The study of oxygen spillover and back spillover on Pt/TiO2 by a potential dynamic sweep method

Oxygen spillover and back spillover on Pt/TiO2 catalysts have been studied by a potential dynamic sweep method. The characteristics of I-V profiles of Pt/TiO2 electrodes in the three potential sweep regions are different from those of Pt and TiO2 electrodes. The catalytic role of Pt/TiO2 in oxygen spillover and back spillover is identified. It decreases, and the electrochemical oxygen adsorption (or desorption) increases with elevating temperature of hydrogen post-treatment of Pt/TiO2; to a certain extent (hydrogen post-treatment of Pt/TiO2 at 700 degrees C), the control step of oxygen electrode process (anodic oxidation or cathodic reduction) changes from oxygen diffusion to electrochemical oxygen adsorption or desorption, respectively. Increasing the amount of Pt supported on TiO2 enhances the processes of oxygen spillover and back spillover. (C) 1999 Elsevier Science B.V. All rights reserved.

Role of bonding time and temperature on the physical properties of coupled anisotropic conductive–nonconductive adhesive film for flip chip on glass technology

Using thermosetting epoxy based conductive adhesive films for the flip chip interconnect possess a great deal of attractions to the electronics manufacturing industries due to the ever increasing demands for miniaturized electronic products. Adhesive manufacturers have taken many attempts over the last decade to produce a number of types of adhesives and the coupled anisotropic conductive-nonconductive adhesive film is one of them. The successful formation of the flip chip interconnection using this particular type of adhesive depends on, among factors, how the physical properties of the adhesive changes during the bonding process. Experimental measurements of the temperature in the adhesive have revealed that the temperature becomes very close to the required maximum bonding temperature within the first 1s of the bonding time. The higher the bonding temperature the faster the ramp up of temperature is. A dynamic mechanical analysis (DMA) has been carried out to investigate the nature of the changes of the physical properties of the coupled anisotropic conductive-nonconductive adhesive film for a range of bonding parameters. Adhesive samples that are pre-cured at 170, 190 and 210°C for 3, 5 and 10s have been analyzed using a DMA instrument. The results have revealed that the glass transition temperature of this type of adhesive increases with the increase in the bonding time for the bonding temperatures that have been used in this work. For the curing time of 3 and 5s, the maximum glass transition temperature increases with the increase in the bonding temperature, but for the curing time of 10s the maximum glass transition temperature has been observed in the sample which is cured at 190°C. Based on these results it has been concluded that the optimal bonding temperature and time for this kind of adhesive are 190°C and 10s, respectively.

Local examination of skin diffusion using FTIR spectroscopic imaging and multivariate target factor analysis

In the context of trans-dermal drug delivery it is very important to have mechanistic insight into the barrier function of the skin's stratum corneum and the diffusion mechanisms of topically applied drugs. Currently spectroscopic imaging techniques are evolving which enable a spatial examination of various types of samples in a dynamic way. ATR-FTIR imaging opens up the possibility to monitor spatial diffusion profiles across the stratum corneum of a skin sample. Multivariate data analyses methods based on factor analysis are able to provide insight into the large amount of spectroscopically complex and highly overlapping signals generated. Multivariate target factor analysis was used for spectral resolution and local diffusion profiles with time through stratum corneum. A model drug, 4-cyanophenol in polyethylene glycol 600 and water was studied. Results indicate that the average diffusion profiles between spatially different locations show similar profiles despite the heterogeneous nature of the biological sample and the challenging experimental set-up.

