Two magmatic systems were investigated using different petrological tools: 1) Origin of Ponza trachyte was studied combining data from MI with trends predicted by thermodynamic modeling. MI data were compared with known phase relations in the ternary feldspar and anorthite-diopside-albite systems to constrain the parameters used in the modeling. MI data are consistent with melt evolution from a basaltic parent via a fractional crystallization mainly of pyroxene and feldspars. These data and the results from the modeling, suggest a genetic link between the Ponza trachyte and coeval alkali olivine basalts on the nearby Ventotene Island. 2) We evaluated the range of magmatic temperatures within the crystallization interval for a basanite with different olivine-spinel geothermometers. While olivine spinel pair records the evolution of the basanite during crystallization, low temperatures calculated with the geothermometers are unrealistic. This is likely due to the presence of significant amounts of Ti in our magmatic spinels. Indeed Ti is not taken into account in the geothermometers. We tested the possibility of accounting for the presence and effects of Ti using a linear correction for the Fe+2 content in our spinels. While this generated more realistic temperatures at the low end of the range, it also increased the dispersion in the data, suggesting that spinel behavior is more complex and that the presence of Ti affects content and site occupancy of other elements as well. / Ph. D.

This work is concerned with a better understanding of the influences that sparse long-chain branching has on the rheological and processing behavior of commercial metallocene polyethylene (mPE) resins. In order to clarify these influences, a series of six commercial polyethylenes was investigated. Four of these resins are mPE resins having varying degrees of long-chain branching and narrow molecular weight distribution. The remaining two resins are deemed controls and include a highly branched low-density polyethylene and a linear low-density polyethylene. Together, the effects of long-chain branching are considered with respect to the shear and extensional rheological properties, the melt fracture behavior, and the ability to accurately predict the flow through an abrupt 4:1 contraction geometry. The effects that sparse long-chain branching (M_branch > M_c) has on the shear and extensional rheological properties are analyzed in two separate treatments. The first focuses on the shear rheological properties of linear, sparsely branched, and highly branched PE systems. By employing a time-molecular weight superposition principle, the effects of molecular weight on the shear rheological properties are factored out. The results show that as little as 0.6 LCB/10⁴ carbons (<1 LCB/molecule) significantly increases the zero-shear viscosity, reduces the onset of shear-thinning behavior, and increases elasticity at low deformation rates when compared to linear materials of equivalent molecular weight. Conversely, a high degree of long-chain branching ultimately reduces the zero-shear viscosity. The second treatment focuses on the relationship between long-chain branching and extensional strain-hardening behavior. In this study, the McLeish-Larson molecular constitutive model is employed to relate long-chain branching to rheological behavior. The results show that extensional strain hardening arises from the presence of LCB in polyethylene resins, and that the frequency of branching in sparsely branched metallocene polyethylenes dictates the degree of strain hardening. This observation for the metallocene polyethylenes agrees well with the proposed mechanism for polymerization. The presence of long-chain branching profoundly alters the melt fracture behavior of commercial polyethylene resins. Results obtained from a sparsely branched metallocene polyethylene show that as few as one long-chain branch per two molecules was found to mitigate oscillatory slip-stick fracture often observed in linear polyethylenes. Furthermore, the presence and severity of gross melt fracture was found to increase with long-chain branching content. These indirect effects were correlated to an early onset of shear-thinning behavior and extensional strain hardening, respectively. Conversely, linear resins exhibiting a delayed onset of shear-thinning behavior and extensional strain softening were found to manifest pronounced slip-stick fracture and less severe gross melt fracture. The occurrence of surface melt fracture appeared to correlate best with the degree of shear thinning arising from both molecular weight distribution and long-chain branching. The ability to predict the flow behavior of long-chain branched and linear polyethylene resins was also investigated. Using the benchmark 4:1 planar contraction geometry, pressure profile measurements and predictions were obtained for a linear and branched polyethylene. Two sets of finite element method (FEM) predictions were obtained using a viscoelastic Phan-Thien/Tanner (PTT) model and an inelastic Generalized Newtonian Fluid (GNF) model. The results show that the predicted profiles for the linear PE resin were consistently more accurate than those of the branched PE resin, all of which were within 15% of the measured vales. Furthermore, the differences in the predictions provided by the two constitutive models was found to vary by less than 5% over the range of numerical simulations obtained. In the case of the branched PE resin, this range was very narrow due to loss of convergence. It was determined that the small differences between the PTT and GNF predictions were the result of the small contraction ratio utilized and the long relaxation behavior of the branched PE resin, which obscured the influence of extensional strain hardening on the pressure predictions. Hence, it was expected that numerical simulations of the 4:1 planar contraction flow for the mildly strain hardening metallocene polyethylenes would not be fruitful. / Ph. D.

