Understanding the Reaction Mechanism of Nanocomposite Thermites

Nanocomposite energetics are a relatively new class of materials that combine nanoscale fuels and oxidizers to allow for the rapid release of large amounts of energy. In thermite systems (metal fuel with metal oxide oxidizer), the use of nanomaterials has been illustrated to increase reactivity by multiple orders of magnitude as a result of the higher specific surface area and smaller diffusion length scales. However, the highly dynamic and nanoscale processes intrinsic to these materials, as well as heating rate dependencies, have limited our understanding of the underlying processes that control reaction and propagation. For my dissertation, I have employed a variety of experimental approaches that have allowed me to probe these processes at heating rates representative of free combustion with the goal of understanding the fundamental mechanisms. Dynamic transmission electron microscopy (DTEM) was used to study the in situ morphological change that occurs in nanocomposite thermite materials subjected to rapid (10^11 K/s) heating. Aluminum nanoparticle (Al-NP) aggregates were found to lose their nanostructure through coalescence in as little as 10 ns, which is much faster than any other timescale of combustion. Further study of nanoscale reaction with CuO determined that a condensed phase interfacial reaction could occur within 0.5-5 µs in a manner consistent with bulk reaction, which supports that this mechanism plays a dominant role in the overall reaction process. Ta nanocomposites were also studied to determine if a high melting point (3280 K) affects the loss of nanostructure and rate of reaction. The condensed phase reaction pathway was further explored using reactive multilayers sputter deposited onto thin Pt wires to allow for temperature jump (T-Jump) heating at rates of ~5x10^5 K/s. High speed video and a time of flight mass spectrometry (TOFMS) were used to observe ignition temperature and speciation as a function of bilayer thickness. The ignition process was modeled and a low activation energy for effective diffusivity was determined. T-Jump TOFMS along with constant volume combustion cell studies were also used to determine the effect of gas release in nanoparticle systems by comparing the reaction properties of CuO and Cu2O.

ENERGETIC BIOCIDAL MATERIALS AND SPORE NEUTRALIZATION

The objective of this dissertation is to explore a more accurate and versatile approach to investigating the neutralization of spores suffered from ultrafast heating and biocide based stresses, and further to explore and understand novel methods to supply ultrafast heating and biocides through nanostructured energetic materials A surface heating method was developed to apply accurate (± 25 ˚C), high heating rate thermal energy (200 - 800 ˚C, ~103 - ~105 ˚C/s). Uniform attachment of bacterial spores was achieved electrophoretically onto fine wires in liquids, which could be quantitatively detached into suspension for spore enumeration. The spore inactivation increased with temperature and heating rate, and fit a sigmoid response. The neutralization mechanisms of peak temperature and heating rate were correlated to the DNA damage at ~104 ˚C/s, and to the coat rupture by ultrafast vapor pressurization inside spores at ~105 ˚C/s. Humidity was found to have a synergistic effect of rapid heating and chlorine gas to neutralization efficiency. The primary neutralization mechanism of Cl2 and rapid heat is proposed to be chlorine reacting with the spore surface. The stress-kill correlation above provides guidance to explore new biocidal thermites, and to probe mechanisms. Results show that nano-Al/K2S2O8 released more gas at a lower temperature and generated a higher maximum pressure than the other nano-Al/oxysalts. Given that this thermite formulation generates the similar amount of SO2 as O2, it can be considered as a potential candidate for use in energetic biocidal applications. The reaction mechanisms of persulfate and other oxysalts containing thermites can be divided into two groups, with the reactive thermites (e.g. Al/K2S2O8) that generate ~10× higher of pressure and ~10× shorter of burn time ignited via a solid-gas Al/O2 reaction, while the less reactive thermites (e.g. Al/K2SO4) following a condensed phase Al/O reaction mechanism. These different ignition mechanisms were further re-evaluated by investigating the roles of free and bound oxygen. A constant critical reaction rate for ignition was found which is independent to ignition temperature, heating rate and free vs. bound oxygen.

An Analysis of the Implementation and Perceived Effectiveness of the SchoolMAX Family Portal

ABSTRACT Title of Document: AN ANALYSIS OF THE IMPLEMENTATION AND PERCEIVED EFFECTIVENESS OF THE SCHOOLMAX FAMILY PORTAL Warren Wesley Watts, Doctor of Education, 2015 Directed By: Margaret J. McLaughlin, Ph.D. Department of Counseling, Higher Education and Special Education School districts have spent millions of dollars implementing student information systems that offer family portals with web-based access to parents and students. One of the main purposes of these systems is to improve school-to-home communication. Research has shown that when school-to-home communication is implemented effectively, parent involvement improves and student achievement increases (Epstein, 2001). The purpose of the study was to (a) understand why parents used or refrained from using the family portal and (b) determine what barriers to use might exist. To this end, this descriptive study identified the information parent users accessed in the SchoolMAX family portal, determined how frequently parents accessed the portal, and ascertained whether parents perceived an increase in communication with their children about academic matters after they began accessing the portal. Finally, the study sought to identify whether barriers existed that prevented parents from using the family portal. The inquiry employed three data sources to answer the aforementioned queries. These sources included (a) a survey sent electronically to 19,108 parents who registered online for the SchoolMAX family portal; (b) SchoolMAX portal usage data from the student information system for system usage between January 1, 2015 and June 30, 2015; and (c) a paper survey sent to 691 parents of students that had never used the SchoolMAX family portal in one elementary school, one middle school and one high school that were representative of other schools in the district. Survey results indicated that parents at all grade levels used the family portal. Usage data also confirmed that approximately 19% of the students had parents who monitored their progress through the family portal. Usage data also showed that parents were monitoring approximately 25% of students in secondary schools (6th – 12th grade) and 16% of students in elementary schools. Of the wide menu of resources available through the SchoolMAX family portal, parents used three areas most frequently: attendance, daily grades, and report cards. Approximately 70% of parents responded that their communication had improved with their children about academic matters since they started using the SchoolMAX family portal, and 90% of parents responded that the SchoolMAX family portal was an effective or somewhat effective tool. Parents also expressed interest in the addition of additional information to the SchoolMAX family portal. Specifically, the top three additions parents wanted to see included homework assignments, high stakes test scores, and graduation requirements. Parents also reported that 92% of them spoke to their children at least 2 to 3 times per week about academics. Due to the low response rate of the parent non-user survey, potential barriers to using the SchoolMAX family portal could not be addressed in this study. However, this issue may be a useful research topic in a future study. Keywords: school to home communication, student information systems, family portal, parent portal