time. This prolonged exposure often results in water uptake, which may give rise to other detrimental effects such as a decrease in modulus, blushing or water-whitening, reduced serviceable life, and softening of the film. In this study, various polymer composition latex design spaces are studied to develop an understanding of how water uptake can be modulated and minimized using common synthetic approaches. Factors including monomer selection, particle size, polymer molecular weight, crosslinking density, surfactant choice and particle stabilization, processing variables and Tg are considered. In addition, some formulation modifications including PVC, film thickness, and choice of coalescent package are explored to gain a more comprehensive understanding of final product performance. In quantifying the total water uptake of the films, gravimetric analysis tends to be the preferred method employed in the coatings industry. However, other analytical approaches can be used to better understand the effect that water has on the properties of the film. These methods may include differential scanning calorimetry, electrochemical impedance spectroscopy, immersion testing using dynamic mechanical analysis, and others. In the work, it has been shown that interparticle crosslinking, surfactant, and monomer selection can have an extreme influence on the water uptake of free films. Film samples exhibit a range of water uptake values from nearly 200% to less than 5% over a one-week soak in deionized water. It is thought that the surfactant may provide hydrophilic channels that allow water to v penetrate the film and form heterogeneous domains within the coating. These domains then grow and scatter light, leading to water-whitening and an increase in mass when compared to the dry film. Utilizing monomers with differing relative solubilities in water, such as methyl methacrylate and styrene, further allow control of this effect. Interparticle crosslinking via keto-hydrazide crosslinking, which is achieved during the film formation process, can also prevent the formation and growth of these large water domains, thus resulting in better performing films.

Ever since the advent of polymer science, polyurethanes have played a huge role in the industrial world. They have been used in endless applications from furniture padding to aircraft coatings, to binders for insensitive munitions. It is therefore important that the chemistry of polyurethanes is well understood as well as the ability to draw relationships between the raw materials selected and the end-use properties of the polymer. Because of the multitude of practical applications, the development of an undergraduate polymer chemistry laboratory focused on polyurethane elastomers is developed and described herein. Polymer chemistry students are exposed to hydroxyterminated polybutadiene (HTPB) polyols as well as di- and multifunctional isocyanates for use in a tin-catalyzed reaction. The effect of catalyst concentration and crosslinking agent on cure time, prepolymer structure on end-use properties, and the effect of crosslink density on physical properties are explored. Students also receive a very important introduction to statistical experimental design. They learn when using statistical experimental design is necessary, and they learn how to manipulate, analyze, and interpret data using two-way ANOVA in Minitab. The development of the lab experiment also led to extrapolating the use of polyurethane elastomers into a new application, the development of a polyurethane spinal muscular atrophy (SMA) brace. SMA is a neurodegenerative disorder that results in the mutation or deletion of the spinal motor neuron gene, resulting in the atrophy of a subject’s spine muscles throughout the continuation of their life. These patients are therefore forced to wear a brace for the entirety of their lives. The current brace technology in use by SMA patients is limited by the fact that SMA affects a very small amount of the population and therefore it is not cost-effective for industry to develop a brace technology designed for these patients. Scoliosis braces such as thoracolumbrosacral orthoses (TLSOs) are too hard and too uncomfortable for patients with SMA; therefore, the polyurethane elastomer was extrapolated to develop a brace with more flexibility and more durability. Two generations of polyurethane elastomeric brace were developed and evaluated by a subject and family with an SMA background. The brace is a much improved technology to the TLSO braces and provides more flexibility, more mobility, greater comfort, and superior modularity to the old technology. An instruction manual is also included with a step-by-step process of how to reproduce the brace.