Melt polymerization and novel monomers enabled the synthesis of polyesters for electronic and biological applications. Inspiration from nature and a passion for environmental preservation instigated an emphasis on the incorporation of renewable resources into polymeric materials. Critical analysis of current research surrounding bisphenol-A replacements and ioncontaining segmented polyurethanes aided in identifying benchmark polymers, including limitations, challenges, and future needs. Structure-property-morphology relationships were investigated to evaluate the polymers for success in the proposed applications as well as to improve understanding of polyester compositions to further design and develop sophisticated polymers for emerging applications. Aiming to utilize the reported [2 + 2] cycloaddition of the known mesogen 4,4’-dimethyltrans-stilbene dicarboxylate (SDE) to overcome ultraviolet (UV) induced degradation issues in electronic encasings, the synthesis of copolyesters containing SDE ensued. 1,6-Hexanediol (HD) and 1,4-butanediol comonomers in varying weight ratios readily copolymerized with SDE under melt transesterification conditions to afford a systematic series of copolyesters. Differential scanning calorimetry revealed all copolyesters exhibited liquid crystalline transitions and melting temperatures ranged from 196 °C – 317 °C. Additionally, melt rheology displayed shear thinning to facilitate melt processing. Compression molded films exhibited high storage moduli, a glassy plateau until the onset of flow, and tensile testing revealed a Young’s iii modulus of ~900 MPa for poly(SDE-HD). These properties enable a wide range of working temperatures and environments for electronic applications. Adding complexity to linear liquid crystalline copolyesters, copolymerization with oligomeric hydroxyl-functionalized polyethers afforded segmented liquid crystalline copolyesters. 4,4’-Biphenyl dicarboxylate (BDE), commercially available diols containing 4, 5, 6, 8, or 10 methylene units, and introducing poly(tetramethylene oxide) or a Pluronic® triblock oligoethers in varying weight % were used to synthesize multiple series of segmented copolyesters. Comparing melting transitions as a function of methylene spacer length elucidated the expected even-odd effect and melting temperatures ranged from 150 °C to 300 °C. Furthermore, incorporating the flexible soft segment did not prevent formation of a liquid crystalline morphology. Complementary findings between differential scanning calorimetry and small-angle X-ray scattering confirmed a microphase-separated morphology. Thermomechanical analysis revealed tunable plateau moduli and temperature windows based on both soft segment content and methylene spacer length, and tensile testing showed the strain at break doubled from 75 weight % to 50 weight % hard segment content. The same compositions Young’s moduli decreased from 107 ± 12 MPa at 75 weight % hard segment to 19 ± 1 MPa with 50 weight % hard segment, demonstrating the mechanical trade-off and range of properties possible with small compositional changes. These segmented copolyesters could find use in high-performance applications including electronic and aerospace industries. A two-step synthesis transformed caffeine into a novel caffeine-containing methacrylate (CMA). Conventional free radical copolymerization with a comonomer known to provide a low glass transition temperature (Tg), 2-ethylhexyl methacrylate (EHMA), allowed the investigation of the effect of small amounts of pendant caffeine on polymer properties. Thermal and iv thermomechanical testing indicated CMA incorporation dramatically increased the storage modulus, however, a microphase-separated morphology was not attained. Association of the pendant caffeine groups through non-covalent π-π stacking could present opportunities for novel thermoplastics and it is proposed that placing the pendant group further from the backbone, and potentially increasing the concentration, could aid in promoting microphase-separation. Alkenes are reactive sites for placing functional groups, particularly those required for polyester synthesis. Methyl 9-decenoate (9-DAME), a plant-based fatty acid, provided a platform for novel biodegradable, renewable, polyesters. A formic acid hydration reaction generated an isomeric mixture of AB hydroxyester or AB hydroxyacid monomers for melt polymerization. Thermal analysis elucidated the plant-based polyesters exhibited a single transition, a Tg of about -60 °C. Aliphatic polyesters commonly crystallize, thus the isomeric mixture of secondary alcohols seemed to introduce enough irregularity to prevent crystallization. These polyesters offer an amorphous, biodegradable, sustainable replacement for applications currently using semi-crystalline poly(ε-caprolactone), which is not obtained from renewable monomers and also exhibits a -60 °C Tg. Additional applications requiring low-Tg polymers such as pressure sensitive adhesives or thermoplastic elastomers could also benefit from these novel polyesters. 9-DAME also was transformed into an ABB’ monomer after an epoxidation and subsequent hydrolysis. Successful gelation under melt transesterification conditions provided evidence that the multifunctional monomer could perform as a renewable, biodegradable, branching and/or crosslinking agent. Novel copolyesters comprised of a bromomethyl imidazolium diol and adipic acid demonstrated potential as non-viral gene delivery vectors. Melt polycondensation produced water dispersible polyesters which bound deoxyribonucleic acid at low N/P ratios. The v polyplexes showed stability in water over 24 h and no cytotoxic effect on human cervical cancer cells (HeLa). A luciferase transfection assay revealed the copolyesters successfully underwent endocytosis and released the nucleic acid better than controls. The copolyesters with pendant imidazolium functionality also provided tunable Tgs, -41 °C to 40 °C, and the ability to electrospin into fibers upon blending with poly(ethylene oxide). These additional properties furthered potential applications to include pressure sensitive adhesives and biocompatible antibacterial bandages. / Ph. D.

