On a novel method of impact by a front-end-coated bullet to evaluate the interface adhesion between film and substrate

A preliminary experiment was carried out to validate the feasibility of the method of impact by a front-end-coated bullet to evaluate the interface adhesion between film and substrate. The theoretical description of the initiation, propagation and evolution of the stress pulse during impact was generalized and formulized. The effects of the crucial parameters on the interface stress were further investigated with FEM. The results found the promising prospect of the application of such a method and provided useful guidance for experimental design.

Proton transfers at the air-water interface

Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes.

Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H₃O⁺(g), can protonate most (non-alkane) organic species, whereas H₃O⁺(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the ‘function’ of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (< 1 nm thick) is an arduous task. While recent advances in surface-specific spectroscopies have provided valuable information regarding the structure of aqueous interfaces, but structure alone is inadequate to decipher the function. By similar analogy, theoretical predictions based on classical molecular dynamics have remained limited in their scope.

Recently, we have adapted an analytical electrospray ionization mass spectrometer (ESIMS) for probing reactions at the gas-liquid interface in real time. This technique is direct, surface-specific,and provides unambiguous mass-to-charge ratios of interfacial species. With this innovation, we have been able to investigate the following:

1. How do anions mediate proton transfers at the air-water interface?

2. What is the basis for the negative surface potential at the air-water interface?

3. What is the mechanism for catalysis ‘on-water’?

In addition to our experiments with the ESIMS, we applied quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the molecular scale. Our results unambiguously demonstrated the role of electrostatic-reorganization of interfacial water during proton transfer events. With our experimental and theoretical results on the ‘superacidity’ of the surface of mildly acidic water, we also explored implications on atmospheric chemistry and green chemistry. Our most recent results explained the basis for the negative charge of the air-water interface and showed that the water-hydrophobe interface could serve as a site for enhanced autodissociation of water compared to the condensed phase.

Reflection and refraction of light at the interface of a uniaxial bicrystal

This paper deals with a theoretical analysis of the reflection and refraction of light at the interface of a bicrystal by use of Maxwell's equations. For a general case, the formulas of Snell's Law and the four Fresnel coefficients for the reflection and refraction of extraordinary light at the interface of a uniaxial bicrystal are derived for the first time, as well as the Brewster angle value. The condition for total reflection is presented and the electromagnetic fields distributions at both sides of a bicrystal are presented when total reflection occurs.

Investigation of the influence of the aberration induced by a plane interface on STED microscopy

The structure of the inhibition patterns is important to the stimulated emission depletion (STED) microscopy. Usually, Laguerre-Gaussian (LG) beam and the central zero-intensity patterns created by inserting phase masks in Gaussian beams are used as the erase beam in STED microscopy. Aberration is generated when focusing beams through an interface between the media of the mismatched refractive indices. By use of the vectorial integral, the effects of such aberration on the shape of depletion patterns and the size of fluorescence emission spot in the STED microscopy are studied. Results are presented as a comparison between the aberration-free case and the aberrated cases. (C) 2009 Optical Society of America

A quase conversação na comentosfera dos j-blogs: um estudo das interações na interface de comentários de quatro blogs jornalísticos institucionais

