Role of carbon nanotube dispersion in fracture toughening of plasma sprayed aluminum oxide-carbon nanotube nanocomposite coating

Aluminum oxide (Al2O3, or alumina) is a conventional ceramic known for applications such as wear resistant coatings, thermal liners, heaters, crucibles, dielectric systems, etc. However applications of Al 2O3 are limited owing to its inherent brittleness. Due to its excellent mechanical properties and bending strength, carbon nanotubes (CNT) is an ideal reinforcement for Al2O3 matrix to improve its fracture toughness. The role of CNT dispersion in the fracture toughening of the plasma sprayed Al2O3-CNT nanocomposite coating is discussed in the current work. Pretreatment of powder feedstock is required for dispersing CNTs in the matrix. Four coatings namely spray dried Al2O 3 (A-SD), Al2O3 blended with 4wt.% CNT (A4C-B), composite spray dried Al2O3-4wt.% CNT (A4C-SD) and composite spray dried A1203-8wt.% CNT (A8C-SD), are synthesized by plasma spraying. Owing to extreme temperatures and velocities involved in the plasma spraying of ceramics, retention of CNTs in the resulting coatings necessitates optimizing plasma processing parameters using an inflight particle diagnostic sensor. A bimodal microstructure was obtained in the matrix that consists of fully melted and resolidified structure and solid state sintered structure. CNTs are retained both in the fully melted region and solid-state sintered regions of processed coatings. Fracture toughness of A-SD, A4C-B, A4C-SD and A8C-SD coatings was 3.22, 3.86, 4.60 and 5.04 MPa m1/2 respectively. This affirms the improvement of fracture toughness from 20% (in A4C-B coating) to 43% (in A4C-SD coating) when compared to the A-SD coating because of the CNT dispersion. Fracture toughness improvement from 43% (in A4C-SD) to 57% (in A8C-SD) coating is evinced because of the CNT content. Reinforcement by CNTs is described by its bridging, anchoring, hook formation, impact alignment, fusion with splat, and mesh formation. The Al2O3/CNT interface is critical in assisting the stress transfer and utilizing excellent mechanical properties of CNTs. Mathematical and computational modeling using ab-initio principle is applied to understand the wetting behavior at the Al2O 3/CNT interface. Contrasting storage modulus was obtained by nanoindentation (∼210, 250, 250-350 and 325-420 GPa in A-SD, A4C-B, A4C-SD, and A8C-SD coatings respectively) depicting the toughening associated with CNT content and dispersion.

Synthesis of M2AC (M = Ti, V, Cr, Nb, Zr, A = Al, Sn, S) (MAX) carbide phases and study of their physical behavior under extreme conditions

Materials known as Mn+1AXn phases, where n is 1, 2, or 3, and M represents an early transition metal, A an A-group element, and X is either Carbon and/or Nitrogen [1], are fast becoming technologically important materials due to the interesting combination of unique properties. However, a lot of important information about the high temperature and high pressure behavior of many of these compounds is still missing, which needs to be determined systematically. ^ In this dissertation the synthesis of M2AC (M = Ti, V, Cr, Nb, Zr) and A = (Al, Sn, S) compounds by arc melting, vacuum sintering and piston cylinder synthesis is presented along with the synthesis of Zr 2SC, which has been synthesized for first time in bulk form, by piston cylinder technique. The microstructural analysis by electron microscopy and phase analysis by x-ray diffraction is presented next. Finally, a critical analysis of the behavior of these compounds under the application of extreme pressure (as high as 50 GPa) and temperature (≈ 1000°C) is presented. ^ The high pressure studies, up to 50 GPa, showed that these compounds were structurally intact and their bulk moduli ranged from 140 to 190 GPa. The high temperature studies in the inert atmosphere showed that the M 2SnC compounds were unstable above 650°C and the expansion along the a-axis was higher than that along the c-axis, unlike the other phases. M2SC compounds on the other hand showed negligible difference in the thermal expansion along the two axes. The oxidation study revealed that Ti2AC (Al, S) compounds had highest resistance to oxidation while the M2SnC compounds had the least. Furthermore, from the oxidation study of these compounds, which were short time oxidation experiments, it was found that all of these compounds oxidized to their respective binary oxides. ^

Melanocytes in the developing and adult atrioventricular valves of the murine heart