Mars is one of the most intriguing planets in the solar system. It is the fourth terrestrial planet and is differentiated into a core, mantle and crust. The crust of Mars is divided into the Southern highlands and the Northern lowlands. The largest volcano in the solar system, Olympus Mons is found on the crustal dichotomy boundary. The presence of isolated volcanism on the surface suggests the importance of internal activity on the planet. In addition to volcanism in the past, there has been evidence of present day volcanic activity. Convective upwelling, including decompression melting, has remained an important contributing factor in melting history of the planet. In this thesis, I investigate the production of melt in the mantle for a Newtonian rheology, and compare it with the melt needed to create Tharsis. In addition to the melt production, I analyze the 3D structure of the mantle for a stagnant lithosphere. I vary different parameters in the Martian mantle to understand the production of low or high degree structures early on to explain the crustal dichotomy. This isothermal structure in the mantle contributes to the geoid and topography on the planet. I also analyze how much of the internal density contributes to the surface topography and areoid of Mars. In contrast to Mars, Ceres is a dwarf planet in the Asteroid belt. Ceres is an icy body and it is unclear if it is differentiated into a core, mantle and crust yet. However, studies show that it is most likely a differentiated body and the mantle consists of ice and silicate. The presence of brucite and serpentine on the surface suggests the presence of internal activity. Being a massive body and also believed to have existed since the beginning of the solar system, studying Ceres will shed light on the conditions of the early solar system. Ceres has been of great interest in the scientific community and its importance has motivated NASA to launch a mission, Dawn, to study the planet. Dawn will collect data from the dwarf planet when it arrives in 2015. In my modeling studies, I implement a similar technique on Ceres, as followed on Mars, and focus on the mantle convection process and the geoid and topography. The silicate-ice mixture in the mantle gives rise to a non-Newtonian rheology that depends on the grain size of the ice particle. The geoid and topography observed for different differentiated scenarios in my modeling can be compared with the data from the Dawn mission when it arrives at Ceres in 2015. / Ph. D.