Este trabalho se situa na fronteira entre as áreas de Comunicação Social e Linguística e é voltado à investigação das interações ocorridas nos espaços dedicados à publicação de comentários de leitores em quatro blogs jornalísticos institucionais: Blog do Noblat, Blog MiriamLeitão.com, Blog do Reinaldo Azevedo e Blog do Josias de Souza. Com ele, pretende-se definir como cada leitor utiliza seus comentários para se relacionar com o jornalista autor do blog (o blogueiro), com outros leitores que também publicam suas opiniões (os leitores-comentaristas) e com o tópico tratado no texto (postagem) escrito pelo blogueiro. Além disso, considerando que autores da área de Comunicação Social discutem os blogs como um dispositivo amplamente conversacional, o propósito desta pesquisa é também esclarecer, à luz dos princípios da Análise da Conversação, se efetivamente ocorre uma conversação entre os participantes no ambiente de troca de mensagens dos blogs. Para a realização do estudo, foi compilado um corpus de 400 comentários cujo conteúdo demonstra a visão crítica de leitores dos blogs acima citados acerca de um mesmo tema: o apagão ocorrido em 10 de novembro de 2009 em 18 estados brasileiros. Tais mensagens foram trabalhadas a partir de um método predominantemente qualitativo e interpretativo, sendo que uma abordagem quantitativa também foi considerada para permitir uma visão mais abrangente e comparativa dos dados. Na ausência de um referencial teórico da Linguística que abrangesse os fenômenos interacionais percebidos nos comentários dos blogs, optou-se por desenvolver uma proposta de análise de base empírica, que norteou todo o desenvolvimento do trabalho. Entre as conclusões preliminares da pesquisa, pode-se dizer que, ao mesmo tempo em que os blogs inauguraram uma nova forma de relacionamento entre o jornalista e sua audiência, há indícios de grande parte dos leitores utilizem os blogs como um espaço restrito à publicação de opiniões isoladas, em vez de enxergá-lo como um ambiente com amplas possibilidades interativas, e, consequentemente, propício à discussão

Eros adormecido : violência e laço social na interface entre literatura e psicanálise?

Esta pesquisa objetivou discutir a violência e o laço social, tomando como fonte de inspiração a relação com o semelhante, desvelada na obra de Rubem Fonseca. A literatura é apreendida como espaço ético no qual os processos de subjetivação são expressos e forjados, dando forma ao mal-estar que a psicanálise institui como próprio do existir humano. Considerando a violência constituinte do dualismo pulsional Eros-Tanatos, hipotetiza-se que as trocas sociais, na atualidade, efetuam-se pelo ódio indiferenciado ao outro, reificando-o e destituindo-o de sua singularidade. As personagens de Rubem Fonseca protagonizam, juntamente com o cenário urbano, a tragédia contemporânea na qual a melancolia parece ser a tônica da trama coletiva e os atos violentos despropositados contra o outro, uma forma de resposta contra a desvitalização e a impotência subjetivas. Em um universo social caracterizado pela retração dos poderes regeneradores e unificadores de Eros, a erótica predominante se afirma pela violência em relação ao próximo, não posto no lugar de parceiro na construção da coletividade.

Investigations of the conductor-semiconductor interface

I. Schottky barriers produced by polymeric sulfur nitride, (SN)_x, on nine common III-V and II-VI compound semiconductors are compared to barriers formed by Au. The conductor (SN)_x produces significantly higher barriers to n-type semiconductors and lower barriers to p-type semiconductors than Au, the most electronegative elemental metal. The barrier height improvement, defined as ɸ(SN)_x - ɸ(Au), is smaller on covalent semiconductors than on ionic semiconductors; (SN)x barriers follow the ionic-covalent transition. Details of (SN)_x film deposition, samples preparation, and barrier height measurements are described.

II. The rate of dissolution of amorphous Si into solid Al is measured. The rate of movement of the amorphous Si/Al interface is found to be much faster than predicted by a simple model of the transport of Si through Al. This result is related to defects in the growth of epitaxial Si using the solid phase epitaxy process.

Comment: Food web interactions and biomanipulation in Australian reservoirs

The authors have been studying the control of phytoplankton biomass in several Australian reservoirs. To manipulate fish communities in order to reduce phytoplankton biomass, one needs a thorough understanding of processes in the plankton-associated food webs. In contrast to the situation found in lakes of the northern hemisphere, the planktivorous fish of Australian reservoirs are relatively small and they may deplete small rather than large zooplankters, so that animals as large as the adults of Daphnia carinata may avoid predation. This would result in promotion of Daphnia, particularly if fish eliminate its smaller competitors. The aim of biomanipulation should be the establishment and maintenance of a proper ratio of planktivores/piscivores, adequate for water quality requirements. Successful selection of the appropriate ratio for a given reservoir will depend on the extent of our understanding of its food web interactions. For practical application of biomanipulation in management, further development of the food web theory under Australian conditions is needed.

