Plasma and cold sprayed aluminum carbon nanotube composites: Quantification of nanotube distribution and multi-scale mechanical properties

Carbon nanotubes (CNT) could serve as potential reinforcement for metal matrix composites for improved mechanical properties. However dispersion of carbon nanotubes (CNT) in the matrix has been a longstanding problem, since they tend to form clusters to minimize their surface area. The aim of this study was to use plasma and cold spraying techniques to synthesize CNT reinforced aluminum composite with improved dispersion and to quantify the degree of CNT dispersion as it influences the mechanical properties. Novel method of spray drying was used to disperse CNTs in Al-12 wt.% Si prealloyed powder, which was used as feedstock for plasma and cold spraying. A new method for quantification of CNT distribution was developed. Two parameters for CNT dispersion quantification, namely Dispersion parameter (DP) and Clustering Parameter (CP) have been proposed based on the image analysis and distance between the centers of CNTs. Nanomechanical properties were correlated with the dispersion of CNTs in the microstructure. Coating microstructure evolution has been discussed in terms of splat formation, deformation and damage of CNTs and CNT/matrix interface. Effect of Si and CNT content on the reaction at CNT/matrix interface was thermodynamically and kinetically studied. A pseudo phase diagram was computed which predicts the interfacial carbide for reaction between CNT and Al-Si alloy at processing temperature. Kinetic aspects showed that Al4C3 forms with Al-12 wt.% Si alloy while SiC forms with Al-23wt.% Si alloy. Mechanical properties at nano, micro and macro-scale were evaluated using nanoindentation and nanoscratch, microindentation and bulk tensile testing respectively. Nano and micro-scale mechanical properties (elastic modulus, hardness and yield strength) displayed improvement whereas macro-scale mechanical properties were poor. The inversion of the mechanical properties at different scale length was attributed to the porosity, CNT clustering, CNT-splat adhesion and Al 4C3 formation at the CNT/matrix interface. The Dispersion parameter (DP) was more sensitive than Clustering parameter (CP) in measuring degree of CNT distribution in the matrix.

Plasma And Cold Sprayed Aluminum Carbon Nanotube Composites: Quantification Of Nanotube Distribution And Multi-Scale Mechanical Properties

Carbon nanotubes (CNT) could serve as potential reinforcement for metal matrix composites for improved mechanical properties. However dispersion of carbon nanotubes (CNT) in the matrix has been a longstanding problem, since they tend to form clusters to minimize their surface area. The aim of this study was to use plasma and cold spraying techniques to synthesize CNT reinforced aluminum composite with improved dispersion and to quantify the degree of CNT dispersion as it influences the mechanical properties. Novel method of spray drying was used to disperse CNTs in Al-12 wt.% Si pre-alloyed powder, which was used as feedstock for plasma and cold spraying. A new method for quantification of CNT distribution was developed. Two parameters for CNT dispersion quantification, namely Dispersion parameter (DP) and Clustering Parameter (CP) have been proposed based on the image analysis and distance between the centers of CNTs. Nanomechanical properties were correlated with the dispersion of CNTs in the microstructure. Coating microstructure evolution has been discussed in terms of splat formation, deformation and damage of CNTs and CNT/matrix interface. Effect of Si and CNT content on the reaction at CNT/matrix interface was thermodynamically and kinetically studied. A pseudo phase diagram was computed which predicts the interfacial carbide for reaction between CNT and Al-Si alloy at processing temperature. Kinetic aspects showed that Al4C3 forms with Al-12 wt.% Si alloy while SiC forms with Al-23wt.% Si alloy. Mechanical properties at nano, micro and macro-scale were evaluated using nanoindentation and nanoscratch, microindentation and bulk tensile testing respectively. Nano and micro-scale mechanical properties (elastic modulus, hardness and yield strength) displayed improvement whereas macro-scale mechanical properties were poor. The inversion of the mechanical properties at different scale length was attributed to the porosity, CNT clustering, CNT-splat adhesion and Al4C3 formation at the CNT/matrix interface. The Dispersion parameter (DP) was more sensitive than Clustering parameter (CP) in measuring degree of CNT distribution in the matrix.

