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.

Source/receptor reconciliation of ambient organic fine particulate matter in Palm Beach County

Airborne particulate matter (PM) is of environmental concern not only in urban but also rural areas that are easily inhalable and have been considered responsible, together with gaseous pollutants, for possible health effects. The objectives of this research study is to generate an extensive data set for ambient PM collected at Belle Glade and Delray Beach that ultimately was used together with published source profiles to predict the contributions of major sources to the overall airborne particle burden in Belle Glade and Delray Beach. ^ The size segregated particle sampling was conducted for one entire year. The samples collected during the months of January and May were further subjected to chemical analysis for organic compounds by Gas Chromatography-Mass Spectrometry. Additional, PM10 sampling was conducted simultaneously with size segregated particle sampling during January and May to analyze for trace elements using Instrumental Neutron Activation Analysis technique. Elements and organic marker compounds were used in Chemical Mass Balance modeling to determine the major source contribution to the ambient fine particle matter burden. ^ Size segregated particle distribution results show bimodal in both sampling sites. Sugarcane pre-harvest burning in the rural site elevated PM10 concentration by about 30% during the sugarcane harvest season compared to sugarcane growing season. Sea salt particles and Saharan dust particles accounted for the external sources. ^ The results of trace element analysis show that Al, Ca, Cs, Eu, Lu, Nd, Sc, Sm, Th, and Yb are more abundant at the rural sampling site. The trace elements Ba, Br, Ce, Cl, Cr, Fe, Gd, Hf, Na, Sb, Ta, V, and W show high abundance at the urban site due to anthropogenic activities except for Na and Cl, which are from sea salt spray. On the other hand, size segregated trace organic compounds measurements show that organic compounds mainly from combustion process were accumulated in PM0.95. ^ In conclusion, major particle sources were determined by the CMB8.2 software as follows: road dust, sugarcane leaf burning, diesel-powered and gasoline powered vehicle exhaust, leaf surface abrasion particles, and a very small fraction of meat cooking. ^

The role of temporal synchrony in the facilitation of perceptual learning during prenatal development

This study explored the critical features of temporal synchrony for the facilitation of prenatal perceptual learning with respect to unimodal stimulation using an animal model, the bobwhite quail. The following related hypotheses were examined: (1) the availability of temporal synchrony is a critical feature to facilitate prenatal perceptual learning, (2) a single temporally synchronous note is sufficient to facilitate prenatal perceptual learning, with respect to unimodal stimulation, and (3) in situations where embryos are exposed to a single temporally synchronous note, facilitated perceptual learning, with respect to unimodal stimulation, will be optimal when the temporally synchronous note occurs at the onset of the stimulation bout. To assess these hypotheses, two experiments were conducted in which quail embryos were exposed to various audio-visual configurations of a bobwhite maternal call and tested at 24 hr after hatching for evidence of facilitated prenatal perceptual learning with respect to unimodal stimulation. Experiment 1 explored if intermodal equivalence was sufficient to facilitate prenatal perceptual learning with respect to unimodal stimulation. A Bimodal Sequential Temporal Equivalence (BSTE) condition was created that provided embryos with sequential auditory and visual stimulation in which the same amodal properties (rate, duration, rhythm) were made available across modalities. Experiment 2 assessed: (a) whether a limited number of temporally synchronous notes are sufficient for facilitated prenatal perceptual learning with respect to unimodal stimulation, and (b) whether there is a relationship between timing of occurrence of a temporally synchronous note and the facilitation of prenatal perceptual learning. Results revealed that prenatal exposure to BSTE was not sufficient to facilitate perceptual learning. In contrast, a maternal call that contained a single temporally synchronous note was sufficient to facilitate embryos’ prenatal perceptual learning with respect to unimodal stimulation. Furthermore, the most salient prenatal condition was that which contained the synchronous note at the onset of the call burst. Embryos’ prenatal perceptual learning of the call was four times faster in this condition than when exposed to a unimodal call. Taken together, bobwhite quail embryos’ remarkable sensitivity to temporal synchrony suggests that this amodal property plays a key role in attention and learning during prenatal development.

Essays on international lending and increasing returns to scale

Standard economic theory suggests that capital should flow from rich countries to poor countries. However, capital has predominantly flowed to rich countries. The three essays in this dissertation attempt to explain this phenomenon. The first two essays suggest theoretical explanations for why capital has not flowed to the poor countries. The third essay empirically tests the theoretical explanations.^ The first essay examines the effects of increasing returns to scale on international lending and borrowing with moral hazard. Introducing increasing returns in a two-country general equilibrium model yields possible multiple equilibria and helps explain the possibility of capital flows from a poor to a rich country. I find that a borrowing country may need to borrow sufficient amounts internationally to reach a minimum investment threshold in order to invest domestically.^ The second essay examines how a poor country may invest in sectors with low productivity because of sovereign risk, and how collateral differences across sectors may exacerbate the problem. I model sovereign borrowing with a two-sector economy: one sector with increasing returns to scale (IRS) and one sector with diminishing returns to scale (DRS). Countries with incomes below a threshold will only invest in the DRS sector, and countries with incomes above a threshold will invest mostly in the IRS sector. The results help explain the existence of a bimodal world income distribution.^ The third essay empirically tests the explanations for why capital has not flowed from the rich to the poor countries, with a focus on institutions and initial capital. I find that institutional variables are a very important factor, but in contrast to other studies, I show that institutions do not account for the Lucas Paradox. Evidence of increasing returns still exists, even when controlling for institutions and other variables. In addition, I find that the determinants of capital flows may depend on whether a country is rich or poor.^

