The purpose of this study was learn how the diffusion, swelling, and crystallization processes are coupled during solvent-induced crystallization of poly(ether ether ketone) (PEEK). Unoriented amorphous PEEK films were immersed in aprotic organic liquids at ambient temperature and bulk properties or characteristics were monitored as a function of immersion time. The sorption behavior, Tg and Tm° suppression, crystallinity, and dynamic mechanical response were correlated as a function of solvent chemistry and immersion time. The saturation time of methylene chloride, 1,3-dichloropropane, tetrahydrofuran, cyclopentanone, chlorobenzene, toluene, diethyl ketone, and ethylbenzene in amorphous PEEK films were found to range from hours to days depending on the level of polymer-solvent interactions. In-situ isochronal DMA spectra show that the Tg of PEEK was suppressed from 150 ° C to below ambient temperature such that crystallization was kinetically feasible during ambient immersion. In addition, an increase in viscoelastic dispersion was attributed to the presence of crystallinity. From dynamic mass uptake and wide-angle x-ray diffraction (WAXD) results, it was found that the bulk sorption rate was equal to the bulk crystallization rate for all solvent systems that promoted SINC and PEEK exhibited diffusion-limited crystallization, irrespective of the nature of the transport mechanism. In addition, the solvent-induced crystals exhibit preferred orientation as supported by photographic WAXD. A distinct sorption front, observed with scanning electron microscopy, further supports the scenario of diffusion-controlled crystallization and one-dimensional diffusion. Isothermal DMA spectra for THF, cyclopentanone, and chlorobenzene, indicate that, as the solvent diffuses into the films, the stiffness of the polymer decreases at short times, begins to increase, and then reaches a relatively time-independent value. It was determined that the initial decrease in the storage modulus was due to the incredible plasticization of the amorphous phase. When the films contained greater than 60 % of the ultimate crystallinity, the storage modulus was observed to increase as a result of the reinforcing effect of the solvent-induced crystals. WAXD and mass uptake results confirm that the plateau in the storage modulus coincides with the completion of bulk crystallization and saturation of the amorphous phase. / Ph. D.

Natural fibers show potential to replace glass fibers in thermoset and thermoplastic composites. Kenaf is a bast-type fiber with high specific strength and great potential to compete with glass fibers. In this research kenaf/epoxy composites were analyzed using Dynamic Mechanical Analysis (DMA). A three-point bend apparatus was used in the DMA testing. The samples were tested at 1 hertz, at a displacement of 10 μm, and at room temperature. The fiber volume content of the kenaf was varied from 20%-40% in 5% increments. Ten samples of each fiber volume fraction were manufactured and tested. The flexural storage modulus, the flexural loss modulus, and the loss factor were reported. Generally as the fiber volume fraction of kenaf increased, the flexural storage and flexural loss modulus increased. The loss factor remained relatively constant with increasing fiber volume fraction. Woven and chopped fiberglass/epoxy composites were manufactured and tested to be compared with the kanaf/epoxy composites were manufactured and tested to be compared with the kenaf/epoxy composites. Both of the fiberglass/epoxy composites reported higher flexural storage and flexural loss modulus values. The kenaf/epoxy composites reported higher loss factor values. The specific flexural storage and specific flexural loss modulus were calculated for both the fiberglass and kenaf fiber composites. Even though the kenaf composites reported a lower density, the fiberglass composites reported higher specific mechanical properties.

This work focuses on polymer glasses relaxation behavior. Polymethylmethacrylate was chosen as a typical representative of polymer glasses. Relaxation processes were studied by dynamical mechanical spectroscopy and differential scanning calorimetry was used as a supplemental analysis. Relaxation process above Tg and high values of rubberlike plateau modulus were observed in thermomechanical spectra. High temperature relaxation transition was studied from the perspective of thermal history, frequency and axial stress dependence and influence of molecular structure was also investigated. Apparent activation energies of studied processes and their axial stress dependence for polymethylmethacrylate were determined. On the basis of obtained data, a hypothesis was developed which connects high temperature relaxation process with molecular process responsible for strain hardening.

No description available.

No description available.

