A unique Raman spectroscopic investigation combining a number of different techniques has been conducted in situ on the composition of the passive film on iron, both during its growth in 0.05 M NaOH by potentiodynamic polarization and during localized breakdown by pitting after addition of 0.05 M NaCl. There are differing theories for the mechanism of pit initiation and formation in the passive film on iron, and while these are in part due to different environmental factors, they are also influenced by differing theories for the nature of the passive film. The detailed information obtained in this study corroborate the two layer model for the passive film on iron, with γ-Fe2O3 forming the inner layer and the outer layer consisting of δ-FeOOH, α-FeOOH, γ-FeOOH, other components such as Fe(OH)2 and other intermediates. In the passive region of anodic polarization the film became increasingly hydrated with increasing anodic potential and with increased cycles became amorphous, comparing well with the Hydrated Polymeric Oxide model. Pre-resonance enhancement of the Raman bands of iron oxides and particularly iron oxy-hydroxides was afforded by excitation at 636.4 nm, and particularly at low wavenumbers. The use of Multivariate Curve Resolution with Alternating Least Squares (MCR-ALS) enabled determination of the relative amounts of the iron oxide and oxy-hydroxide components from the complex spectra recorded during potentiodynamic polarization. The amount of water incorporated in the passive film under the same conditions was also monitored in situ at similar potentials using excitation at 514.5 nm. Addition of chloride ions resulted in an increase in hydration and a change of the composition of the passive film to comprise mainly β-FeOOH and Green complex with some γ-Fe2O3 and γ-FeOOH. At the pitting potential significant changes in the composition occurred along with reduction in hydration, so that re-passivation could no longer be maintained at the same rate as dissolution by the chloride ions, enabling stable pitting. These observations indicate that water plays a protective role in the passive film and reinforce the mechanisms for pit initiation based on the De-passivation–Re-passivation theory and Chemical Dissolution theory.

All-aluminum microchannel heat exchangers are designed to significantly reduce refrigerant charge requirements, weight, reduced brazed joints, and decreased potential for leakage by increasing reliability. Al 3003 alloy is corrosion resistant and can be formed, welded, and brazed but the issue with all-aluminum heat exchangers is localized corrosion (pitting) in corrosive environments. Currently, there is no universally accepted corrosion test that all coil manufacturers use to characterize their products. Electrochemical testing method of cyclic polarization was employed in this investigation and relevant parameters including electrolyte corrosive agent and its concentration, electrolyte pH, and applied potential scan rate was varied to find an optimal set of parameters. Results of cyclic polarization of Al 3003 in electrolytes containing various concentrations of NaCl were compared with those of the tests in Sea Water Acidified Accelerated Test (SWAAT) electrolyte and it is shown the SWAAT electrolyte (4.2% sea salt acidified to pH of 2.9) is by far stronger (in terms of corrosivity) than typical 3.5% NaCl solution used in most corrosion testing. Corrosion rates (g/m2yr) of Al 3003 measured in this investigation were comparable to those provided by ISO 9223 standard corresponding to C1 through CX categories. Duration of cyclic polarization test is much shorter than that of SWAAT and results obtained in this test is more reproducible compared to those of SWAAT. Scanning electron microscopy micrographs show typical pit depths of about 50 μm.

While numerous studies have examined the role of group identity, particularly partisan identity, in influencing individuals’ socio-political attitudes and policy preferences, the impact of relational identity — individuals’ self-concept rooted in interpersonal relationships, roles, and responsibilities — is rarely examined. This dissertation outlines the different effects of group identity and relational identity on message processing and attitude change in socio-political contexts. This dissertation first draws on the social identity approach and motivated reasoning to understand how categorizing oneself in terms of group membership contributes to group polarization. Next, building on Brewer and Gardner’s (1996) notion of a relational self and interpersonal relationship literature, this dissertation examines the influence of relational identity on attitudes toward socio-political issues. Additionally, this dissertation offers a relational identity-based strategic communication solution that could potentially mitigate polarization resulting from group identity. Three online survey experiments were conducted in three different contexts, including immigration, climate change, and the COVID-19 pandemic. These three studies primed different group identities (e.g., partisan identity and national identity) and relational identities (e.g., being a friend and being a parent) and then presented issue-specific factual information. Results suggest that individuals’ partisan identities bias a broad range of judgments and lead to polarization over politicized issues, even when presented with factual information. However, linking a controversial socio-political issue and an issue-relevant relational identity has the potential to mitigate polarization resulting from group identity such as partisanship. / Media & Communication

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Background: Pregnant individuals who participate in physical activity throughout gestation have been shown to experience a wide spectrum of health benefits, along with the fetus. In nonpregnant populations, PA influences the polarization state of tissue resident macrophages, resulting in increased regulatory and decreased inflammatory profiles. The effects of PA on placenta-resident macrophages, or Hofbauer cells (HBCs), remains unknown. My thesis aimed to explore this novel area. Methods: The first objective of my thesis was to identify any associations between gestational PA and HBC polarization. PA was objectively measured in both mid (24-28 weeks) and late (34-38 weeks) pregnancy using accelerometry. Immunofluorescent localization of the panmacrophage marker CD68 and the anti-inflammatory macrophage marker CD206 was used to assess polarization states. Protein and gene expression of CD68 and CD206 were assessed using Western blot and qPCR, respectively. The second objective was to explore the relationships between gestational PA, HBC polarization, and angiogenic factors in the placenta. Western blot measured the relative protein expression of FGF2 and SPRY2, and the localization of FGF2, SPRY2, and VEGF within HBCs was explored using immunofluorescent colocalization in term placenta tissue and primary HBC cultures. Results: While there were no differences in the absolute numbers of total or CD206+ HBCs, the proportion of CD206+ HBCs was elevated in active individuals. There were no significant differences in the gene expression of CD68 or CD206, nor in the gene expression of CD206; however, CD206 protein expression was observed to be lower in active participants. Both CD206+ and CD206- HBCs expressed VEGF. Active individuals had significantly higher low molecular weight-FGF2. There were no differences in the protein expression of SPRY2, total FGF2, or high molecular weight FGF2 based on PA. HBCs both in vitro and in vivo of all polarizations expressed VEGF, SPRY2, and FGF2, and were observed to create intracellular junctions and multi-nucleated giant cells. Conclusions: In conclusion, PA was associated with a higher proportion of CD206+ HBCs and reduced levels of CD206 protein. In combination with the lack of significant difference in CD206 mRNA based on PA levels, this suggests a potential effect mediated by PA on the transcriptional regulation of CD206. HBCs were seen to express SPRY2, VEGF, and FGF2, identifying them as potential players in angiogenesis regulation in the placenta. The elevated levels of low molecular weight FGF2 in active individuals suggests the PA may play a role in the modulation of placental angiogenesis. Future research should continue to explore the relationships between PA, HBC polarization, and angiogenesis.

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The growth of internet communication has affected deliberative democracy by introducing new public spheres. One emerging public sphere is the discussion forum linked to online news sources. By analyzing 1,768 comments posted to a regional online news website, I discuss five key frameworks that commenters used to simplify the debate over immigration. I also find that extreme comments decreased in frequency over a two-year period while more moderate comments increased. In light of group polarization theory, this finding suggests that the forum is more like a single community with a fairly moderate average position to which people with differing opinions converge, rather than a divided community consisting of two distinct groups, each polarizing toward more extreme positions. The forum appears to have moderated itself in response to triggers of discourse change by means of temporary reframing of arguments. I develop a theoretical framework for understanding how group interactions produce self-regulatory behavior that can prevent polarized discourse.