Development of face recognition: Infancy to early childhood

Perception and recognition of faces are fundamental cognitive abilities that form a basis for our social interactions. Research has investigated face perception using a variety of methodologies across the lifespan. Habituation, novelty preference, and visual paired comparison paradigms are typically used to investigate face perception in young infants. Storybook recognition tasks and eyewitness lineup paradigms are generally used to investigate face perception in young children. These methodologies have introduced systematic differences including the use of linguistic information for children but not infants, greater memory load for children than infants, and longer exposure times to faces for infants than for older children, making comparisons across age difficult. Thus, research investigating infant and child perception of faces using common methods, measures, and stimuli is needed to better understand how face perception develops. According to predictions of the Intersensory Redundancy Hypothesis (IRH; Bahrick & Lickliter, 2000, 2002), in early development, perception of faces is enhanced in unimodal visual (i.e., silent dynamic face) rather than bimodal audiovisual (i.e., dynamic face with synchronous speech) stimulation. The current study investigated the development of face recognition across children of three ages: 5 – 6 months, 18 – 24 months, and 3.5 – 4 years, using the novelty preference paradigm and the same stimuli for all age groups. It also assessed the role of modality (unimodal visual versus bimodal audiovisual) and memory load (low versus high) on face recognition. It was hypothesized that face recognition would improve across age and would be enhanced in unimodal visual stimulation with a low memory load. Results demonstrated a developmental trend (F(2, 90) = 5.00, p = 0.009) with older children showing significantly better recognition of faces than younger children. In contrast to predictions, no differences were found as a function of modality of presentation (bimodal audiovisual versus unimodal visual) or memory load (low versus high). This study was the first to demonstrate a developmental improvement in face recognition from infancy through childhood using common methods, measures and stimuli consistent across age.

Tests of the Intersensory Redundancy Hypothesis across early postnatal development

The Intersensory Redundancy Hypothesis (IRH; Bahrick & Lickliter, 2000, 2002, 2012) predicts that early in development information presented to a single sense modality will selectively recruit attention to modality-specific properties of stimulation and facilitate learning of those properties at the expense of amodal properties (unimodal facilitation). Vaillant (2010) demonstrated that bobwhite quail chicks prenatally exposed to a maternal call alone (unimodal stimulation) are able to detect a pitch change, a modality-specific property, in subsequent postnatal testing between the familiarized call and the same call with altered pitch. In contrast, chicks prenatally exposed to a maternal call paired with a temporally synchronous light (redundant audiovisual stimulation) were unable to detect a pitch change. According to the IRH (Bahrick & Lickliter, 2012), as development proceeds and the individual's perceptual abilities increase, the individual should detect modality-specific properties in both nonredundant, unimodal and redundant, bimodal conditions. However, when the perceiver is presented with a difficult task, relative to their level of expertise, unimodal facilitation should become evident. The first experiment of the present study exposed bobwhite quail chicks 24 hr after hatching to unimodal auditory, nonredundant audiovisual, or redundant audiovisual presentations of a maternal call for 10min/hr for 24 hours. All chicks were subsequently tested 24 hr after the completion of the stimulation (72 hr following hatching) between the familiarized maternal call and the same call with altered pitch. Chicks from all experimental groups (unimodal, nonredundant audiovisual, and redundant audiovisual exposure) significantly preferred the familiarized call over the pitch-modified call. The second experiment exposed chicks to the same exposure conditions, but created a more difficult task by narrowing the pitch range between the two maternal calls with which they were tested. Chicks in the unimodal and nonredundant audiovisual conditions demonstrated detection of the pitch change, whereas the redundant audiovisual exposure group did not show detection of the pitch change, providing evidence of unimodal facilitation. These results are consistent with predictions of the IRH and provide further support for the effects of unimodal facilitation and the role of task difficulty across early development.