Laser annealing of sputtered silicon for wafer-bonding applications

Sputtered silicon is investigated as a bonding layer for transfer of pre-processed silicon layers to various insulating substrates. Although the material appears suitable for low temperature processing, previous work has shown that gas trapped in the pores of the sputtered material is released at temperatures above 350 degrees C and further increases of temperature lead to destruction of any bonded interface. Pre-annealing at 1000 degrees C before bonding drives out gas and/or seals the surface, but for device applications where processing temperatures must be kept below about 300 degrees C, this technique cannot be used. In the current work, we have investigated the effect of excimer laser-annealing to heat the sputtered silicon surface to high temperature whilst minimising heating of the underlying substrate. Temperature profile simulations are presented and the results of RBS, TEM and AFM used to characterise the annealed layers. The results verify that gases are present in the sub-surface layers and suggest that while sealing of the surface is important for suppression of the out-diffusion of gases, immediate surface gas removal may also play a role. The laser-annealing technique appears to be an effective method of treating sputtered silicon, yielding a low roughness surface suitable for wafer bonding, thermal splitting and layer transfer.

Microstructure evolution of 6061 O Al alloy during ultrasonic consolidation:An insight from electron backscatter diffraction

6061 O Al alloy foils were welded to form monolithic and SiC fibre-embedded samples using the ultrasonic consolidation (UC) process. Contact pressures of 135, 155 and 175 MPa were investigated at 20 kHz frequency, 50% of the oscillation amplitude, 34.5 mm s sonotrode velocity and 20 °C. Deformed microstructures were analysed using electron backscatter diffraction (EBSD). At all contact pressures deformation occurs by non-steady state dislocation glide. Dynamic recovery is active in the upper and lower foils. Friction at the welding interface, instantaneous internal temperatures (0.5-0.8 of the melting temperature, T), contact pressure and fast strain rates result in transient microstructures and grain size reduction by continuous dynamic recrystallization (CDRX) within the bonding zone. Bonding occurs by local grain boundary migration, which allows diffusion and atom interlocking across the contact between two clean surfaces. Textures weaken with increasing contact pressure due to increased strain hardening and different grain rotation rates. High contact pressures enhance dynamic recovery and CDRX. Deformation around the fibre is intense within 50 μm and extends to 450 μm from it. © 2009 Acta Materialia Inc.

Dynamic properties of bright points in an active region

Context. Bright points (BPs) are small-scale, magnetic features ubiquitous across the solar surface. Previously, we have observed and noted their properties for quiet Sun regions. Here, we determine the dynamic properties of BPs using simultaneous quiet Sun and active region data.

Aims. The aim of this paper is to compare the properties of BPs in both active and quiet Sun regions and to determine any difference in the dynamics and general properties of BPs as a result of the varying magnetic activity within these two regions.

Methods. High spatial and temporal resolution G-band observations of active region AR11372 were obtained with the Rapid Oscillations in the Solar Atmosphere instrument at the Dunn Solar Telescope. Three subfields of varying polarity and magnetic flux density were selected with the aid of magnetograms obtained from the Helioseismic and Magnetic Imager on board the Solar Dynamics Observatory. Bright points within these subfields were subsequently tracked and analysed.

Results. It is found that BPs within active regions display attenuated velocity distributions with an average horizontal velocity of ~0.6 km s-1, compared to the quiet region which had an average velocity of 0.9 km s-1. Active region BPs are also ~21% larger than quiet region BPs and have longer average lifetimes (~132 s) than their quiet region counterparts (88 s). No preferential flow directions are observed within the active region subfields. The diffusion index (γ) is estimated at ~1.2 for the three regions.

Conclusions. We confirm that the dynamic properties of BPs arise predominately from convective motions. The presence of stronger field strengths within active regions is the likely reason behind the varying properties observed. We believe that larger amounts of magnetic flux will attenuate BP velocities by a combination of restricting motion within the intergranular lanes and by increasing the number of stagnation points produced by inhibited convection. Larger BPs are found in regions of higher magnetic flux density and we believe that lifetimes increase in active regions as the magnetic flux stabilises the BPs.