The Neural Crest (NC) is a multipotential group of cells that arises from the dorsal aspect of the neural tube early in development. It is well established that a group of NC cells named Cardiac Neural Crest (CNC) migrates to the heart and plays a critical role in the remodeling of the aortic arch arteries and septation of the outflow tract. In this study, using the mouse mutant Pax3sp/sp that has CNC deficits I have identified a putative novel role for the CNC in regulating apoptosis in the atrioventricular (AV) endocardial cushion. The AV endocardial cushion undergoes remodeling to give rise to the cardiac AV valves. Using a transgenic mouse that carries the LacZ reporter gene under the control of the Dopachrome tautomerase promoter (Dct-LacZ), I found that another NC derived population, melanocyte precursors, also contribute to the AV endocardial cushion and developing AV valves. The analysis of Dct-LacZ embryos at different stages showed that NC cells already committed to the melanocytic fate migrate to the heart along the same initial pathway taken by those that will populate the skin. Hypopigmented mice carrying mutations in the Kit and Endothelin receptor b genes, that are critical for the proper development of skin melanocytes, do not have cardiac melanocytes indicating that cardiac and skin melanocyte precursors share the same initial signaling requirements. The analysis of murine adult hearts showed that melanocytes are mostly found in the atrial sides of the tricuspid and mitral valve leaflets. The distribution of melanocytes in the AV valves corresponds exactly to areas of high Versican B expression, a proteoglycan essential for the process of AV valve remodeling. To evaluate a potential role for melanocytes in the AV valves, a nanoindentation analysis of the tricuspid valves of wild type, hypopigmented and hyperpigmented mice was performed. The storage modulus, a measure of stiffness, for the leaflets obtained from hyperpigmented mice was considerably higher (10.5GPa) than that for the leaflets from wild type (7.5GPa) and hypopigmented animals (between 3.5 and 5.5 GPa) suggesting that melanocytes may contribute to the mechanical properties of the AV valves.

Cognitive and noncognitive variables that predict Florida community college radiography program graduates' success on the Registry

This study examined the predictive merits of selected cognitive and noncognitive variables on the national Registry exam pass rate using 2008 graduates (n = 175) from community college radiography programs in Florida. The independent variables included two GPAs, final grades in five radiography courses, self-efficacy, and social support. The dependent variable was the first-attempt results on the national Registry exam. The design was a retrospective predictive study that relied on academic data collected from participants using the self-report method and on perceptions of students' success on the national Registry exam collected through a questionnaire developed and piloted in the study. All independent variables except self-efficacy and social support correlated with success on the national Registry exam ( p < .01) using the Pearson Product-Moment Correlation analysis. The strongest predictor of the national Registry exam success was the end-of-program GPA, r = .550, p < .001. The GPAs and scores for self-efficacy and social support were entered into a logistic regression analysis to produce a prediction model. The end-of-program GPA (p = .015) emerged as a significant variable. This model predicted 44% of the students who failed the national Registry exam and 97.3% of those who passed, explaining 45.8% of the variance. A second model included the final grades for the radiography courses, self efficacy, and social support. Three courses significantly predicted national Registry exam success; Radiographic Exposures, p < .001; Radiologic Physics, p = .014; and Radiation Safety & Protection, p = .044, explaining 56.8% of the variance. This model predicted 64% of the students who failed the national Registry exam and 96% of those who passed. The findings support the use of in-program data as accurate predictors of success on the national Registry exam.

Explaining the effects of class size on faculty and students

This study explored the effects of class size on faculty and students. Specifically, it examined the relationship of class size and students' participation in class, faculty interactive styles, and academic environment and how these behaviors affected student achievement (percentage of students passing). The sample was composed of 629 students in 30 sections of Algebra I at a large, urban community college. A survey was administered to the students to solicit their perceptions on their participation in class, their faculty interaction style, and the academic environment in their classes. Selected classes were observed to triangulate the findings. The relationship of class size to student participation, faculty interactive styles, and academic environment was determined by using hierarchical linear modeling (HLM). A significant difference was found on the participation of students related to class size. Students in smaller classes participated more and were more engaged than students in larger classes. Regression analysis using the same variables in small and large classes showed that faculty interactive styles significantly predicted student achievement. Stepwise regression analyses of student and faculty background variables showed that (a) students' estimate of GPA was significantly related to their achievement (r = .63); (b) older students reported more participation than did younger ones, (c) students in classes taught by female, Hispanic faculty earned higher passing grades, and (d) students' participation was greater with adjunct professors. Class observations corroborated these findings. The analysis and observational data provided sufficient evidence to warrant the conclusion that small classes were not always most effective in promoting achievement. It was found that small classes may be an artifact of ineffectual teaching, actual or by reputation. While students in small classes participate and are more engaged than students in larger classes, the class-size effect is essentially due to what happens in instruction to promote learning. The interaction of the faculty with students significantly predicted students' achievement regardless of class size. Since college students select their own classes, students do not register for classes taught by faculty with poor teaching reputation, thereby leading to small classes. Further studies are suggested to determine reasons why classes differ in size.