Of all of the bodies in the solar system, Europa is perhaps the most enticing. Based on several lines of evidence, Europa, a moon of Jupiter, is believed to have an ocean of liquid water beneath several kilometers of ice. This ocean is likely in contact with Europa's rocky core, making Europa's ocean one of the most likely places for life to exist in the solar system outside of Earth. This thesis provides an outline of the technology required for a mission that travels to Europa, penetrates the ice, and explores the ocean below. In order to create this outline, this thesis first provides background on previous missions to the outer planets. A discussion of the science requirements is presented and then a value system by which designs are evaluated is developed. Current technologies and the design alternatives are presented and evaluated using the value system. A final mission architecture and concept of operations are then presented. / Master of Science

2-D numerical computer models based on thermodynamic and kinematic principles have become invaluable tools for simulating geodynamic processes at these systems. Numerical models have proven effective for allowing the examination and computation of multiple factors simultaneously, providing scientists with an important resource with which to study complex systems. Previously, for instance, numerical models have been used for examining different factors involved in magma production at subduction zones and mid ocean ridges by modelling the influence and interplay of factors such as the effect of hydration and the influence of the depth of the fault between the two plates on the melting (van Keken, 2003; van Keken 2008). Additional models have explored the thermal structure of subduction zones and its relationship to the processes involved at convergent boundaries, including magma production (van Keken, 2023a). Syracuse et al. (2010) used numerical models for subduction zones, creating thermal models that examined dehydration and melting in subduction zones with a variety of slab geometries, convergence velocities, ages and structures. Still others have shown that thermal structure affects melt production, formation of arc volcanoes, dehydration, and seismicity, modelling the effects of varying slab dip, plate convergence velocity, plate age, etc. (Syracuse et al., 2010; Hayes et al, 2018). However, none have yet utilized models to systematically investigate magma production at either subduction zones or mid-ocean ridges to specifically examine both batch and fractional melting with the combination of multiple controlling factors including slab dip, convergence rate, hydration, minerology, and slab age. This project investigated the processes surrounding magma production at subduction and mid-ocean ridge systems through the creation of a numerical model and utilization of the developed model to explore the effects of a multitude of parameters on fractional and batch melting, as well as investigated the incorporation of incompatible elements, and other processes of interest in subduction and mid ocean ridge systems.

Microfluidics are devices with channels or reservoirs that have dimensions in the range of micrometers. They have an increasing role in biological analysis processes due to their ability to use very small sample volumes. Many microfluidic processes rely heavily on precise temperature measurement and control. Advances in 3D printing have led to high resolution digital light processing stereolithography (DLP-SLA) printers capable of using bio-compatible materials, available at BYU. This custom 3D printer has a resolution of 7.6 µm in the XY plane and 10 µm in the Z axis. Combined with a custom-made resin, we can produce microfluidic features as small as 18 µm x 20 µm. These advances allow for more complex internal geometries with multiple overlapping channels. As the internal geometry becomes more complex, traditional microfluidic temperature measurement tools are limited in their application. This dissertation considers the use of temperature sensitive quantum dots (QDs), nano-scale semiconductor crystals that fluoresce, as an internal temperature measurement tool. This work presents two types of QDs, CdTe and CdSe/ZnS, and their performance as a temperature sensor by relating either photoluminescence peak intensity to temperature or a feed-forward neural network combining multiple features of the fluorescent spectra to temperature. Additionally, 3D printing's ability to create arbitrary 3D structures with an arbitrary 3D orientation, as opposed to traditional microfluidic fabrication methods, enables new three-dimensional heater geometries to be created that provide better internal heat distributions. We present new heater geometries only feasible through 3D printing that can isothermally heat a precisely defined volume. One such design is for a device that can control the temperature of a 5 µL internal chamber to within 0.2°C. This last design is aimed at a new microfluidic device for high resolution DNA melt curve analysis for the detection of single nucleotide polymorphisms. This set of tools we developed will enable the expansion of 3D printed microfluidics beyond the current planar limitations and fluid flow processes into temperature sensitive analyses.

