No description available.

No description available.

No description available.

The phase behavior and phase separation kinetics in polymer solutions in binary mixtures of supercritical carbon dioxide (CO2) and organic solvents were studied for two systems. Solutions of polyethylene (PE) in CO2 + n-pentane were selected as one model system to study both the solid-fluid (S-F) and liquid-liquid (L-L) phase transitions as well as the interplay of these two types of phase separations on the final morphological and thermal properties of PE crystals. Solutions of polysulfone (PSF) in CO2 + tetrahydrofuran (THF) were selected as another model system because of the technological importance of this membrane forming polymer and because of the broad interest in developing new solvent/non-solvent systems for forming microporous materials. These phase boundaries were determined using a high-pressure view-cell and optical techniques over a temperature range of 90-165 oC and pressures up to 55 MPa for PE/n-pentane/CO2 system, and over a temperature range of 25 to 155 oC and pressures up to 70 MPa for PSF/THF/CO2 system. For PE solutions, it has been found that the addition of CO2 to the PE/n-pentane system shifts the L-L phase boundary to significantly higher pressures, but moves the S-F phase boundary only slightly to higher temperatures. The S-F phase boundary which represents the crystallization/melting process in the polymer solution was about 10 oC lower than the crystallization/melting temperatures of the neat polyethylene samples determined by differential scanning calorimetry (DSC). It was further found that the S-F phase boundary in n-pentane displays a unique sensitivity to the pressure-temperature conditions and moves to lower temperatures in the pressure range from 38 to 42 MPa. This effect even though not as augmented remains also for the S-F boundary in the solutions in CO2 + n-pentane mixtures. The miscibility of PSF in THF + CO2 was investigated at CO2 levels up to 14 wt %. This system shows lower critical solution temperature (LCST)-type phase behavior at low CO2 content, which is shifted to upper critical solution temperature (UCST)-type at higher CO2 levels along with an increase in the miscibility pressures. In contrast to the PE system, this system was found to display multiple miscibility windows. A "U"-shaped phase boundary in 92 % THF + 8 % CO2 mixture was observed to transfer to a "W"-shaped phase boundary at 10 wt % CO2, which was further separated into a double "U"-shaped phase boundary at 13 wt % CO2. The specific volume of the polysulfone solutions were found to display a variation parallel to this changing pattern in the phase boundaries, with reduced miscibility being accompanied with an increase in the specific volume. The phase separation kinetics in these two polymer solutions were investigated using time- and angle-resolved light scattering techniques. With the PE solutions, the focus was on the kinetics of S-F phase separation (crystallization) and miscibility and (melting) in n-pentane. Experiments were conducted with relatively dilute solutions at concentrations up to 2.3 wt %. The results show that the crystallization which was induced by cooling at constant pressure is dominated by a nucleation and growth process. In the majority of the experiments the particle growth process was observed to last for about 1 minute with a slight dependence on the crystallization pressure. The phase separation kinetics in PSF solutions were conducted only in a solvent mixture containing 90 wt % THF and 10 wt % CO2. Polymer concentrations were varied up to 3.3 wt %. This system was also observed to undergo phase separation by only nucleation and growth mechanism under these conditions upon reducing the pressure at constant temperature. Several experiments were conducted using a multiple rapid pressure drop technique to identify the depth of the metastable region. PE crystals that were produced by crossing the S-F boundary by different paths were collected and characterized by field emission scanning electron microscopy (FESEM) and DSC. Crystallization was carried out either by cooling at constant pressure, or by cooling without pressure adjustment, or by first crossing the L-L boundary via pressure reduction at a constant temperature followed by cooling. For crystal recovery, the system was depressurized to ambient conditions irrespective of the path. It was found that all of the crystals formed from these solutions show multiple melting peaks in their first DSC heating scans, which however collapse into one crystallization peak in the cooling scans and one melting peak in the second heating scans. The temperatures corresponding to the multiple melting peaks were lower than the single melting temperature of the original PE sample and the melting temperature observed in the second heating scans for all samples. The multiple melting peaks were attributed to the presence of different lamellar thickness that are formed in the crystallization, final depressurization and sample collection stages. Depending upon the crystallization path some differences were noted. The crystals formed by first going through L-L phase separation displayed predominately double melting peaks in the first DSC scan. It was observed that the overall crystallinity is increased by more than 10 % to about 75 % compared to the crystallinity of the original PE sample, which is about 63 %. FESEM characterization showed that the prevailing morphology is composed of plate-like lamellae that show different level of agglomeration depending on the crystallization conditions. The overall structures of the particles were ellipsoid for crystals formed from dilute solutions. For crystals formed from the 1% PE solution, crystal sizes ranged from 4 mm ´ 10 mm for crystals formed at 14 MPa to 30 mm ´ 45 mm at 45 MPa. The crystals formed from 5 wt % solutions in n-pentane at pressures in the range of 38-54 MPa showed different morphologies with features of shish-kebab like structures which were however absent in crystals formed from n-pentane + CO2 solutions. The crystals that were formed from first crossing the L-L phase boundary followed by cooling showed two distinct particle size ranges that were attributed to crystals formed from the polymer-rich and polymer-lean phases that evolve when the L-L phase boundary is crossed. / Ph. D.