High pressure studies on group VI metal hexacarbonyl molecular solids

Group VI metal hexacarbonyls, M(CO)6 (M = Cr, Mo and W), are of extreme importance as catalysts in industry and also of fundamental interest due to the established charge transfer mechanism between the carbon monoxide and the metal. They condense to molecular solids at ambient conditions retaining the octahedral (Oh) symmetry of gas phase and have been extensively investigated by previous workers to understand their fundamental chemical bonding and possible industrial applications. However little is known about their behavior at high pressures which is the focus of this dissertation. Metal hexacarbonyls were subjected to high pressures in Diamond-Anvil cells to understand the pressure effect on chemical bonding using Raman scattering in situ. The high-pressure results on each of the three metal hexacarbonyls are presented and are followed by a critical analysis of the entire family. The Raman study was conducted at pressures up to 45 GPa and X-ray up to 58 GPa. This is followed by a discussion on infra red spectra in conjunction with Raman and X-ray analysis to provide a rationale for polymerization. Finally the probable synthesis of extremely reactive species under high-pressures and as identified via Raman is discussed. The high-pressure Raman scattering, up to 30 GPa, demonstrated the absence of Π-backbonding. The disappearance of parental Raman spectra for (M = Cr, Mo and W) at 29.6, 23.3 and 22.2 GPa respectively was attributed to the total collapse of the Oh symmetry. This collapse under high-pressure lead to metal-mediated polymeric phase characterized by Raman active δ(OCO) feature, originating from intermolecular vibrational coupling in the parent sample. Further increase in pressures up to 45 GPa, did not affect this feature. The pressure quenched Raman spectra, revealed various chemical groups non-characteristic of the parent sample and adsorption of CO in addition to the characteristic δ(OCO) feature. The thus recorded Raman, complemented with the far and mid-infrared pressure quenched spectra, reveal the formation of novel metal-mediated polymers. The X-ray diffraction on W(CO)6 up to 58 GPa revealed the generation of amorphous polymeric pattern which was retained back to ambient conditions.

Investigation of Mantle Dynamics from Platinum Group Elements and Rhenium-Osmium Isotope Systematics of Mantle Xenoliths from Oahu, Hawaii

Intraplate volcanism that has created the Hawaiian-Emperor seamount chain is generally thought to be formed by a deep-seated mantle plume. While the idea of a Hawaiian plume has not met with substantial opposition, whether or not the Hawaiian plume shows any geochemical signal of receiving materials from the Earth’s Outer Core and how the plume may or may not be reacting with the overriding lithosphere remain debatable issues. In an effort to understand how the Hawaiian plume works I report on the first in-situ sulfides and bulk rock Platinum Group Element (PGE) concentrations, together with Os isotope ratios on well-characterized garnet pyroxenite xenoliths from the island of Oahu in Hawaii. The sulfides are Fe-Ni Monosulfide Solid Solution and show fractionated PGE patterns. Based on the major elements, Platinum Group Elements and experimental data I interpret the Hawaiian sulfides as an immiscible melt that separated from a melt similar to the Honolulu Volcanics (HV) alkali lavas at a pressure-temperature condition of 1530 ± 100OC and 3.1±0.6 GPa., i.e. near the base or slightly below the Pacific lithosphere. The 187Os/188Os ratios of the bulk rock vary from subchondritic to suprachondritic (0.123-0.164); and the 187Os/188Os ratio strongly correlates with major element, High Field Strength Element (HFSE), Rare Earth Element (REE) and PGE abundances. These correlations strongly suggest that PGE concentrations and Os isotope ratios reflect primary mantle processes. I interpret these correlations as the result of melt-mantle reaction at the base of the lithosphere: I suggest that the parental melt that crystallized the pyroxenites selectively picked up radiogenic Os from the grain boundary sulfides, while percolating through the Pacific lithosphere. Thus the sampled pyroxenites essentially represent crystallized melts from different stages of this melt-mantle reaction process at the base of the lithosphere. I further show that the relatively low Pt/Re ratios of the Hawaiian sulfides and the bulk rock pyroxenites suggest that, upon ageing, such pyroxenites plus their sulfides cannot generate the coupled 186Os- 187Os isotope enrichments observed in Hawaiian lavas. Therefore, recycling of mantle sulfides of pyroxenitic parentage is unlikely to explain the enriched Pt-Re-Os isotope systematics of plume-derived lavas.