The Role of Temporal Synchrony in the Facilitation of Perceptual Learning during Prenatal Development

This study explored the critical features of temporal synchrony for the facilitation of prenatal perceptual learning with respect to unimodal stimulation using an animal model, the bobwhite quail. The following related hypotheses were examined: (1) the availability of temporal synchrony is a critical feature to facilitate prenatal perceptual learning, (2) a single temporally synchronous note is sufficient to facilitate prenatal perceptual learning, with respect to unimodal stimulation, and (3) in situations where embryos are exposed to a single temporally synchronous note, facilitated perceptual learning, with respect to unimodal stimulation, will be optimal when the temporally synchronous note occurs at the onset of the stimulation bout. To assess these hypotheses, two experiments were conducted in which quail embryos were exposed to various audio-visual configurations of a bobwhite maternal call and tested at 24 hr after hatching for evidence of facilitated prenatal perceptual learning with respect to unimodal stimulation. Experiment 1 explored if intermodal equivalence was sufficient to facilitate prenatal perceptual learning with respect to unimodal stimulation. A Bimodal Sequential Temporal Equivalence (BSTE) condition was created that provided embryos with sequential auditory and visual stimulation in which the same amodal properties (rate, duration, rhythm) were made available across modalities. Experiment 2 assessed: (a) whether a limited number of temporally synchronous notes are sufficient for facilitated prenatal perceptual learning with respect to unimodal stimulation, and (b) whether there is a relationship between timing of occurrence of a temporally synchronous note and the facilitation of prenatal perceptual learning. Results revealed that prenatal exposure to BSTE was not sufficient to facilitate perceptual learning. In contrast, a maternal call that contained a single temporally synchronous note was sufficient to facilitate embryos’ prenatal perceptual learning with respect to unimodal stimulation. Furthermore, the most salient prenatal condition was that which contained the synchronous note at the onset of the call burst. Embryos’ prenatal perceptual learning of the call was four times faster in this condition than when exposed to a unimodal call. Taken together, bobwhite quail embryos’ remarkable sensitivity to temporal synchrony suggests that this amodal property plays a key role in attention and learning during prenatal development.

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

Aluminum oxide (A1203, or alumina) is a conventional ceramic known for applications such as wear resistant coatings, thermal liners, heaters, crucibles, dielectric systems, etc. However applications of A1203 are limited owing to its inherent brittleness. Due to its excellent mechanical properties and bending strength, carbon nanotubes (CNT) is an ideal reinforcement for A1203 matrix to improve its fracture toughness. The role of CNT dispersion in the fracture toughening of the plasma sprayed A1203-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 A1203 (A-SD), A1203 blended with 4wt.% CNT (A4C-B), composite spray dried A1203-4wt.% CNT (A4C-SD) and composite spray dried A1203-8wt.% CNT (A8CSD), 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 A1203/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 A1203/CNTinterface. 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.

The Effect of Prenatal Auditory Enrichment on Perceptual Narrowing in Bobwhite Quail Neonates

The development of species-typical perceptual preferences has been shown to depend on a variety of socially and ecologically derived sensory stimulation during both the pre- and postnatal periods. The prominent mechanism behind the development of these seemingly innate tendencies in young organisms has been hypothesized to be a domain-general pan-sensory selectivity process referred to as perceptual narrowing, whereby regularly experienced sensory stimuli are honed in upon, while simultaneously losing the ability to effectively discriminate between atypical or unfamiliar sensory stimulation. Previous work with precocial birds has been successful in preventing the development of species-typical perceptual preferences by denying the organism typical levels of social and/or self-produced stimulation. The current series of experiments explored the mechanism of perceptual narrowing to assess the malleability of a species-typical auditory preference in avian embryos. By providing a variety of different unimodal and bimodal presentations of a mixed-species vocalizations at the onset of prenatal auditory function, the following project aimed to 1) keep the perceptual window from narrowing, thereby interfering with the development of a species-typical auditory preference, 2) investigate how long differential prenatal stimulation can keep the perceptual window open postnatally, 3) explore how prenatal auditory enrichment effected preferences for novelty, and 4) assess whether prenatal auditory perceptual narrowing is affected by modality specific or amodal stimulus properties during early development. Results indicated that prenatal auditory enrichment significantly interferes with the emergence of a species-typical auditory preference and increases openness to novelty, at least temporarily. After accruing postnatal experience in an environment rich with species-typical auditory and multisensory cues, the effect of prenatal auditory enrichment rapidly was found to rapidly fade. Prenatal auditory enrichment with extraneous non-synchronous light exposure was shown to both keep the perceptual narrowing window open and impede learning in the postnatal environment, following hatching. Results are discussed in light of the role experience plays in perceptual narrowing during the perinatal period.

Can Intersensory Redundancy and Social Contingency Enhance Memory in Bobwhite Quail Hatchlings?

Recent findings indicate that bimodal-redundant stimulation promotes perceptual learning and recruits attention to amodal properties in non-human as well as human infants. However it is not clear if bimodal-redundant stimulation can also facilitate memory during the postnatal period. Moreover, most animal and human studies have employed an operant paradigm to study memory, but have not compared the effectiveness of contingent versus passive presentation of information on memory. The current study investigated the role of unimodal versus bimodal presentation and, the role of a contingent versus passive exposure in memory retention in the bobwhite quail (Colinus virginianus). Results revealed that contingently trained chicks demonstrated a preference for the familiarized call under both unimodal and bimodal conditions. Between-group analyses revealed that the contingent-bimodal group preferred the familiarized call as compared to the passive-bimodal group. These results indicate that the contingency paradigm accompanied with the bimodal stimulus type facilitated memory during early development.