Diffusion coefficients in dense and supercritical fluids

Os coeficientes de difusão (D 12) são propriedades fundamentais na investigação e na indústria, mas a falta de dados experimentais e a inexistência de equações que os estimem com precisão e confiança em fases comprimidas ou condensadas constituem limitações importantes. Os objetivos principais deste trabalho compreendem: i) a compilação de uma grande base de dados para valores de D 12 de sistemas gasosos, líquidos e supercríticos; ii) o desenvolvimento e validação de novos modelos de coeficientes de difusão a diluição infinita, aplicáveis em amplas gamas de temperatura e densidade, para sistemas contendo componentes muito distintos em termos de polaridade, tamanho e simetria; iii) a montagem e teste de uma instalação experimental para medir coeficientes de difusão em líquidos e fluidos supercríticos. Relativamente à modelação, uma nova expressão para coeficientes de difusão a diluição infinita de esferas rígidas foi desenvolvida e validada usando dados de dinâmica molecular (desvio relativo absoluto médio, AARD = 4.44%) Foram também estudados os coeficientes de difusão binários de sistemas reais. Para tal, foi compilada uma extensa base de dados de difusividades de sistemas reais em gases e solventes densos (622 sistemas binários num total de 9407 pontos experimentais e 358 moléculas) e a mesma foi usada na validação dos novos modelos desenvolvidos nesta tese. Um conjunto de novos modelos foi proposto para o cálculo de coeficientes de difusão a diluição infinita usando diferentes abordagens: i) dois modelos de base molecular com um parâmetro específico para cada sistema, aplicáveis em sistemas gasosos, líquidos e supercríticos, em que natureza do solvente se encontra limitada a apolar ou fracamente polar (AARDs globais na gama 4.26-4.40%); ii) dois modelos de base molecular biparamétricos, aplicáveis em todos os estados físicos, para qualquer tipo de soluto diluído em qualquer solvente (apolar, fracamente polar e polar). Ambos os modelos dão origem a erros globais entre 2.74% e 3.65%; iii) uma correlação com um parâmetro, específica para coeficientes de difusão em dióxido de carbono supercrítico (SC-CO2) e água líquida (AARD = 3.56%); iv) nove correlações empíricas e semi-empíricas que envolvem dois parâmetros, dependentes apenas da temperatura e/ou densidade do solvente e/ou viscosidade do solvente. Estes últimos modelos são muito simples e exibem excelentes resultados (AARDs entre 2.78% e 4.44%) em sistemas líquidos e supercríticos; e v) duas equações preditivas para difusividades de solutos em SC-CO2, em que os erros globais de ambas são inferiores a 6.80%. No global, deve realçar-se o facto de os novos modelos abrangerem a grande variedade de sistemas e moléculas geralmente encontrados. Os resultados obtidos são consistentemente melhores do que os obtidos com os modelos e abordagens encontrados na literatura. No caso das correlações com um ou dois parâmetros, mostrou-se que estes mesmos parâmetros podem ser ajustados usando um conjunto muito pequeno de dados, e posteriormente serem utilizados na previsão de valores de D 12 longe do conjunto original de pontos. Uma nova instalação experimental para medir coeficientes de difusão binários por técnicas cromatográficas foi montada e testada. O equipamento, o procedimento experimental e os cálculos analíticos necessários à obtenção dos valores de D 12 pelo método de abertura do pico cromatográfico, foram avaliados através da medição de difusividades de tolueno e acetona em SC-CO2. Seguidamente, foram medidos coeficientes de difusão de eucaliptol em SC-CO2 nas gamas de 202 – 252 bar e 313.15 – 333.15 K. Os resultados experimentais foram analisados através de correlações e modelos preditivos para D12.

Valuing equity-linked death benefits in jump diffusion models

The paper is motivated by the valuation problem of guaranteed minimum death benefits in various equity-linked products. At the time of death, a benefit payment is due. It may depend not only on the price of a stock or stock fund at that time, but also on prior prices. The problem is to calculate the expected discounted value of the benefit payment. Because the distribution of the time of death can be approximated by a combination of exponential distributions, it suffices to solve the problem for an exponentially distributed time of death. The stock price process is assumed to be the exponential of a Brownian motion plus an independent compound Poisson process whose upward and downward jumps are modeled by combinations (or mixtures) of exponential distributions. Results for exponential stopping of a Lévy process are used to derive a series of closed-form formulas for call, put, lookback, and barrier options, dynamic fund protection, and dynamic withdrawal benefit with guarantee. We also discuss how barrier options can be used to model lapses and surrenders.