Evaluation of wind-induced internal pressure in low-rise buildings: A multi scale experimental and numerical approach

Hurricane is one of the most destructive and costly natural hazard to the built environment and its impact on low-rise buildings, particularity, is beyond acceptable. The major objective of this research was to perform a parametric evaluation of internal pressure (IP) for wind-resistant design of low-rise buildings and wind-driven natural ventilation applications. For this purpose, a multi-scale experimental, i.e. full-scale at Wall of Wind (WoW) and small-scale at Boundary Layer Wind Tunnel (BLWT), and a Computational Fluid Dynamics (CFD) approach was adopted. This provided new capability to assess wind pressures realistically on internal volumes ranging from small spaces formed between roof tiles and its deck to attic to room partitions. Effects of sudden breaching, existing dominant openings on building envelopes as well as compartmentalization of building interior on the IP were systematically investigated. Results of this research indicated: (i) for sudden breaching of dominant openings, the transient overshooting response was lower than the subsequent steady state peak IP and internal volume correction for low-wind-speed testing facilities was necessary. For example a building without volume correction experienced a response four times faster and exhibited 30–40% lower mean and peak IP; (ii) for existing openings, vent openings uniformly distributed along the roof alleviated, whereas one sided openings aggravated the IP; (iii) larger dominant openings exhibited a higher IP on the building envelope, and an off-center opening on the wall exhibited (30–40%) higher IP than center located openings; (iv) compartmentalization amplified the intensity of IP and; (v) significant underneath pressure was measured for field tiles, warranting its consideration during net pressure evaluations. The study aimed at wind driven natural ventilation indicated: (i) the IP due to cross ventilation was 1.5 to 2.5 times higher for Ainlet/Aoutlet>1 compared to cases where Ainlet/Aoutlet<1, this in effect reduced the mixing of air inside the building and hence the ventilation effectiveness; (ii) the presence of multi-room partitioning increased the pressure differential and consequently the air exchange rate. Overall good agreement was found between the observed large-scale, small-scale and CFD based IP responses. Comparisons with ASCE 7-10 consistently demonstrated that the code underestimated peak positive and suction IP.

Salient factors in child molestation: Moral development, social competence, and type of offender

The current study was designed to build on and extend the existing knowledge base of factors that cause, maintain, and influence child molestation. Theorized links among the type of offender and the offender's levels of moral development and social competence in the perpetration of child molestation were investigated. The conceptual framework for the study is based on the cognitive developmental stages of moral development as proposed by Kohlberg, the unified theory, or Four-Preconditions Model, of child molestation as proposed by Finkelhor, and the Information-Processing Model of Social Skills as proposed by McFall. The study sample consisted of 127 adult male child molesters participating in outpatient group therapy. All subjects completed a Self-Report Questionnaire which included questions designed to obtain relevant demographic data, questions similar to those used by the researchers for the Massachusetts Treatment Center: Child Molester Typology 3's social competency dimension, the Defining Issues Test (DIT) short form, the Social Avoidance and Distress Scale (SADS), the Rathus Assertiveness Schedule (RAS), and the Questionnaire Measure of Empathic Tendency (Empathy Scale). Data were analyzed utilizing confirmatory factor analysis, t-tests, and chi-square statistics. Partial support was found for the hypothesis that moral development is a separate but correlated construct from social competence. As predicted, although the actual mean score differences were small, a statistically significant difference was found in the current study between the mean DITP scores of the subject sample and that of the general male population, suggesting that child molesters, as a group, function at a lower level of moral development than does the general male population, and the situational offenders in the study sample demonstrated a statistically significantly higher level of moral development than the preferential offenders. The data did not support the hypothesis that situational offenders will demonstrate lower levels of social competence than preferential offenders. Relatively little significance is placed on this finding, however, because the measure for the social competency variable was likely subject to considerable measurement error in that the items used as indicators were not clearly defined. The last hypothesis, which involved the potential differences in social anxiety, assertion skills, and empathy between the situational and preferential offender types, was not supported by the data. ^

Human impacts on pig frog (Rana grylio) populations in south Florida wetlands: Harvest, water management and mercury contamination