GRE as a predictor of graduate student success at a Hispanic serving institution of higher education

Accurately predicting the success of graduate students is an important aspect of determining which students should be admitted into graduate programs. The GRE is a pivotal factor to examine since it is one of the most widely used criteria for graduate school admission. Even though the GRE is advertised as an accurate tool for predicting first year graduate GPA, there is a lack of research on long term success factors such as time to degree and graduate rate (Luthy, 1996; Powers, 2004). Furthermore, since most studies have low minority sample sizes, the validity of the GRE may not be the same across all groups (ETS, 2008b; Kuncel, Hezlett, & Ones, 2001). Another gap in GRE studies is that few researchers analyze student characteristics, which may alter or moderate the prediction validity of the GRE. Thus, student characteristics such as degree of academic involvement, mentorship interactions, and other academic and social experiences have not been widely examined in this context. These gaps in the analysis of GRE validity are especially relevant given the high attrition rates within of some graduate programs (e.g., an estimated 68% of doctoral student never complete their programs in urban universities; Lovitts, 2001). A sequential mixed methods design was used to answer the research questions in two phases. The quantitative phase used student data files to analyze the relationship of two success variables (graduation rate and graduate GPA) to the GRE scores as well as other academic and demographic graduate student characteristics. The qualitative phase served to complement the first phase by describing a wider range of characteristics from the 11 graduate students who were interviewed. Both proximal and distal moderators influence student behaviors and success in graduate school. In the first phase of the study, the GRE was the distal facilitator under analysis. Findings suggested that both the GRE Quantitative and the GRE Verbal were predictors of success for master’s students, but the GRE Quantitative was not predictive of success for doctoral students. Other student characteristics such as demographic variables and disciplinary area were also predictors of success for the population of students studied. In the second phase of the study, it was inconclusive whether the GRE was predictive of graduate student success; though it did influence access to graduate programs. Furthermore, proximal moderators such as student involvement, faculty/peer interactions, motivational factors, and program structure were perceived to be facilitators and/or detractors for success.

Development of an instrument to measure high school students' global awareness and attitudes: Looking through the lens of social sciences

The purpose of this study was to develop an instrument to measure high school students’ perspectives on global awareness and attitudes toward social issues. The research questions that guided this study were: (a) Can acceptable validity and reliability estimates be established for an instrument developed to measure high schools students' global awareness? (b) Can acceptable validity and reliability estimates be established for an instrument developed to measure high schools students' attitudes towards global social issues? (c) What is the relationship between high school students’ GPA, race/ethnicity, gender, socio-economic status, parents’ education, getting the news, reading and listening habits, the number of classes taken in the social sciences, whether they speak a second language, and have experienced living in or visiting other countries, and their perception of global awareness and attitudes toward global social issues. ^ An ex post facto research design was used and the data were collected using a 4-part Likert-type survey. It was administered to 14 schools in the Miami-Dade County, Florida area to 704 students. A factor analysis with an orthogonal varimax rotation was vii used to select the factors that best represented the three constructs – global education, global citizenship, and global workforce. This was done to establish construct validity. Cronbach’s alpha was used to determine the reliability of the instrument. Descriptive statistics and a hierarchical multiple regression were used for the demographics to establish their relationship, if any, to the findings. ^ Key findings of the study were that reliable and valid estimates can be developed for the instrument. The multiple regression analysis for model 1 and 2 accounted for a variance of 3% and 5% for self-perceptions of global awareness (factor 1). The regression model also accounted for a 5% and 13% variance in the two models for attitudes toward global social issues (factor 2). The demographics that were statistically significant were: ethnicity, gender, SES, parents’ education, listening to music, getting the news, speaking a second language, GPA, classes taken in the social sciences, and visiting other countries. An important finding for the study was those attending public schools (as opposed to private schools) had more positive attitudes towards global social issues (factor 2) The statistics indicated that these students had taken history, economics, and social studies – a curriculum infused with global perspectives.^

The relationship between a retention program and the persistence and graduation rates of first-generation low-income students at an urban, public university