Le recours à des environnements numériques pour la diffusion de connaissances relatives au patrimoine bâti: une exploration du potentiel de la modélisation de systèmes typologiques

Un fichier intitulé Charbonneau_Nathalie_2008_AnimationAnnexeT accompagne la thèse. Il contient une séquence animée démontrant le type de parcours pouvant être effectué au sein des environnements numériques développés. Il s'agit d'un fichier .wmv qui a été compressé.

Espacer l'organisation : trajectoires d'un projet de diffusion de la science et de la technologie au Chili

Comprendre le mode d’existence de l’organisation est certainement l’un des plus grands défis que se sont donnés les chercheurs qui s’intéressent à ce domaine d’étude. La littérature nous présente ainsi plusieurs images, métaphores et perspectives qui, combinées, dressent un portrait hybride de ce type de collectif. Je propose, dans cette thèse, de reconnaître et exploiter ce caractère hybride de l’organisation en partant d’une réflexion centrée sur l'espace. En m’inspirant particulièrement des travaux de la géographe Doreen Massey (1999, 2005), le concept d'espace auquel je souscris est celui d’un espace ouvert et dynamique (qui incorpore le temps), basé sur une relationalité matérielle et hétérogène, supposant des acteurs humains et non humains en interaction. L'espace peut donc être compris comme la coexistence d’ontologies hétérogènes, ce que Massey (2005) nomme une coexistence de trajectoires comme stories-so-far. Il s’agit ici d’une vision performative de l’espace organisationnel qui est constitué dans la relation de trajectoires distinctes qui coexistent, se rencontrent, s’affectent, entrent en conflit ou coopèrent (Massey, 1999). Je postule que pour assurer une certaine continuité et cohérence dans la coexistence de trajectoires hétérogènes, un travail d’alignement et d’ordonnancement est mis à l’oeuvre, et ce, par le suivi d’une trajectoire principale — ce que je nomme une trajectoire scriptée. Suivre cette trajectoire permet ainsi à l’organisation de s’étendre, de se rendre présente dans le temps et dans l’espace, sans pour autant perdre son identité : to be here and there at the same time, now and then at the same place. À partir de cette définition de l’espace, je propose d’« espacer l’organisation », et plus particulièrement d’« espacer » Explora, un programme d’éducation non formelle du gouvernement du Chili visant la diffusion et la valorisation de la science et de la technologie. Cette proposition est double : elle renvoie aux pratiques d’espacements — des pratiques hybrides, collectives et situées — des agents organisationnels (dans ce cas, aux pratiques des agents d’Explora impliqués dans l’organisation d’un projet, celui de la Semaine de la science 2006),mais aussi à une pratique de recherche. « Espacer l’organisation » veut donc dire déployer ces espaces pleins, déplier l’organisation, accroître la série des simultanéités-successions pour ainsi créer plus d’espace-temps.

Action collective patronale : les mécanismes de diffusion entre les niveaux sectoriel et local