This study investigated how harvest and water management affected the ecology of the Pig Frog, Rana grylio. It also examined how mercury levels in leg muscle tissue vary spatially across the Everglades. Rana grylio is an intermediate link in the Everglades food web. Although common, this inconspicuous species can be affected by three forms of anthropogenic disturbance: harvest, water management and mercury contamination. This frog is harvested both commercially and recreationally for its legs, is aquatic and thus may be susceptible to water management practices, and can transfer mercury throughout the Everglades food web. ^ This two-year study took place in three major regions: Everglades National Park (ENP), Water Conservation Areas 3A (A), and Water Conservation Area 3B (B). The study categorized the three sites by their relative harvest level and hydroperiod. During the spring of 2001, areas of the Everglades dried completely. On a regional and local scale Pig Frog abundance was highest in Site A, the longest hydroperiod, heavily harvested site, followed by ENP and B. More frogs were found along survey transects and in capture-recapture plots before the dry-down than after the dry-down in Sites ENP and B. Individual growth patterns were similar across all sites, suggesting differences in body size may be due to selective harvest. Frogs from Site A, the flooded and harvested site, had no differences in survival rates between adults and juveniles. Site B populations shifted from a juvenile to adult dominated population after the dry-down. Dry-downs appeared to affect survival rates more than harvest. ^ Total mercury in frog leg tissue was highest in protected areas of Everglades National Park with a maximum concentration of 2.3 mg/kg wet mass where harvesting is prohibited. Similar spatial patterns in mercury levels were found among pig frogs and other wildlife throughout parts of the Everglades. Pig Frogs may be transferring substantial levels of mercury to other wildlife species in ENP. ^ In summary, although it was found that abundance and survival were reduced by dry-down, lack of adult size classes in Site A, suggest harvest also plays a role in regulating population structure. ^

The knowledge and promotion of exercise to older adults with type 2 diabetes by dietitian diabetes educators

The extent to which Registered Dietitians (RD) promote exercise as part of diabetes self-management education to older diabetic adults has not been established. This study explored the exercise-related knowledge, design, and content of educational programs among RDs who were Certified Diabetes Educators (CDEs) and non-CDEs. The Exercise Teaching Questionnaire was completed by 94 CDEs and 73 non-CDEs in Florida, California, and Texas. ^ CDEs had significantly (p < 0.001) higher mean Knowledge, Design, and Content scores (11.8 ± 1.1, 33.5 ± 9.4, 26.9 ± 4.8, respectively) than non-CDEs (11.1 ± 1.6, 29.2 ± 11.1, 22.4 ± 7.4, respectively). However, Knowledge means for both CDEs and non-CDEs were above the 85 percentile. Design and content scale responses showed that while dietitians provided basic information about safety and benefits related to exercise, they frequently reported “never” or only “sometimes” making exercise recommendations. ^ Although these results suggest that RDs are knowledgeable about exercise for older adults with Type 2 diabetes, greater importance should be made on training RDs to promote exercise, perhaps with an emphasis on a comprehensive team approach. ^

Molecular phylogenetics of the palm tribe Geonomeae, and differentiation of Geonoma macrostachys western Amazonian varieties

Phylogenetic analyses were performed on six genera and 46 species of the Neotropical palm tribe Geonomeae. The analyses were based on two low copy nuclear DNA sequences from the genes encoding phosphoribulokinase and RNA polymerase II. The basal node of the tribe was polytomous. Pholidostachys formed a monophyletic group. The currently accepted genera Calyptronoma and Calyptrogyne formed a well-supported clade with Calyptronoma resolved as paraphyletic to Calyptrogyne. Geonoma formed a strongly supported monophyletic group consisting of two main clades. ^ An evaluation of the genetic distinctness between Geonoma macrostachys varieties at a local and regional scale using inter-simple sequence repeat (ISSR) markers was performed. Clustering, ordination, and AMOVA suggested a lack of genetic distinctness between varieties at the regional level. A hierarchical AMOVA revealed that the genetic diversity mainly lies among the four localities sampled. A significant genetic differentiation between sympatric varieties occurred in one locality only. The current taxonomy of G. macrostachys, which recognizes only one species, was therefore supported. ^ The preferred habitat of sympatric G. macrostachys varieties with respect to edaphic, topographic, and light factors in three Peruvian lowland forests was studied. The two varieties were mostly encountered in different physiographically defined habitats, with variety acaulis occurring more often in floodplain forest and variety macrostachys in the tierra firme. Comparison of means tests revealed that nine to eleven of the 16 environmental variables were significantly different between varieties. Edaphic factors, mainly soil texture and K content, were better contributors than light conditions to distinguish the habitats occupied by the two varieties in all three study sites. It is concluded that habitat differentiation plays a role in the coexistence of these closely related species taxa. ^