Thermosetting polymers can cure at a gradient of cure temperatures due to a variety of factors, including heat transfer in the thermoset during heating and the exotherm due to the chemical reaction occurring during the cure. A new method for assessing the effect of cure conditions on mechanical behavior of toughened thermosets has been developed. Modeling of the phase separation process of a model thermoset system provided detailed understanding of the mechanism of property variation with cure temperature for this material. Subsequent characterization of gradient temperature cured samples has shown important variations, illustrating not only the importance of cure conditions, but the possibility of producing materials with new and useful properties. A special mold was developed to cure samples in a controlled gradient of temperature. Example systems known to show pronounced variations in microstructure cured in this gradient mold showed large variations of microstructure as a function of position within the sample, corresponding to the cure temperature at that point. A model toughened thermoset system was developed to demonstrate gradients of properties following cure in the gradient temperature mold. Cyanate ester materials were modified with hydroxyl-terminated butadiene-acrylonitrile copolymers as well as low Tg amorphous polyesters. The polyesters showed very desirable properties for a toughener, including relatively good thermo-oxidative stability in comparison with the butadiene-acrylonitrile toughener. However, the variation of properties of the cured materials with temperature was small, and to better understand the property variation possible using a gradient cure temperature technique, the butadiene-acrylonitrile toughened cyanate ester system was chosen for further study. This system showed a significant variation of glass transition temperature of the cyanate-rich phase as a function of cure temperature. Modeling of the phase separation process of this material was varied out employing a modeling procedure developed for epoxy materials. Various characteristics of the system were determined in order to apply the model to the chosen toughened thermoset. These included viscosity, surface, and thermodynamic parameters in addition to a careful characterization of the morphological parameters developed during cure at the chosen temperatures. Results show excellent predictive capability of the model for microstructure. Prediction of phase composition as a function of cure temperature is also possible, again with good agreement with experiment results. Higher cure temperatures result in a non-equilibrium phase composition, depressing the glass transition temperature of the continuous cyanate ester rich phase. This provides a mechanism by which properties of the system change as a function of position within a gradient temperature cured sample. Dynamic mechanical analysis was employed to characterize the relaxation properties of gradient and isothermally cured samples. The Havriliak Negami equation was chosen to describe the relaxation behavior of these samples. Comparison of the fitting of isotherms over the small, experimentally accessible range of frequencies showed that the use of time-temperature superpositioning could more reliably discern relatively small differences. The breadth of the relaxation corresponding to the glass transition of the polycyanurate phase was increased with a gradient cure temperature relative to isothermally cured samples. This increased broadness was expressed in an alternative way through the use of an autocorrelation function, which allows direct comparison of the time-dependent transition from a fully unrelaxed condition to a fully relaxed one. / Ph. D.

The overall objective of the project, on which this thesis is based, is to develop a novel hydrocarbon-based proton exchange membrane (PEM) material that can produce a proton conductivity of 0.1 S/cm at the operating conditions of 50 % relative humidity and 120 oC, which is the performance target set by the U.S. DOE for automotive application. As a part of this project, our efforts have been focused on the investigation of the effects of solution-casting conditions on the final morphology and properties of disulfonated poly(arylene ether sulfone) multiblock copolymer films from the viewpoint of phase separation of block copolymers. Of equal importance to this work, is a possibility of utilizing a rheological technique for monitoring the transformation and kinetics of block copolymers during solvent removal process, which was initially examined in order to provide fundamental quantitative understanding and practical information on the solvent removal process. Our results demonstrated that solvent selectivity and drying temperature as well as the block length had considerable effects on the final morphology and properties. The proton conductivity could be significantly increased by simply utilizing a selective solvent, dimethylacetamide (DMAC), which is good and marginal for the sulfonated and unsulfonated blocks, respectively, rather than N-methyl-2-pyrrolidone (NMP), a neutral solvent for both blocks. The drying temperature was also observed to have considerable effects on the final properties, being coupled with the effects of solvent selectivity. Also, it was shown that the multiblock copolymer consisting of longer blocks was more sensitive to the processing conditions. From the morphological study using transmission electron microscopy and small-angle X-ray scattering, evidences for the above observations were obtained. In the second part of this dissertation, the evolution of GÎ and GË of the solutions of a styrene-butadiene-styrene (SBS) triblock copolymer in toluene was obtained as a function of concentration using a modified parallel-plate device and a rheology test scheme developed in this study in an effort to quantify the phase separation kinetics. Then, the information on the phase transformation and kinetics of the SBS block copolymer in the solution was obtained by analyzing the GÎ and GË data with the Avrami equation. The Avrami exponent was found to be approximately 1, which indicates that the phase transformation occurred by a one-dimensional growth mechanism. The rate constant showed a strong concentration-dependence. After the initial increase up to 45 vol %, the rate constant drastically decreased and, finally, converged to 0 at 70 vol %. It is believed that, at the concentration range below 45 vol %, the phase separation became more intense as the polymer molecules had more chances to interact owing to the concentration increase. However, above 45 vol %, the phase transformation became weaker due to the limited mobility of the polymer molecules, which finally led to a “kinetically frozen-in” structure, in which the polymer molecules could not move any longer. Thus, it can be concluded that the solvent removal rate is one of the dominant factors that decide the final microstructures of solution-cast block copolymer films. / Ph. D.