Oxidation of Volatile Organic Compounds in Aqueous Solution and at the Air-water Interface of Aqueous Microdroplets

Isoprene (ISO),the most abundant non-methane VOC, is the major contributor to secondary organic aerosols (SOA) formation. The mechanisms involved in such transformation, however, are not fully understood. Current mechanisms, which are based on the oxidation of ISO in the gas-phase, underestimate SOA yields. The heightened awareness that ISO is only partially processed in the gas-phase has turned attention to heterogeneous processes as alternative pathways toward SOA.

During my research project, I investigated the photochemical oxidation of isoprene in bulk water. Below, I will report on the λ > 305 nm photolysis of H₂O₂ in dilute ISO solutions. This process yields C₁₀H₁₅OH species as primary products, whose formation both requires and is inhibited by O₂. Several isomers of C₁₀H₁₅OH were resolved by reverse-phase high-performance liquid chromatography and detected as MH⁺ (m/z = 153) and MH⁺-18 (m/z = 135) signals by electrospray ionization mass spectrometry. This finding is consistent with the addition of ·OH to ISO, followed by HO-ISO· reactions with ISO (in competition with O₂) leading to second generation HO(ISO)₂· radicals that terminate as C₁₀H₁₅OH via β-H abstraction by O₂.

It is not generally realized that chemistry on the surface of water cannot be deduced, extrapolated or translated to those in bulk gas and liquid phases. The water density drops a thousand-fold within a few Angstroms through the gas-liquid interfacial region and therefore hydrophobic VOCs such as ISO will likely remain in these relatively 'dry' interfacial water layers rather than proceed into bulk water. In previous experiments from our laboratory, it was found that gas-phase olefins can be protonated on the surface of pH < 4 water. This phenomenon increases the residence time of gases at the interface, an event that makes them increasingly susceptible to interaction with gaseous atmospheric oxidants such as ozone and hydroxyl radicals.

In order to test this hypothesis, I carried out experiments in which ISO(g) collides with the surface of aqueous microdroplets of various compositions. Herein I report that ISO(g) is oxidized into soluble species via Fenton chemistry on the surface of aqueous Fe(II)Cl₂ solutions simultaneously exposed to H₂O₂(g). Monomer and oligomeric species (ISO)1-8H⁺ were detected via online electrospray ionization mass spectrometry (ESI-MS) on the surface of pH ~ 2 water, and were then oxidized into a suite of products whose combined yields exceed ~ 5% of (ISO)1-8H⁺. MS/MS analysis revealed that products mainly consisted of alcohols, ketones, epoxides and acids. Our experiments demonstrated that olefins in ambient air may be oxidized upon impact on the surface of Fe-containing aqueous acidic media, such as those of typical to tropospheric aerosols.

Related experiments involving the reaction of ISO(g) with ·OH radicals from the photolysis of dissolved H₂O₂ were also carried out to test the surface oxidation of ISO(g) by photolyzing H₂O₂(aq) at 266 nm at various pH. The products were analyzed via online electrospray ionization mass spectrometry. Similar to our Fenton experiments, we detected (ISO)1-7H⁺ at pH < 4, and new m/z⁺ = 271 and m/z^- = 76 products at pH > 5.

Effects of self energy of the ions on the double layer structure and properties at the dielectric interface

Although numerous theoretical efforts have been put forth, a systematic, unified and predictive theoretical framework that is able to capture all the essential physics of the interfacial behaviors of ions, such as the Hofmeister series effect, Jones-Ray effect and the salt effect on the bubble coalescence remain an outstanding challenge. The most common approach to treating electrostatic interactions in the presence of salt ions is the Poisson-Boltzmann (PB) theory. However, there are many systems for which the PB theory fails to offer even a qualitative explanation of the behavior, especially for ions distributed in the vicinity of an interface with dielectric contrast between the two media (like the water-vapor/oil interface). A key factor missing in the PB theory is the self energy of the ion.