Free-standing ultra-thin films and micro to nanoscale fibers offer a unique geometry in which to study the dynamics of thin film stability and polymer chain dynamics. By melting these films and investigating the subsequent processes of hole formation and growth, and fiber thinning and breakup, many interesting phenomena can be explored, including the nucleation of holes, shear-thinning during hole formation, finite-extensibility of capillary thinning viscoelastic fibers, and confinement effects on entanglement of polymer chains. Free-standing films in the melt are unstable and rupture due to instabilities. The mechanism of membrane failure and hole nucleation is modeled using an energy barrier approach which is shown to capture the dependence of hole nucleation on thickness. The formed holes grow exponentially and are found to grow under a shear thinning, nonlinear viscoelastic, high shear strain regime. These holes impinge upon each other to form suspended fibers. The fibers thin according to a model for the elasto-capillary thinning of the suspended viscoelastic fluid filaments. Monitoring fiber thinning allows for the acquisition of rheological properties as well as the transient, apparent extensional viscosity giving insight into strain hardening and eventual steady-state extensional viscosity. The decay and breakup of these fibers and their interconnected branched structure indicates the effects of confinement on chain entanglement in ultra-thin films. A transition below a critical film thickness, comparable to the dimensions of a polymer chain, shows drastically reduced interchain entanglements and a remarkably faster breakup of suspended fibers. The processes of fiber formation from the melting of ultra-thin films are explored in high detail and produce a new technique for the investigation of rheological and material properties, confinement effects, and the dynamics of thin films and polymer chains.

Styrenic block copolymer thermoplastic elastomers are one of the most widely used thermoplastic elastomers (TPEs) today. The focus of this research is to fundamentally understand the structure-processs-property relationships in these materials. Deformation behavior of the block copolymers with cylindrical and lamellar morphologies has been investigated in detail using unique techniques like deformation calorimetry, transmission electron microscopy (TEM), combined in-situ small angle x-ray and wide angle x-ray scattering (SAXS/WAXS). The research involves the study of structural changes that occur at different length scales along with the energetics involved upon deformation. The structural changes in the morphology of these systems on deformation have been investigated using combined SAXS/WAXS setup. Small angle x-ray scattering probed the changes at the nano-scale of polystyrene (PS) cylinders, while wide angle x-ray scattering probed the changes at molecular length scales of the amorphous/crystalline domains of the elastomeric mid-block in these systems. TEM analysis of the crosslinked elastomers (by UV curing) further confirms the interpretation of structural details as obtained from SAXS upon deformation. New structural features at both these length scales have been observed and incorporated into the overall deformation mechanisms of the material. Characteristic structural parameters have been correlated to differences in their mechanical response in the commercially relevant cylindrical block copolymers. Effect of various process conditions and thermal treatments has been investigated. The process conditions affect the structure at both micro-scopic (grain size) and nano-scopic (domain size) length scales. A correlation has been obtained between a mechanical property (elastic modulus) and an easily measurable structural parameter (d-spacing). Effect of various phase transitions such as order-to-order transition has been studied. Selective solvents can preferentially swell one phase of the block copolymer relative to other and thus bring a change in morphology. Such kinetically trapped structures when annealed at higher temperature try to achieve their thermodynamic equilibrium state. Such changes in morphology significantly affect their tensile and hysteretic response. In another work it has been shown that by carefully compounding these styrenic block copolymers having different morphologies, it is possible to completely disrupt the local scale order and remove the grain boundaries present in these materials. Finally, a new test technique has been developed, by modifying an existing Charpy device to test polymeric films at a high strain rate. A custom designed load-cell is used for force measurements which imposes harmonic oscillations on a monotonic loading signal. The data obtained from this device can be used to analyze visco-elastic response of polymeric films at frequencies much higher than the conventional dynamic mechanical analyzer (DMA).