The effects of polymer concentration and solvents on cocrystal morphology of low solubility drugs were investigated, both of which had an impact. The melting temperatures also decreased with increasing polymer concentration. Placing the binding agent, benzene, at different interfaces induced morphological changes, such as formation of porous cocrystals. Previously liquid-liquid phase separation (LLPS) has been reported as a hindrance in the crystallisation process impeding further development. A phase diagram was constructed, and different phases were categorised into 4 types. After separation of the highly concentrated amorphous Oil Phase II, it was prone to gradual crystallisation. Crystallisation took place over 30-60 minutes; this allowed the in-situ monitoring. A novel cocrystallisation technique was developed; from (LLPS). Cocrystals of indomethacin with saccharin and nicotinamide were obtained by mixing Oil Phase II with the coformers. In-situ monitoring by spectroscopic had gradual changes in spectra; characteristic peaks increased in height and area with the formation of crystals until the reaction was complete. With crystal formation, the XRD spectra gradually had a sharper baseline due to a decrease in the amorphous indomethacin. The photoluminescence (PL) spectra displayed several peaks coupling into one large hump together with increasing intensity as the sample crystallised. There was a shift in the peak absorbance of the pure drug crystals obtained from LLPS and the indomethacin:saccharin cocrystal obtained from LLPS. Amorphous stabilisation was achieved by mixing polymer (PVP) with Oil Phase II. There were no changes to the XRD diffractogram as the sample did not undergo crystallisation.

No / Molecular mobility and physical form of co-spray-dried sugar:lysozyme formulations were evaluated. Co-spray-dried trehalose:lysozyme and sucrose:lysozyme formulations in 1:9, 1:1 and 9:1 ratios (w:w) were stored at 0% RH and 75% RH for 5-6 days. Molecular mobility and physical form of the co-spray-dried formulations after storage were determined by using 13C and 1H solid-state NMR as well as X-ray powder diffractometry. The results showed that increasing sugar content in co-spray-dried formulations stored at 0% RH decreased molecular mobility of the amorphous formulations indicating a close association of the protein and sugar. Exposure of sugar:lysozyme 1:1 and 9:1 formulations to 75% RH led to separation of sugar and protein phases, where the sugar phase was crystalline. The intimate sugar:lysozyme interaction of the formulations stored at 0% RH and the phase separation of the sugar-rich formulations stored at 75% RH were also confirmed by using 13C solid-state NMR spin-lattice relaxation time-filter (T1-filter) measurements. The propensity of sucrose and trehalose to crystallise was similar; however, the results suggest that part of the sugar in the phase-separated formulations remained amorphous and in close association with lysozyme.

Yes / Binary and ternary blends of a polylactic acid matrix with polycaprolactone (PCL) and polybutylene succinate (PBS) were produced by twin screw extrusion, containing up to 30 wt% loading. Mechanical, thermal and rheological characterisation techniques were used to quantify properties of the different blend formulations and miscibility was investigated using scanning electron microscopy. PCL is known to act as an impact modifier in PLA but to cause a corresponding reduction in strength. Results showed that addition of both PBS and PCL seperatly caused a reduction in melt viscosity, elastic modulus and tensile strength, but an increase in impact strength and strain at break. Analysis of morphology suggested that immiscibility was evident, particularly at higher PCL and PBS loadings. Results indicated that incorporation of a small loading of PBS had a synergistic effect on the PLA-PCL blend properties. Miscibility was improved and enhanced mechanical properties were observed for a ternary blend containing 5 wt% of both PBS and PCL compared to blends containing 10% of each polymer alone. / Financial support of Floreon- Transforming Packaging Ltd through the PhD sponsorship and materials provision.

Investigamos o sistema formado por dois condensados aprisionados em estados hiperfinos diferentes do Rubídio, num potencial em forma de charuto, ou seja, num sistema físico real e quase-unidimensional. É investigada a dependência das soluções das equações de Gross-Pitaevski com a separação entre as armadilhas, bem como com o parâmetro de acoplamento de Josephson, para três valores diferentes do número total de átomos aprisionados. Para alguns conjuntos de parâmetros constatamos a existência de estados metaestáveis. O observável que escolhemos para caracterizar tal sistema físico foi a separação média entre os pacotes, pois os dois ramos de soluções encontramos correspondem a soluções mais juntas ou mais separadas espacialmente. / We study the system formed by two coupled condensates of different Rubidium hyperfine states trapped in a cigar shaped potential, that is, a real quasi one-dimensional system. The dependency of the solution of the Gross-Pitaevski equations is investigated as a function of trap displacement and Josephson coupling parameter for three different values of the total trapped atoms number. For some sets of parameters we report the existence of metastable states. The observable we chose to characterize this system was the mean separation between the packages, because we found two branches which correspond to closer or more separated solutions.