In this thesis, we develop a self-consistent theory that treats the electrostatic self energy (including both the short-range Born solvation energy and the long-range image charge interactions), the nonelectrostatic contribution of the self energy, the ion-ion correlation and the screening effect systematically in a single framework. By assuming a finite charge spread of the ion instead of using the point-charge model, the self energy obtained by our theory is free of the divergence problems and gives a continuous self energy across the interface. This continuous feature allows ions on the water side and the vapor/oil side of the interface to be treated in a unified framework. The theory involves a minimum set of parameters of the ion, such as the valency, radius, polarizability of the ions, and the dielectric constants of the medium, that are both intrinsic and readily available. The general theory is first applied to study the thermodynamic property of the bulk electrolyte solution, which shows good agreement with the experiment result for predicting the activity coefficient and osmotic coefficient.

Next, we address the effect of local Born solvation energy on the bulk thermodynamics and interfacial properties of electrolyte solution mixtures. We show that difference in the solvation energy between the cations and anions naturally gives rise to local charge separation near the interface, and a finite Galvani potential between two coexisting solutions. The miscibility of the mixture can either increases or decreases depending on the competition between the solvation energy and translation entropy of the ions. The interfacial tension shows a non-monotonic dependence on the salt concentration: it increases linearly with the salt concentration at higher concentrations, and decreases approximately as the square root of the salt concentration for dilute solutions, which is in agreement with the Jones-Ray effect observed in experiment.

Next, we investigate the image effects on the double layer structure and interfacial properties near a single charged plate. We show that the image charge repulsion creates a depletion boundary layer that cannot be captured by a regular perturbation approach. The correct weak-coupling theory must include the self-energy of the ion due to the image charge interaction. The image force qualitatively alters the double layer structure and properties, and gives rise to many non-PB effects, such as nonmonotonic dependence of the surface energy on concentration and charge inversion. The image charge effect is then studied for electrolyte solutions between two plates. For two neutral plates, we show that depletion of the salt ions by the image charge repulsion results in short-range attractive and long-range repulsive forces. If cations and anions are of different valency, the asymmetric depletion leads to the formation of an induced electrical double layer. For two charged plates, the competition between the surface charge and the image charge effect can give rise to like- charge attraction.

Then, we study the inhomogeneous screening effect near the dielectric interface due to the anisotropic and nonuniform ion distribution. We show that the double layer structure and interfacial properties is drastically affected by the inhomogeneous screening if the bulk Debye screening length is comparable or smaller than the Bjerrum length. The width of the depletion layer is characterized by the Bjerrum length, independent of the salt concentration. We predict that the negative adsorption of ions at the interface increases linearly with the salt concentration, which cannot be captured by either the bulk screening approximation or the WKB approximation. For asymmetric salt, the inhomogeneous screening enhances the charge separation in the induced double layer and significantly increases the value of the surface potential.

Finally, to account for the ion specificity, we study the self energy of a single ion across the dielectric interface. The ion is considered to be polarizable: its charge distribution can be self-adjusted to the local dielectric environment to minimize the self energy. Using intrinsic parameters of the ions, such as the valency, radius, and polarizability, we predict the specific ion effect on the interfacial affinity of halogen anions at the water/air interface, and the strong adsorption of hydrophobic ions at the water/oil interface, in agreement with experiments and atomistic simulations.

The theory developed in this work represents the most systematic theoretical technique for weak-coupling electrolytes. We expect the theory to be more useful for studying a wide range of structural and dynamic properties in physicochemical, colloidal, soft-matter and biophysical systems.