It is estimated that roughly 103, 515 tons of peach waste is produced annually in the US. The majority of the waste is disposed of in landfills, which contributes to climate change as they release 93 million metric tons of CO2 equivalent. Peach waste principally consists of remaining stone and seed after flesh removal. The agro-waste includes both cellulose and lignin, which can be utilized as a filler in plastic packaging to reduce carbon footprints and material cost. The objectives of this research are (1) to develop peach flour (PF)-filled biocomposites with a polyolefin matrix using maleic anhydride-g-high density polyethylene (MAH-g-HDPE) coupling agent resin and (2) to investigate the composites’ physicomechanical, thermal, and water absorbance changes. First, preliminary experiments examined a range of PF concentrations (5-50%) and MAH concentrations (0-17%) were tested to narrow the variability of PF and MAH loading mixture in an HDPE matrix. Preliminary experiments suggested that a 2:1 ratio of PF:CR provides maximum tensile properties. Response surface methodology (RSM) was utilized to analyze and optimize the tensile strength of the PW composite. The RSM parameters were MAH loading (5-20%), PF loading (2.5-10%), and polyolefin matrix (HDPE or polypropylene). The properties of PF-HDPE biocomposites were analyzed using several instrumental analyses. Mechanical strength (including tensile strength, elongation, and Young’s modulus) and thermal properties (thermal degradation, melting point, and crystallinity), and water resistance with the addition of PF and MAH were investigated. Biocomposite mechanical properties generally resulted in a nonsignificant decrease compared to the controls. Water absorption significantly increased with PF loading (P<0.01, =0.05). PF-PP biocomposites demonstrated a shift in thermal stability with an average 9.6% increase in Td compared to its control, whereas PF-HDPE biocomposites displayed no change in Td compared to its control. PF-PP and PF-HDPE biocomposites experienced a 36.7% and 16.0% decrease, respectively, in crystallinity with PF addition. The results provided evidence that peach byproduct can be diverted from landfills and utilized a filler in a polyolefin matrix. Polyolefin biocomposites with 2.5% PF would possess comparable tensile strength to a commercially available control. PF-polyolefin biocomposites can be used for packaging, automotive, and non-weightbearing construction parts.

Three different polymers (a high-density polymer and two other polymers) were tested for use as an x-ray catheter in a radiation therapy application. This report describes the testing of these three materials to determine which material is the best option for a long use catheter. Tests included tensile, simulated clinical life, and other tests. Some testing was performed using nitrogen and an industrial coolant. Testing revealed significant non-circularities for some catheters. With increasing pressure, the circularity of these catheters increased. The tensile tests were performed on samples with varying doses of radiation. Tensile testing showed significant decreases in ultimate tensile strength with increasing radiation dose for both polyurethanes. Other testing was performed on the two polyurethanes to determine their compatibility with the industrial coolant. The test showed good compatibility with the coolant. Simulated clinical life tests were performed on a test fixture and with software to run the radiation source automatically for several hours at a time. Overall, one material was found to have very low ductility, made lower with increasing radiation. The material with the higher ductility was chosen as the better catheter material despite some disadvantages when compared to the stiffer polymer. This report describes necessary tests for thin polymer geometries used in applications where resistance to radiation, mechanical integrity, and coolant compatibility are the main considerations.

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.

No description available.

<p><p lang="en-US">This experimental research thesis describes the combination of conjugated polymers and carbon nanotubes with the fields of electrophoretic deposition (EPD) and organic solar cells. Prior to these contributions, soluble conjugated polymers and carbon nanotubes that have been functionalized by them had not yet been deposited by EPD from solution or by using non-toxic solvents. Additionally, EPD had not yet been utilized to deposit the active layer in a solid organic photovoltaic device. <p lang="en-US">The EPD of soluble conjugated polymer functionalized carbon nanotubes from non-toxic solvents was achieved through an iterative process of experimentation and technique refinement. The developed EPD technique utilized the high pH region at the cathode substrate to neutralize positively charged weak polyelectrolytes macromolecules. Their functional groups were protonated using a minimized amount of acetic acid which also enabled their solubility. Deprotonation of the quaternary ammonium functional groups rendered them neutrally charged and insoluble tertiary amines. This mechanism facilitated the formation of coatings that were predictable and uniform in appearance and thickness. <p lang="en-US">Control over coating thickness was demonstrated by coatings spanning 100 nm to 10 μm. These coatings were produced by adjusting the applied voltage, solution concentration, and tuning the deposition duration. <p lang="en-US">Techniques for the fabrication of a photovoltaic device using an active layer produced by EPD were established though modifications of general organic photovoltaic device fabrication procedures. These modifications involved redesigning the photolithographic ITO etching pattern, adding an insulating barrier strip, thickening the aluminum electrode layer, and switching the top buffer layer from LiF to BCP.</p> / Master of Applied Science (MASc)