A comparative analysis of self-determined evaluations of work performance and support needs by adults with mental retardation in supported work and in sheltered workshop environments

The purpose of this study was to determine if there was a difference in the self-determined evaluations of work performance and support needs by adults with mental retardation in supported employment and in sheltered workshop environments. The instrument, Job Observation and Behavior Scale: Opportunity for Self-Determination (JOBS: OSD; Brady, Rosenberg, & Frain, 2006), was administered to 38 adults with mental retardation from sheltered workshops and 32 adults with mental retardation from supported employment environments. Cross-tabulations with Chi-square tests and independent samples t-tests were conducted to evaluate differences between the two groups, sheltered workshop and supported work. Two Multivariate Analyses of Variance (MANOVAs) were conducted to determine the effect of work environment on Quality of Performance (QP) and Types of Support (TS) test scores and their subscales. ^ This study found that there were significant differences between the groups on the QP Behavior and Job Duties subscales. The sheltered workshop group perceived themselves as performing significantly better on job duties than the supported work group. Conversely, the supported work group perceived themselves to have better behavior than the sheltered workshop group. However, there were no significant differences between groups in their perception of support needs for the three subscales. ^ The findings imply that work environment affects the self-determined evaluations of work performance by adults with mental retardation. Recommendations for further study include (a) detailing the characteristics of supported work and sheltered workshops that support and/or discourage self-determined behaviors, (b) exploring the behavior of adults with mental retardation in sheltered workshops and supported work environments, and (c) analysis of the support needs for and understanding of them by adults with mental retardation in sheltered workshops and in supported work environments. ^

Development of risk based treatability and engineering measures for reducing exposure to lead contaminated media in the Miami inner city, Florida

A major consequence of contamination at the local level’s population as it relates to environmental health and environmental engineering is childhood lead poisoning. Environmental contamination is one of the pressing environmental concerns facing the world today. Current approaches often focus on large contaminated industrial size sites that are designated by regulatory agencies for site remediation. Prior to this study, there were no known published studies conducted at the local and smaller scale, such as neighborhoods, where often much of the contamination is present to remediate. An environmental health study of local lead-poisoning data in Liberty City, Little Haiti and eastern Little Havana in Miami-Dade County, Florida accounted for a disproportionately high number of the county’s reported childhood lead poisoning cases. An engineering system was developed and designed for a comprehensive risk management methodology that is distinctively applicable to the geographical and environmental conditions of Miami-Dade County, Florida. Furthermore, a scientific approach for interpreting environmental health concerns, while involving detailed environmental engineering control measures and methods for site remediation in contained media was developed for implementation. Test samples were obtained from residents and sites in those specific communities in Miami-Dade County, Florida (Gasana and Chamorro 2002). Currently lead does not have an Oral Assessment, Inhalation Assessment, and Oral Slope Factor; variables that are required to run a quantitative risk assessment. However, various institutional controls from federal agencies’ standards and regulation for contaminated lead in media yield adequate maximum concentration limits (MCLs). For this study an MCL of .0015 (mg/L) was used. A risk management approach concerning contaminated media involving lead demonstrates that the linkage of environmental health and environmental engineering can yield a feasible solution.

Regional processes in mangrove ecosystems: spatial scaling relationships, biomass, and turnover rates following catastrophic disturbance

Physiological processes and local-scale structural dynamics of mangroves are relatively well studied. Regional-scale processes, however, are not as well understood. Here we provide long-term data on trends in structure and forest turnover at a large scale, following hurricane damage in mangrove ecosystems of South Florida, U.S.A. Twelve mangrove vegetation plots were monitored at periodic intervals, between October 1992 and March 2005. Mangrove forests of this region are defined by a −1.5 scaling relationship between mean stem diameter and stem density, mirroring self-thinning theory for mono-specific stands. This relationship is reflected in tree size frequency scaling exponents which, through time, have exhibited trends toward a community average that is indicative of full spatial resource utilization. These trends, together with an asymptotic standing biomass accumulation, indicate that coastal mangrove ecosystems do adhere to size-structured organizing principles as described for upland tree communities. Regenerative dynamics are different between areas inside and outside of the primary wind-path of Hurricane Andrew which occurred in 1992. Forest dynamic turnover rates, however, are steady through time. This suggests that ecological, more-so than structural factors, control forest productivity. In agreement, the relative mean rate of biomass growth exhibits an inverse relationship with the seasonal range of porewater salinities. The ecosystem average in forest scaling relationships may provide a useful investigative tool of mangrove community biomass relationships, as well as offer a robust indicator of general ecosystem health for use in mangrove forest ecosystem management and restoration.