The purpose of this study was to examine the relationship between participation in a retention program designed to promote academic and social integration and the persistence rates of first generation, low-income college students at an urban, public multiethnic university. Archival data were collected from the university’s Office of Institutional Research and the retention program office and included SAT/ACT scores, GPA, gender, ethnicity, and program participation data. A total of 292 first-generation, low-income students who were admitted to the university in the summer of 1999 were identified for the study. A group of 166 students were selected for the comparison group because they had not participated in the retention program; 126 students had participated in the retention program. ^ Three major research questions guided this study: (a) Are there differences in persistence rates and other academic characteristics of underprepared, low-income, first generation college students who participate and do not participate in the retention program?; (b) Does involvement in the retention program predict student persistence of first generation low-income, underprepared students?, and (c) Can predictors of GPA be identified for students in the retention program using program and descriptive variables? ^ A series of logistic regression analyses were conducted to assess the relationship between various retention services and the persistence and graduation rates of participants. The results showed that there were statistically significant relationships between participation and non-participation in the retention program and having higher GPAs and higher graduation and persistence rates. Of the four program features, participation in tutoring, workshops, and social events were found to be predictors of graduation. College GPA was also found to be a predictor of graduation for all students. The results also showed that women were more likely to graduate than men.^

The role of emotional intelligence in college students' success

The purpose of this study was to determine if higher academic performance was positively correlated to higher emotional intelligence among traditional age male and female college students enrolled in an Introduction to Business course at a large multi-campus state college in Florida. The Bar-On 2004 (Emotional Quotient Inventory) EQ-i 133-item inventory was used to assess students’ emotional intelligence. Within the scope of this ex-post facto study, a quasi-experimental design was included to further determine if emotional intelligence could be increased through the inclusion of a curricular component on emotional intelligence. Four groups of students (N=111) participated in the three-phase study over two semesters. The first phase (pre-intervention) was limited to students with an established GPA and an attempted-to-completed credit hour ratio within the institution (N=82). Results showed a slight positive correlation between the two factors and the students’ emotional intelligence pretest assessment scores. The second phase of the study involved establishing a control and an experimental group in each of two semesters to compare the attainment of overall emotional intelligence scores as measured by the EQ-i. The third phase of the study examined four measures of academic success (GPA, the attempted-to-completed credit hour ratio, grade in the business course, and persistence in college) to determine if these factors were positively correlated with the students’ posttest EQ-i scores. The study also included a research question to determine if significant differences in overall EQ-i scores existed between male and female students during the three phases. Findings from the study indicated that (a) there was a slight positive correlation in the pre-intervention stage between emotional intelligence and traditional measures of academic success specifically, GPA and the attempted-to-completed credit hour ratio; (b) curricular intervention made a significant difference at the p <.05 level, with an .5 effect size, in one semester but failed to meet that threshold in the following semester with the second pair of groups; (c) at the post-intervention phase, the four measures of traditional academic success yielded a low positive correlation with the students’ emotional intelligence assessment scores, and (d) female students showed significant gains in their overall EQ-i scores.

Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

Predictors of success: Medical Laboratory Associate in Science Degree Program

Hospitals and healthcare facilities in the United States are facing serious shortages of medical laboratory personnel, which, if not addressed, stand to negatively impact patient care. The problem is compounded by a reduction in the numbers of academic programs and resulting decrease in the number of graduates to keep up with the increase in industry demands. Given these challenges, the purpose of this study was to identify predictors of success for students in a selected 2-year Medical Laboratory Technology Associate in Science Degree Program. ^ This study examined five academic factors (College Placement Test Math and Reading scores, Cumulative GPA, Science GPA, and Professional [first semester laboratory courses] GPA) and, demographic data to see if any of these factors could predict program completion. The researcher examined academic records for a 10-year period (N =158). Using a retrospective model, the correlational analysis between the variables and completion revealed a significant relationship (p < .05) for CGPA, SGPA, CPT Math, and PGPA indicating that students with higher CGPA, SGPA, CPT Math, and PGPA were more likely to complete their degree in 2 years. Binary logistic regression analysis with the same academic variables revealed PGPA was the best predictor of program completion (p < .001). ^ Additionally, the findings in this study are consistent with the academic part of the Bean and Metzner Conceptual Model of Nontraditional Student Attrition which points to academic outcome variables such as GPA as affecting attrition. Thus, the findings in this study are important to students and educators in the field of Medical Laboratory Technology since PGPA is a predictor that can be used to provide early in-program intervention to the at-risk student, thus increasing the chances of successful timely completion.^