<p>The phenomenon of image blurring on laser-printed or electro-photocopied paper has been discovered since the 1980s. In the 1990s, the problem was confirmed to be associated with the undesired surface conduction along the unique photoconductive polymer surface during the photoconduction process. Other than this, little progress has been made in investigating this phenomenon, due to the limited experimental techniques.</p> <p>In this thesis, the electrical properties of a commercially available photoconductor as a result of Corona charging were studied. Various techniques including vacuum deposition and step-function impedance spectroscopy were employed, to overcome the nature of the photoconductor that prevented the use of conventional techniques such as AC impedance spectroscopy. Negative dielectric constant (NDC) has been prevalently discovered at a broad range of frequencies (below 1Hz and up to 1 MHz) and it was questioned in the form of a physically-impossible inductor. This precipitous sign switch of dielectric constant is found in various areas ranging from physics, chemistry, biology to electronics. The magnitude of the NDC decreased drastically with the decrease of electric field frequency. The system obeyed the proposed free-carrier plasma model with a resonance frequency at MHz level.</p> <p>Commercially available polymeric photoconducting materials showing NDC at extremely low frequency are expected to provide unusual scattering to electromagnetic waves and therefore demonstrate profound implications with reduced cost. It has paved the way for many applications such as inductors in integrated chips without bulky coils and provides an insight into a possible revolution in electronics and photonics.</p> / Doctor of Philosophy (PhD)

Algae can be used as a feedstock for agricultural fertilizers, livestock/poultry feeds, anaerobic digestion, and biofuel production. Regardless of the end product, water removal is necessary and difficult to do cost effectively. For each product the requirements for moisture content (or solids content) vary, such that a desirable water removal strategy would need to be adaptable to varying levels of water removal. Flocculation, with sedimentation and drying was evaluated as a possible strategy for algae dewatering. Anionic and nonionic flocculants are known to be ineffective at flocculating algal culture, which was confirmed for this case by electro-osmotic flow testing of the algae and jar tests with three flocculant charge types. Electrophoretic mobility of the algae indicated that it has a negative charge and no flocs were present in the jars. The effectiveness of the cationic flocculant was determined by measuring settling rates, supernatant turbidity, and filtration rates. Sedimentation and filtration rates of Scenedesmus acutus were measured with varying dosages (0-25 ppm) of a synthetic cationic polymeric flocculant. The results of this study should assist in predicting the time it takes to thicken algae at a concentration range of 0.4-1.0 g/L to a product at a concentration range of 15-250 g/L.

Various techniques of fabricating surface patterns of small scales have been widely studied due to the potential applications of surface patterns in a variety of areas. It is a challenge to fabricate well-ordered surface area efficiently and economically. Evaporation-induced surface patterning is a promising approach to fabricate well-ordered surface patterns over a large area at low cost. In this study, the evaporation-induced surface patterns with controllable geometrical characteristics have been constructed. The dewetting kinetics on deformable substrate is also investigated. Using simple templates to control the geometry and the evaporation behavior of a droplet of volatile solvent, various gradient surface patterns, such as concentric rings, multiple straight stripes formed with a straight copper wire, etc. have been constructed on PMMA films. The wavelength and amplitude are found to decreases with the decrease of the distance to the objects used in templates. There is also a nearly linear relation between the amplitude and wavelength. The effects of several experimental parameters on the geometrical characteristics of the surface structures are studied, i.e. dimensions of the template, film thickness (solution concentration), substrate temperature, etc. The wavelength and amplitude increase with the increase of the film thickness (solution concentration), with the increase of the dimension of the template. However with the increase of the substrate temperature, the wavelength increases, while the amplitude decrease. Hexagonal network in pre-cast PMMA film have been fabricated by a “breath figure” approach at low humidity and low substrate temperature. The dimensions of the hexagonal holes are dependent on the template size and film thickness. The kinetics of the evaporative dewetting of a liquid (toluene) film on a deformable substrate (PMMA film) with the confinement of a circular copper ring is also studied. The liquid film first dewets from the outside towards the copper ring. When a critical volume is reached, an internal contact line appears, which dewets from the center to the copper ring smoothly with a constant velocity, then switches to a “stick-slip” motion. The average velocity of the smooth motion increases with the increase of the copper ring size and film thickness.