Correspondence of historic salinity fluctuations in Florida Bay, USA, to atmospheric variability and anthropogenic changes

Florida Bay is a highly dynamic estuary that exhibits wide natural fluctuations in salinity due to changes in the balance of precipitation, evaporation and freshwater runoff from the mainland. Rapid and large-scale modification of freshwater flow and construction of transportation conduits throughout the Florida Keys during the late nineteenth and twentieth centuries reshaped water circulation and salinity patterns across the ecosystem. In order to determine long-term patterns in salinity variation across the Florida Bay estuary, we used a diatom-based salinity transfer function to infer salinity within 3.27 ppt root mean square error of prediction from diatom assemblages from four ~130 year old sediment records. Sites were distributed along a gradient of exposure to anthropogenic shifts in the watershed and salinity. Precipitation was found to be the primary driver influencing salinity fluctuations over the entire record, but watershed modifications on the mainland and in the Florida Keys during the late-1800s and 1900s were the most likely cause of significant shifts in baseline salinity. The timing of these shifts in the salinity baseline varies across the Bay: that of the northeastern coring location coincides with the construction of the Florida Overseas Railway (AD 1906–1916), while that of the east-central coring location coincides with the drainage of Lake Okeechobee (AD 1881–1894). Subsequent decreases occurring after the 1960s (east-central region) and early 1980s (southwestern region) correspond to increases in freshwater delivered through water control structures in the 1950s–1970s and again in the 1980s. Concomitant increases in salinity in the northeastern and south-central regions of the Bay in the mid-1960s correspond to an extensive drought period and the occurrence of three major hurricanes, while the drop in the early 1970s could not be related to any natural event. This paper provides information about major factors influencing salinity conditions in Florida Bay in the past and quantitative estimates of the pre- and post-South Florida watershed modification salinity levels in different regions of the Bay. This information should be useful for environmental managers in setting restoration goals for the marine ecosystems in South Florida, especially for Florida Bay.

Relationships between gifted selection criteria and performance in sixth -grade gifted science

This study examined the relationships between gifted selection criteria used in the Dade County Public Schools of Miami, Florida and performance in sixth grade gifted science classes.^ The goal of the study was to identify significant predictors of performance in sixth grade gifted science classes. Group comparisons of performance were also made. Performance in sixth grade gifted science was defined as the numeric average of nine weeks' grades earned in sixth grade gifted science classes.^ The sample consisted of 100 subjects who were formerly enrolled in sixth grade gifted science classes over two years at a large, multiethnic public middle school in Dade County.^ The predictors analyzed were I.Q. score (all scales combined), full scale I.Q. score, verbal scale I.Q. score, performance scale I.Q. score, combined Stanford Achievement Test (SAT) score (Reading Comprehension plus Math Applications), SAT Reading Comprehension score, and SAT Math Applications score. Combined SAT score and SAT Math Applications score were significantly positively correlated to performance in sixth grade gifted science. Performance scale I.Q. score was significantly negatively correlated to performance in sixth grade gifted science. The other predictors examined were not significantly correlated to performance.^ Group comparison results showed the mean average of nine weeks grades for the full scale I.Q. group was greater than the verbal and performance scale I.Q. groups. Females outperformed males to a highly significant level. Mean g.p.a. for ethnic groups was greatest for Asian students, followed by white non-Hispanic, Hispanic, and black. Students not receiving a lunch subsidy outperformed those receiving subsidies.^ Comparisons of performance based on gifted qualification plan showed the mean g.p.a. for traditional plan and Plan B groups were not different. Mean g.p.a. for students who qualified for gifted using automatic Math Applications criteria was highest, followed by automatic Reading Comprehension criteria and Plan B Matrix score. Both automatic qualification groups outperformed the traditional group. The traditional group outperformed the Plan B Matrix group. No significant differences in mean g.p.a. between the Plan B subgroups and the traditional plan group were found. ^