No / Purpose The purpose of the article was to study melt sonocrystallization (MSC) for a drug forming a viscous melt when processed below its glass transition temperature. Methods A molten mass of drug was poured in a vessel containing deionized water, maintained at 40°C using cryostatic bath, and sonicated for 1 min using probe ultrasonicator at an amplitude of 80% and a cycle of 0.8 per second. The product obtained after solidification of dispersed droplets was separated by filtration and dried at room temperature. MSC celecoxib was characterized by solubility determination, scanning electron microscopy, differential scanning calorimetry, X-ray powder diffraction, and stability study. Results The MSC technique was designed for celecoxib, which undergoes fast solidification. The particles obtained by MSC were porous, irregular in shape, and amorphous in nature. An increase in the apparent solubility was observed for the MSC particles. These amorphous particles also exhibited a higher stability in the amorphous state as compared with particles obtained by melt quenching. Conclusions The reported MSC technique for celecoxib demonstrates advantages over other approaches and can be exploited in area of particle design for the amorphization of drugs.

No / Co-crystal screening is routinely undertaken using high-throughput solution growth. We report a low- to medium throughput approach, encompassing both a melt and solution crystallization step as a route to the identification of co-crystals. Prior to solution studies, a melt growth step was included utilizing the Kofler mixed fusion method. This method allowed elucidation of the thermodynamic landscape within the binary phase diagram and was found to increase overall screening efficiency. The pharmaceutically acceptable adduct nicotinamide was selected and screened against a small set of active pharmaceutical ingredients (APIs) (ibuprofen (both the racemic compound (R/S) and S-enantiomer), fenbufen, flurbiprofen (R/S), ketoprofen (R/S), paracetamol, piracetam, and salicylic acid) as part of a larger systematic study of synthon stability. From the screen, three new co-crystal systems have been identified (ibuprofen (R/S and S) and salicylic acid) and their crystal structures determined. Because of poor crystal growth synchrotron radiation was required for structure solution of the S-ibuprofen nicotinamide co-crystal. Two further potential systems have also been discovered (fenbufen and flurbiprofen), but crystals suitable for structure determination have yet to be obtained. A greater ability to control crystallization kinetics is required to yield phase-pure single-crystalline material for full verification of this crystal engineering strategy.

No / Hot melt extrusion is a continuous process with wide industrial applicability. Till current date, there have been no reports on the formulation of extrudates for topical treatment of dermatological diseases. The aim of the present work was to prepare and characterize medicated hot melt extrudates based on Soluplus polymer and nicotinamide, and to explore their applicability in acne treatment. The extrudates were characterized using DSC, FTIR, XRD, and DVS. The extrudates were also tested for their skin adhesion potential, ability to deposit nicotinamide in different skin layers, and their clinical efficacy in acne patients. The 10% nicotinamide extrudates exhibited amorphous nature which was reserved during storage, with no chemical interaction between nicotinamide and Soluplus. Upon contrasting the skin adhesion and drug deposition of extrudates and nicotinamide gel, it was evident that the extrudates displayed significantly higher adhesion and drug deposition reaching 4.8 folds, 5.3 folds, and 4.3 folds more in the stratum corneum, epidermis and dermis, respectively. Furthermore, the extrudates significantly reduced the total number of acne lesions in patients by 61.3% compared to 42.14% with the nicotinamide gel. Soluplus extrudates are promising topical drug delivery means for the treatment of dermatological diseases.