Reaction Control in Quiescent Systems of Free-Radical Retrograde-Precipitation Polymerization

Free-radical retrograde-precipitation polymerization, FRRPP in short, is a novel polymerization process discovered by Dr. Gerard Caneba in the late 1980s. The current study is aimed at gaining a better understanding of the reaction mechanism of the FRRPP and its thermodynamically-driven features that are predominant in controlling the chain reaction. A previously developed mathematical model to represent free radical polymerization kinetics was used to simulate a classic bulk polymerization system from the literature. Unlike other existing models, such a sparse-matrix-based representation allows one to explicitly accommodate the chain length dependent kinetic parameters. Extrapolating from the past results, mixing was experimentally shown to be exerting a significant influence on reaction control in FRRPP systems. Mixing alone drives the otherwise severely diffusion-controlled reaction propagation in phase-separated polymer domains. Therefore, in a quiescent system, in the absence of mixing, it is possible to retard the growth of phase-separated domains, thus producing isolated polymer nanoparticles (globules). Such a diffusion-controlled, self-limiting phenomenon of chain growth was also observed using time-resolved small angle x-ray scattering studies of reaction kinetics in quiescent systems of FRRPP. Combining the concept of self-limiting chain growth in quiescent FRRPP systems with spatioselective reaction initiation of lithography, microgel structures were synthesized in a single step, without the use of molds or additives. Hard x-rays from the bending magnet radiation of a synchrotron were used as an initiation source, instead of the more statistally-oriented chemical initiators. Such a spatially-defined reaction was shown to be self-limiting to the irradiated regions following a polymerization-induced self-assembly phenomenon. The pattern transfer aspects of this technique were, therefore, studied in the FRRP polymerization of N-isopropylacrylamide (NIPAm) and methacrylic acid (MAA), a thermoreversible and ionic hydrogel, respectively. Reaction temperature increases the contrast between the exposed and unexposed zones of the formed microgels, while the irradiation dose is directly proportional to the extent of phase separation. The response of Poly (NIPAm) microgels prepared from the technique described in this study was also characterized by small angle neutron scattering.

Technique to measure heats of reaction of Ti-B, Al-Ti-B, and Al-Ti-B4C powder blends

In this research, a modification to initiation aid ignition in bomb calorimetry that involves systemically blending levels of boron and potassium nitrate initiation aids with a bulk structural energetic elemental power blend is developed. A regression is used to estimate the nominal heat of reaction for the primary reaction. The technique is first applied to the synthesis of TiB2 as a validation study to see if close proximity to literature values can be achieved. The technique is then applied to two systems of interest, Al-Ti-B, and Al-Ti-B4C. In all three investigations, x-ray diffraction is used to characterize the product phases of the reactions to determine the extent and identity of the product phases and any by-products that may have formed as a result of adding the initiation aid. The experimental data indicates the technique approximates the heat of reaction value for the synthesis of TiB2 from Ti-B powder blends and the formation of TiB2 is supported by volume fraction analysis by x-ray diffraction. Application to the Al-Ti-B and Al-Ti-B4C blends show some correlation with variation of the initiation aid, with x-ray diffraction showing the formation of equilibrium products. However, these blends require further investigation to resolve more complex interactions and rule out extraneous variables.

Dynamics of settling charged particles in turbulence : theory and experiments

It has been proposed that inertial clustering may lead to an increased collision rate of water droplets in clouds. Atmospheric clouds and electrosprays contain electrically charged particles embedded in turbulent flows, often under the influence of an externally imposed, approximately uniform gravitational or electric force. In this thesis, we present the investigation of charged inertial particles embedded in turbulence. We have developed a theoretical description for the dynamics of such systems of charged, sedimenting particles in turbulence, allowing radial distribution functions to be predicted for both monodisperse and bidisperse particle size distributions. The governing parameters are the particle Stokes number (particle inertial time scale relative to turbulence dissipation time scale), the Coulomb-turbulence parameter (ratio of Coulomb ’terminalar speed to turbulence dissipation velocity scale), and the settling parameter (the ratio of the gravitational terminal speed to turbulence dissipation velocity scale). For the monodispersion particles, The peak in the radial distribution function is well predicted by the balance between the particle terminal velocity under Coulomb repulsion and a time-averaged ’drift’ velocity obtained from the nonuniform sampling of fluid strain and rotation due to finite particle inertia. The theory is compared to measured radial distribution functions for water particles in homogeneous, isotropic air turbulence. The radial distribution functions are obtained from particle positions measured in three dimensions using digital holography. The measurements support the general theoretical expression, consisting of a power law increase in particle clustering due to particle response to dissipative turbulent eddies, modulated by an exponential electrostatic interaction term. Both terms are modified as a result of the gravitational diffusion-like term, and the role of ’gravity’ is explored by imposing a macroscopic uniform electric field to create an enhanced, effective gravity. The relation between the radial distribution functions and inward mean radial relative velocity is established for charged particles.

STATE-AND-TRANSITION MODELING AND ADAPTIVE MANAGEMENT: TOOLS FOR FUTURE CO-DEVELOPMENT OF MADAGASCAR’S NATURAL RESOURCES AND PEOPLE

Madagascar’s terrestrial and aquatic ecosystems have long supported a unique set of ecological communities, many of whom are endemic to the tropical island. Those same ecosystems have been a source of valuable natural resources to some of the poorest people in the world. Nevertheless, with pride, ingenuity and resourcefulness, the Malagasy people of the southwest coast, being of Vezo identity, subsist with low development fishing techniques aimed at an increasingly threatened host of aquatic seascapes. Mangroves, sea grass bed, and coral reefs of the region are under increased pressure from the general populace for both food provisions and support of economic opportunity. Besides purveyors and extractors, the coastal waters are also subject to a number of natural stressors, including cyclones and invasive, predator species of both flora and fauna. In addition, the aquatic ecosystems of the region are undergoing increased nutrient and sediment runoff due, in part, to Madagascar’s heavy reliance on land for agricultural purposes (Scales, 2011). Moreover, its coastal waters, like so many throughout the world, have been proven to be warming at an alarming rate over the past few decades. In recognizing the intimate interconnectedness of the both the social and ecological systems, conservation organizations have invoked a host of complimentary conservation and social development efforts with the dual aim of preserving or restoring the health of both the coastal ecosystems and the people of the region. This paper provides a way of thinking more holistically about the social-ecological system within a resiliency frame of understanding. Secondly, it applies a platform known as state-and-transition modeling to give form to the process. State-and-transition modeling is an iterative investigation into the physical makeup of a system of study as well as the boundaries and influences on that state, and has been used in restorative ecology for more than a decade. Lastly, that model is sited within an adaptive management scheme that provides a structured, cyclical, objective-oriented process for testing stakeholders cognitive understanding of the ecosystem through a pragmatic implementation and monitoring a host of small-scale interventions developed as part of the adaptive management process. Throughout, evidence of the application of the theories and frameworks are offered, with every effort made to retool conservation-minded development practitioners with a comprehensive strategy for addressing the increasingly fragile social-ecological systems of southwest Madagascar. It is offered, in conclusion, that the seascapes of the region would be an excellent case study worthy of future application of state-and-transition modeling and adaptive management as frameworks for conservation-minded development practitioners whose multiple projects, each with its own objective, have been implemented with a single goal in mind: preserve and protect the state of the supporting environment while providing for the basic needs of the local Malagasy people.