The increase and change in traffic loading in recent years has resulted in the introduction of a new range of high performance asphalt binders. These new binders known as modified asphalt binders, have a more complex behavior than traditional binders. A review of the current mathematical models shows that most of them suffer from different drawbacks that make them inadequate for their intended application. To describe the behavior of straight and modified binders in the thermorheologically simple linear viscoelastic region, two models are proposed. Models to characterize the absolute value of the complex shear modulus (|G*|) and the phase angle (d) were developed using the matching function approach and validated by an experimental program. The dynamic mechanical properties of two typical paving grade binders and three modified binders were tested at intermediate and high service temperatures. Short-term and long-term aging were simulated by the rolling thin film oven test and the pressure aging vessel test, respectively. A dynamic shear rheometer with parallel plate configuration was used to conduct the dynamic mechanical tests at frequencies between 0.06 to 188.5 rad/sec and temperatures ranging from 5 to 75°C. Prior to the frequency sweeps, strain sweeps were performed to establish the linear viscoelastic region. Results indicated a strong susceptibility to the defined strain at intermediate temperatures; however, strain susceptibility was less pronounced at high temperatures. Frequency sweeps were then conducted at a constant strain corresponding to greater than 95% of the initial complex shear modulus as established by AASHTO TP5 for straight asphalts. The Time-Temperature Superposition Principle was used to construct the master curves. The shift factors were determined based on the complex shear modulus master curves and verified for the phase angle, storage shear modulus and loss shear modulus. After construction of the master curves, non-linear regression was used to fit the proposed models to the experimental data. Comparison between the measured and predicted values indicated a good agreement for frequencies higher than 10⁵ rad/sec. The phase angle model was found to adequately describe unmodified binder with a small percentage of errors (less than 6%). On the other hand, the phase angle model was found unable to simulate the plateau region observed for polymer-modified binders. However, the error in this case was found to be relatively small (from zero to 10%). The ability of the models to estimate other viscoelastic functions, e.g. storage shear modulus (G'), loss shear modulus (G"), and relaxation spectrum (H(t)), was found to be adequate. / Master of Science

The frequent use of high-density polyethylene pipes over the last decades has been possible because these pipes are lightweight, corrosion resistant, unlikely to have leaks, and are low cost. The chain structure of the polymer, the extrusion and cooling conditions, the resulting morphology and the ambient conditions all play an important role in the pipe's performance. A new generation of high density polyethylene resins has improved the performance of pipes, but brought new challenges to their testing and characterization. There is a need to understand the rheological behavior of the resins, their processing, and their associated properties in a finished pipe. The rheological behavior of the resins was studied to characterize the effect of high molecular weight tails in a bimodal molecular weight distribution. The use of cone-and-plate and parallel-plate geometries in a rheometer provided simple flow that characterized the steady and dynamical response of the polymer melts. The rheological measurements detected differences in the resins: the resin with higher molecular weight tail showed increased zero shear-rate viscosity, a much slower relaxation of stresses and a resin that more readily deviates from linear viscoelastic behavior. The rheology of the resins allowed modeling their flow through different extrusion dies. The flow channels for pipe dies are thick, so velocities and shear rates are low. Using a different die had a larger impact in shear rates and stresses compared to using different resins. The resin with higher molecular weight shows much higher shear stresses for the same die and temperature, which makes processing harder. The flow of a fluid through a pipe causes constant stress, which at long enough times is one the reasons for pipe failure. Tests that characterize the service lifetime of pipes take long times and are expensive. Dynamical mechanical analysis allows characterizing the viscoelastic properties of the pipe and creep testing confirms that shift factors work for viscoelastic properties measured inde-pendently. For the characterized pipes, one hour of testing at 80 °C is equivalent to a month of test-ing at 25 °C. This works characterizes pipes made from two resins and two different dies. The meas-urements showed that the pipes were statistically the same. / Doctor of Philosophy / The use of high-density polyethylene pipes has thrived over the last decades. This has been possible because these pipes are lightweight, corrosion resistant, unlikely to have leaks, and are low cost. The structure of the polymer and the manufacturing process both affect the pipe's performance. A new generation of high density polyethylene resins has improved the performance of the pipes, but brought new challenges to their testing and characterization. There is a need to understand the flow characteristics of the resins and their properties as a finished pipe. The flow behavior of the polymers in simple geometries gave insights into the polymer's structure. A higher molecular weight resin showed increased resistance to flow and deviated from ideal behavior more readily. These flow characteristics let one model certain aspects of the manufacturing process. Pipe manufacturing is a slow process because of the high resistance to flow of the polymer. Changing the processing equipment, and to a minor degree changing the resins, had an important impact in the manufacturing process. The tests that characterize the service lifetime of pipes take long times and are expensive. When pipes have fluids flowing at high pressures, it takes decades for them to fail. There are viscoelastic tests that allow much quicker characterization of pipes and help predict their long term behavior. This works characterizes pipes made from two resins and two different dies. This works characterizes pipes made from two resins and two different dies. The measurements showed that the pipes were statistically the same.