Single polymer passage through geometrically confined regions is ubiquitous in biology. Recent technological advances have made the direct study of its dynamics possible. We studied the capture of DNA molecules by the electroosmotic flow of a nanopore induced by its surface charge under an applied electric field. We showed theoretically that the DNA molecules underwent coil-stretch transitions at a critical radius around the nanopore and the transition assisted the polymer passage through the pore. To understand how a polymer worms through a narrow channel, we investigated the translocation dynamics of a Gaussian chain between two compartments connected with a cylindrical channel. The number of segments inside the channel changed throughout the translocation process according to the overall free energy of the chain. We found a change in the entropic driving force near the end of the process due to the partitioning of the chain end into the channel rather than the initial compartment. We also developed a theory to account for the electrophoretic mobility of DNA molecules passing through periodic confined regions. We showed that the decrease in the translocation time with the molecular weight was due to the propensity of hairpin entries into the confined regions. To further explore the dynamics of polymer translocation through nanopores, we performed experimental studies of sodium polystyrene sulfonate translocation through α-hemolysin protein nanopores. By changing the polymer-pore interaction using different pH conditions, we identified the physical origins of the three most common event types. We showed that increasing the polymer-pore attraction increased the probability of successful translocation. Motivated by understanding the dynamics of a polymer in a crowded environment, we investigated the dynamics of a chain inside a one dimensional array of periodic cavities. In our theory, the chain occupied different number of cavities according to its confinement free energy which consisted of entropic and excluded volume parts. By assuming that the chain moved cooperatively, the diffusion constant exhibited Rouse dynamics. Finally, we performed computer simulations of a chain inside a spherical cavity. We found that the confinement effect was best described by the hard sphere chain model. We further studied the escape dynamics of the chain out of the cavity through a small hole. The equilibrium condition of the chain during the escape was discussed.

Co-continuous structures generated from the phase separation of polymer blends present many opportunities for practical application. Due to the large interfacial area in such structures and the incompatibility between the components, such non-equilibrium structures tend to coarsen spontaneously into larger sizes and eventually form dispersed morphologies. Here, we utilize various strategies to kinetically stabilize the co-continuous structures in polymer blend systems at nano- to micro- size scales. In the partially miscible blend of polystyrene and poly(vinyl methyl ether), we took advantage of the spinodal decomposition (SD) process upon thermal quenching, and arrested the co-continuous micro-structures by the addition of nanoparticles. In this approach, the critical factor for structural stabilization is that the nanoparticles are preferentially segregated into one phase of a polymer mixture undergoing SD and form a percolated network (colloidal gel) beyond a critical loading of nanoparticles. Once formed, this network prevents further structural coarsening and thus arrests the co-continuous structure with a characteristic length scale of several microns. Our findings indicate that a key to arresting the co-continuous blend morphology at modest volume fractions of preferentially-wetted particles is to have attractive, rather than repulsive, interactions between particles. For the immiscible blend of polystyrene and poly(2-vinyl pyridine) (PS/P2VP), we presented a strategy to compatibilize the blend by using random copolymers of styrene and 2-vinylpyridine, controlling the degree of immiscibility between PS and P2VP. Based on such compatibilization, co-continuous structured membranes, having characteristic size down to tens of nanometers, were fabricated in a facile way, via the solvent-induced macrophase separation of polymer blend thin films. The feature size was controlled by controlling the film thickness and varying the molecular weight of the PS homopolymer and the random copolymers. As the processing method (solution casting) is simple and the structures are insensitive to the solvent or substrate choices, this approach shows great potential in the large scale fabrication of co-continuous nanoscopic templates on flexible substrates via roll-to-roll processes. Moreover, we proposed a quasi-binary blend system based on the PS/P2VP pair with the addition of a common solvent. An experimentally accessible phase mixing temperature was achieved, and the co-continuous morphologies were generated via thermally induced spinodal decomposition. The addition of solid particles significantly slowed down the coarsening kinetics and, in some cases, arrested the co-continuous structures at ~6 &mum for a short period of time. This study suggests an alternative means to achieve co-continuous structures in polymer solutions and also provides better understanding of the thermodynamics and kinetics of polymer blend phase separation. Our research demonstrates several means of kinetically trapping the non-equilibrium interconnected structures at sub-micron to tens-of-nanometer size scales that are germane to several functions including active layers of photovoltaic cells and polymer-based membranes.