Cette recherche s'intéresse à l'acteur patronal organisé, encore peu étudié en Amérique du Nord. Pourtant, cet acteur est fortement organisé au Québec et il exerce une influence reconnue sur les politiques publiques et les relations industrielles. Cette recherche vise à mieux comprendre la logique d’action des employeurs et les lieux où ils exercent leur influence. Plus important encore, la recherche s’interroge sur les mécanismes de diffusion utilisés par les associations patronales pour transmettre à leurs membres des orientations et des lignes directrices à adopter. Tout comme pour l’acteur syndical qui doit développer sa capacité représentative (Dufour, Hege, Levesque et Murray, 2009), nous croyons qu’il en est de même pour l’acteur patronal. Bref, cette étude cherche à comprendre comment les associations patronales vont s'assurer que leurs membres adoptent des pratiques en lien avec les positions défendues dans les institutions du marché du travail et dans la sphère des politiques publiques. Notre question de recherche est la suivante : Quels sont les mécanismes développés par les associations patronales pour diffuser leurs orientations en matière de politiques publiques et de relations du travail en vue d’influencer les pratiques locales de gestion de leurs membres? Au plan théorique, cette étude mobilise les idées développées par les approches néo-institutionnalistes pour mieux expliquer comment les acteurs vont utiliser les institutions en place pour façonner les règles dans leurs intérêts, ce qui suppose d’abord une capacité de représentation et une cohérence dans les actions entre les niveaux où se situent l’acteur. On cherche à comprendre comment les associations peuvent coordonner les actions patronales en réaction aux changements qui s’opèrent dans l’environnement institutionnel. Les associations patronales sont des entrepreneurs institutionnels (Crouch, 2005) qui sont à la recherche active d’opportunités et de leviers de pouvoir à utiliser pour maximiser leurs intérêts de leurs membres et par la même occasion, réduire les incertitudes en provenance de l’environnement (Campbell, 2004; Streeck et Thelen, 2005; Crouch, 2005). Toujours au niveau théorique, cette étude se base sur les idées avancées par la sociologie des logiques d’action. Cette approche théorique nous permet de rendre compte des niveaux sectoriel et local où s’enracinent les comportements des employeurs. Au niveau sectoriel, il existe une pluralité d’instances qui contribuent à façonner les logiques d’actions des associations patronales. La sociologie des logiques d’actions nous permet d’envisager l’association patronale comme un groupe qui dispose d’une vie qui lui est propre avec une relative autonomie de fonctionnement. La capacité d’influence de l’association serait tributaire des mécanismes de coordination de l’action utilisés pour susciter l’accord au sein du groupe. Les mécanismes de coordination de l’action devraient permettre une connexion régulière et stable entre l’association et ses membres. Cette recherche s’intéresse aux associations patronales qui ont recours à un ensemble de moyens pour diffuser les orientations privilégiées aux entreprises membres. Au plan empirique, cette recherche propose de répondre aux trois objectifs suivants : (1) mieux comprendre les formes d’organisation patronales dans les mines au Québec; (2) mieux saisir la structure et la logique d’action des associations patronales sur les politiques publiques, les relations de travail et le marché du travail et finalement (3) mieux comprendre les mécanismes développés par les associations patronales pour diffuser leurs orientations en vue d’influencer les pratiques locales de gestion de leurs membres. Pour atteindre nos objectifs de recherche, nous avons utilisé une méthodologie qualitative de recherche soit une étude de cas du secteur des mines au Québec. Cette dernière a été conduite en trois étapes : la préparation, la collecte des données et l’interprétation (Merriam, 1998). Les données de cette étude ont été recueillies à l’hiver 2012, par le biais d’entretiens semi-directifs auprès de gestionnaires d’entreprises minières et de dirigeants d’associations minières. Une analyse qualitative du contenu de ces entrevues a été effectuée en lien avec la revue de littérature et nos propositions de recherche. À cette fin, nous avons utilisé la technique de l’appariement logique de Yin (1994), ce qui nous a permis de comparer nos observations à nos propositions de recherche. Au niveau des résultats, nous avons pu constater que les associations patronales du secteur des mines au Québec, endossent davantage le rôle de porte-parole de l’industrie auprès du gouvernement que celui de développeur de services aux membres. Les actions des associations patronales s’exercent à tous les niveaux décisionnels afin d’assurer la meilleure promotion possible des intérêts des employeurs. La représentation politique représente le champ d’activité le plus important qui compose la logique d’action des associations patronales de la filière minérale québécoise. Mentionnons également que la représentation des intérêts des entreprises auprès du public et des médias est également vitale à l’action collective patronale dans un souci d’acceptabilité sociale. Les associations d’employeurs vont tenter principalement d’influencer les pratiques en relations industrielles qui permettent d’assurer une meilleure image de l’industrie et qui sont jugées prioritaires en fonction du contexte institutionnel en place. La recherche nous a permis d’observer un impact favorable et significatif à la capacité de diffusion pour cinq des sept mécanismes de diffusion faisant partie de notre modèle d’analyse. Trois de ces cinq mécanismes favorisent la capacité de diffusion descendante (transposition de la logique d’action sectorielle sur les pratiques locales des membres) et les deux autres favorisent plutôt la capacité de diffusion ascendante (transposition des enjeux locaux jugés prioritaires sur la logique d’action sectorielle). Les mécanismes qui supportent au mieux la cohésion au sein de l’association sont ceux qui impliquent une relation dynamique entre les représentants et les membres et entre les membres eux-mêmes d’où la pertinence d’une diffusion descendante et ascendante des orientations. Il est à noter qu’étant donné que cette recherche consiste en une étude de cas, des limites méthodologiques liées à la généralisation des résultats sont présentes. Il n’est pas aisé d’affirmer que les résultats de cette microanalyse soient généralisables en raison des spécificités du secteur à l’étude. En contrepartie, les analyses ont servi à l’élaboration d’un modèle qui pourra être utilisé dans des études futures.