The relaxation characteristics of rubbery poly(ethylene oxide) [PEO] networks have been investigated as a function of network composition and architecture via dynamic mechanical analysis and broadband dielectric spectroscopy. A series of model networks were prepared via UV photopolymerization using poly(ethylene glycol) diacrylate [PEGDA] as crosslinker: variations in crosslink density were achieved either by the introduction of water in the prepolymerization reaction mixture, or by the inclusion of mono-functional acrylate such as poly(ethylene glycol) methyl ether acrylate [PEGMEA] or poly(ethylene glycol) acrylate [PEGA]. Copolymerization with mono-functional acrylate led to the insertion of flexible branches along the network backbone, and the corresponding glass-rubber relaxation properties of the copolymers (i.e., Tg, relaxation breadth, fragility) were a sensitive function of network architecture and corresponding fractional free volume. Relatively subtle variations in network structure led to significant differences in relaxation characteristics, and a systematic series of studies was undertaken to examine the influence of branch length, branch end-group, and crosslinker flexibility on viscoelastic response. Dielectric spectroscopy was especially useful for the elucidation of localized, sub-glass relaxations in the polymer networks: the imposition of local constraint in the vicinity of the crosslink junctions led to the detection of a distinctive fast relaxation process in the networks that was similar to a comparable sub-glass relaxation observed in crystalline PEO and in the confined regions of PEO nanocomposites. Gas permeation studies on the model PEGDA networks confirmed their utility as highly-permeable, reverse-selective membrane materials, and strategic control of the network architecture could be used to optimize gas separation performance. Dynamic mechanical and dielectric measurements have also been performed on a semicrystalline polyester, poly(trimethylene terephthalate) [PTT], in order to assess the influence of processing history on the resultant morphology and corresponding viscoelastic relaxation characteristics. Studies on both quenched and annealed PTT revealed the presence of a substantial fraction of rigid amorphous phase (RAP) material in the crystalline samples: dielectric measurements showed a strong increase in relaxation intensity above the glass transition indicating a progressive mobilization of the rigid amorphous phase with increasing temperature prior to crystalline melting.

The dynamic relaxation characteristics of Matrimid® (BTDA-DAPI) polyimide and several functionalized aromatic polyimides have been investigated using dynamic mechanical and dielectric methods. The functionalized polyimides were thermally rearranged to generate polybenzoxazole membranes with controlled free volume characteristics. All polyimides have application in membrane separations and exhibit three motional processes with increasing temperature: two sub-glass relaxations (ƴ and β transitions), and the glass-rubber (α) transition. For Matrimid, the low-temperature ƴ transition is purely non-cooperative, while the β sub-glass transition shows a more cooperative character as assessed via the Starkweather method. For the thermally rearranged polyimides, the ƴ transition is a function of the polymer synthesis method, thermal history, and ambient moisture. The β relaxation shows a dual character with increasing thermal rearrangement, the emerging lower-temperature component reflecting motions encompassing a more compact backbone contour. For the glass-rubber (α) transition, dynamic mechanical studies reveal a strong shift in Tα to higher temperatures and a progressive reduction in relaxation intensity with increasing degree of thermal rearrangement. The dynamic relaxation characteristics of poly(ether imide) and poly(methyl methacrylate) nanocomposites were investigated by dynamic mechanical analysis and dielectric spectroscopy. The nanoparticles used were native and surface-modified fumed silicas. The nanocomposites display a dual glass transition behavior encompassing a bulk polymer glass transition, and a second, higher-temperature transition reflecting relaxation of polymer chain segments constrained owing to their proximity to the particle surface. The position and intensity of the higher-temperature transition varies with particle loading and surface chemistry, and reflects the relative populations of segments constrained or immobilized at the particle-polymer interface. Dielectric measurements, which were used to probe the time-temperature response across the local sub-glass relaxations, indicate no variation in relaxation characteristics with particle loading. Nanocomposite studies were also conducted on rubbery poly(ethylene oxide) networks crosslinked in the presence of MgO or SiO2 nanoparticles. The inclusion of nanoparticles led to a systematic increase in rubbery modulus and a modest positive offset in the measured glass transition temperature (Tα) for both systems. The sizeable increases in gas transport with particle loading reported for certain other rubbery nanocomposite systems were not realized in these crosslinked networks.

Neste trabalho foi estudada a influência da adição de quitosana e sílica a monômeros dimetacrílicos, BisEMA e TEGDMA, por meio das técnicas de fotocalorimetria, termogravimetria e análise dinâmico mecânica. Os resultados dos experimentos de fotocalorimetria demonstraram que a quitosana pode aumentar a velocidade de polimerização e o máximo de conversão para alguns sistemas em determinadas concentrações da mesma, já a sílica tem pouco efeito nas reações de fotopolimerização das amostras. Para os experimentos de termogravimetria, a quitosana tem pouca influência na degradação das amostras não alterando significativamente as curvas TGA/DTG, por outro lado a sílica acelerou a degradação térmica das amostras. A avaliação das propriedades mecânicas demonstrou que a quitosana diminui a temperatura de transição vítrea e a resposta elástica dos sistemas não afetando os valores dos módulos de armazenamento e módulos de perda. A sílica apresentou a tendência de aumento de temperatura de transição vítrea e não alteração da resposta elástica das amostras. / In this work we studied the influence of the addition of chitosan and silica in dimethacrylic monomers, BisEMA and TEGDMA, by photocalorimetry, thermogravimetric analysis and dynamic mechanical analysis. The results of photocalorimetry experiments demonstrated that chitosan can increase the polymerization rate and the degree of conversion for some concentrations. Silica has little effect on photopolymerization reactions of samples. For thermogravimetric experiments, chitosan has little influence on the degradation of samples and does a slightly change the TGA / DTG curves, on the other hand silica accelerated thermal degradation of the samples. The evaluation of mechanical properties showed that chitosan reduces the glass transition temperature and elastic response of the samples but does not affect the values of the storage modulus and loss modulus. Silica showed an effect of increasing glass transition temperature and almost no change in the elastic response of the samples.