Room temperature ionic liquids (ILs) are a unique class of solvents which are characterized by non-volatility, non-flammability, electrochemical stability and high ionic conductivity. These properties are highly desirable for ion-conducting electrolytes, and much work has focused on realizing their application in practical devices. In addition, hydrophilic and ionophilic polymers are generally miscible with ILs. The miscibility of ILs with ion-coordinating polymers makes ILs effective plasticizers for gel polymer electrolytes. Due to their unique properties, ILs present a means to realize the next generation of energy storage technology. In this dissertation, the fundamental interactions between poly(ethylene oxide) (PEO) and a variety of room temperature ILs were investigated. ILs with acidic protons were demonstrated to form a stronger interaction with PEO than ILs without such protons, suggesting that hydrogen bonding plays a dominant role for PEO miscibility with ILs. The hydrogen bonding interaction is selective for the PEO block of a PEO-b-PPO-b-PEO block copolymer (BCP). Therefore, blending these copolymers with the strongly interacting IL 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF6]) induced microphase separation into a well-ordered structure, whereas the neat copolymer is phase mixed. At sufficient quantities, the interaction between [BMI][PF6] and PEO suppresses PEO crystallinity entirely. In addition, the induced microphase separation may prove beneficial for ion conduction. Therefore, microphase separated copolymer/IL blends were investigated as potential gel polymer electrolytes. Cross-linkable block copolymers which microphase separate when blended with [BMI][PF6] were synthesized by modifying PPO-b-PEO-b-PPO copolymers with methacrylate end-groups. Cross-linking these copolymers while swollen with an IL generates ion gels with high ionic conductivities. The copolymer/IL blends vary from a well-ordered, strongly microphase separated state to a poorly ordered and weakly microphase separated state, depending upon the molecular weight. Stronger microphase separation results in higher mechanical strength upon cross-linking. However, this does not greatly affect ion conductivity. Nor is conductivity affected by forming gels from cross-linked PEO homopolymers when compared to BCPs. It was found that BCPs can be beneficial in producing gel electrolytes by allowing sequestration of phase selective cross-linkers away from the conducting block. Cross-linker molecules that are selective for the PPO blocks can be used to increase the mechanical strength of the gels with only a small effect on the conductivity. When cross-linkers that partition to the mixed PEO/IL block are used, the conductivity decreases by nearly a factor of 2. These studies show how ILs interact with PEO and how gel polymer electrolytes can be constructed with the IL [BMI][PF6]. While BCPs cannot directly be used to increase ion conductivity, they do allow for greater mechanical strength without sacrificing conductivity. This suggests many new approaches that may be used to simultaneously achieve high ionic conductivity and mechanical strength in solid and gel polymer electrolytes.

The main theme of this research is to understand the structure-property evolution during crystallization of a semicrystalline thermoplastic polymer. A combination of techniques including rheology, small angle light scattering, differential scanning calorimetry and optical microscopy are applied to follow the mechanical and optical properties along with crystallinity and the morphology. Isothermal crystallization experiments on isotactic poly-1-butene at early stages of spherulite growth provide quantitative information about nucleation density, volume fraction of spherulites and their crystallinity, and the mechanism of connecting into a sample spanning structure. Optical microscopy near the fluid-to-solid transition suggests that the transition, as determined by time-resolved mechanical spectroscopy, is not caused by packing/jamming of spherulites but by the formation of a percolating network structure. The effect of strain, Weissenberg number (We) and specific mechanical work (w) on rate of crystallization (nucleation followed by growth) and on growth of anisotropy was studied for shear-induced crystallization of isotactic poly-1-butene. The samples were sheared for a finite strain at the beginning of the experiment and then crystallized without further flow (Janeschitz-Kriegl protocol). Strain requirements to attain steady state/ leveling off of the rate of crystallization were found to be much larger than the strain needed to achieve steady state of flow. The large strain and We >1 criteria were also observed for morphological transition from spherulitic growth to oriented growth. An apparatus for small angle light scattering (SALS) and light transmission measurements under shear was built and tested at the University of Massachusetts Amherst. As a new development, the polarization direction can be rotated by a liquid crystal polarization rotator (LCPR) with a short response time of 20 ms. The experiments were controlled and analyzed with a LabVIEWTM based code (LabVIEWTM 7.1) in real time. The SALS apparatus was custom built for ExxonMobil Research in Clinton NJ.