Site specific growth of metal catalyzed silica nanowires for biological and chemical sensing

In this research the integration of nanostructures and micro-scale devices was investigated using silica nanowires to develop a simple yet robust nanomanufacturing technique for improving the detection parameters of chemical and biological sensors. This has been achieved with the use of a dielectric barrier layer, to restrict nanowire growth to site-specific locations which has removed the need for post growth processing, by making it possible to place nanostructures on pre-pattern substrates. Nanowires were synthesized using the Vapor-Liquid-Solid growth method. Process parameters (temperature and time) and manufacturing aspects (structural integrity and biocompatibility) were investigated. Silica nanowires were observed experimentally to determine how their physical and chemical properties could be tuned for integration into existing sensing structures. Growth kinetic experiments performed using gold and palladium catalysts at 1050°C for 60 minutes in an open-tube furnace yielded dense and consistent silica nanowire growth. This consistent growth led to the development of growth model fitting, through use of the Maximum Likelihood Estimation (MLE) and Bayesian hierarchical modeling. Transmission electron microscopy studies revealed the nanowires to be amorphous and X-ray diffraction confirmed the composition to be SiO2 . Silica nanowires were monitored in epithelial breast cancer media using Impedance spectroscopy, to test biocompatibility, due to potential in vivo use as a diagnostic aid. It was found that palladium catalyzed silica nanowires were toxic to breast cancer cells, however, nanowires were inert at 1μg/mL concentrations. Additionally a method for direct nanowire integration was developed that allowed for silica nanowires to be grown directly into interdigitated sensing structures. This technique eliminates the need for physical nanowire transfer thus preserving nanowire structure and performance integrity and further reduces fabrication cost. Successful nanowire integration was physically verified using Scanning electron microscopy and confirmed electrically using Electrochemical Impedance Spectroscopy of immobilized Prostate Specific Antigens (PSA). The experiments performed above serve as a guideline to addressing the metallurgic challenges in nanoscale integration of materials with varying composition and to understanding the effects of nanomaterials on biological structures that come in contact with the human body.

Site Specifc Growth of Metal Catalyzed Silica Nanowires for Biological and Chemical Sensing

In this research the integration of nanostructures and micro-scale devices was investigated using silica nanowires to develop a simple yet robust nanomanufacturing technique for improving the detection parameters of chemical and biological sensors. This has been achieved with the use of a dielectric barrier layer, to restrict nanowire growth to site-specific locations which has removed the need for post growth processing, by making it possible to place nanostructures on pre-pattern substrates. Nanowires were synthesized using the Vapor-Liquid-Solid growth method. Process parameters (temperature and time) and manufacturing aspects (structural integrity and biocompatibility) were investigated. Silica nanowires were observed experimentally to determine how their physical and chemical properties could be tuned for integration into existing sensing structures. Growth kinetic experiments performed using gold and palladium catalysts at 1050 ˚C for 60 minutes in an open-tube furnace yielded dense and consistent silica nanowire growth. This consistent growth led to the development of growth model fitting, through use of the Maximum Likelihood Estimation (MLE) and Bayesian hierarchical modeling. Transmission electron microscopy studies revealed the nanowires to be amorphous and X-ray diffraction confirmed the composition to be SiO2 . Silica nanowires were monitored in epithelial breast cancer media using Impedance spectroscopy, to test biocompatibility, due to potential in vivo use as a diagnostic aid. It was found that palladium catalyzed silica nanowires were toxic to breast cancer cells, however, nanowires were inert at 1µg/mL concentrations. Additionally a method for direct nanowire integration was developed that allowed for silica nanowires to be grown directly into interdigitated sensing structures. This technique eliminates the need for physical nanowire transfer thus preserving nanowire structure and performance integrity and further reduces fabrication cost. Successful nanowire integration was physically verified using Scanning electron microscopy and confirmed electrically using Electrochemical Impedance Spectroscopy of immobilized Prostate Specific Antigens (PSA). The experiments performed above serve as a guideline to addressing the metallurgic challenges in nanoscale integration of materials with varying composition and to understanding the effects of nanomaterials on biological structures that come in contact with the human body.