Front spreading in population dynamic models. Theory and application to the Neolithic transition

This thesis presents population dynamics models that can be applied to predict the rate of spread of the Neolithic transition (change from hunter-gathering to farming economics) across the European continent, which took place about 9000 to 5000 years ago. The first models in this thesis provide predictions at a continental scale. We develop population dynamics models with explicit kernels and apply realistic data. We also derive a new time-delayed reaction-diffusion equation which yields speeds about a 10% slower than previous models. We also deal with a regional variability: the slowdown of the Neolithic front when reaching the North of Europe. We develop simple reaction-diffusion models that can predict the measured speeds in terms of the non-homogeneous distribution of pre-Neolithic (Mesolithic) population in Europe, which were present in higher densities at the North of the continent. Such models can explain the observed speeds.

Influence of mass diffusion in sea ice dynamical models

The mixing of floes of different thickness caused by repeated deformation of the ice cover is modeled as diffusion, and the mass balance equation for sea ice accounting for mass diffusion is developed. The effect of deformational diffusion on the ice thickness balance is shown to reach 1% of the divergence effect, which describes ridging and lead formation. This means that with the same accuracy the mass balance equation can be written in terms of mean velocity rather than mean mass-weighted velocity, which one should correctly use for a multicomponent fluid such as sea ice with components identified by floe thickness. Mixing (diffusion) of sea ice also occurs because of turbulent variations in wind and ocean drags that are unresolved in models. Estimates of the importance of turbulent mass diffusion on the dynamic redistribution of ice thickness are determined using empirical data for the turbulent diffusivity. For long-time-scale prediction (≫5 days), where unresolved atmospheric motion may have a length scale on the order of the Arctic basin and the time scale is larger than the synoptic time scale of atmospheric events, turbulent mass diffusion can exceed 10% of the divergence effect. However, for short-time-scale prediction, for example, 5 days, the unresolved scales are on the order of 100 km, and turbulent diffusion is about 0.1% of the divergence effect. Because inertial effects are small in the dynamics of the sea ice pack, diffusive momentum transfer can be disregarded.

On the role of specific interactions in the diffusion of nanoparticles in aqueous polymer solutions

Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(Nvinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions.

Anomalous dependence on the diffusion coefficients of the ionic relaxation time in electrolytes

We show, by using a numerical analysis, that the dynamic toward equilibrium for an electrolytic cell subject to a step-like external electric field is a multirelaxation process when the diffusion coefficients of positive and negative ions are different. By assuming that the diffusion coefficient of positive ions is constant, we observe that the number of involved relaxation processes increases when the diffusion coefficient of the negative ions diminishes. Furthermore, two of the relaxation times depend nonmonotonically on the ratio of the diffusion coefficients. This result is unexpected, because the ionic drift velocity, by means of which the ions move to reach the equilibrium distribution, increases with increasing ionic mobility.