Understanding the CO Preoxidation and the Intrinsic Catalytic Activity of Step Sites in Stepped Pt Surfaces in Acidic Medium

In order to deepen the knowledge about the origin of the CO preoxidation process and the intrinsic catalytic activity of Pt superficial steps toward CO oxidation, a series of CO stripping experiments were performed on stepped Pt electrodes in acidic medium. For the occurrence of CO preoxidation, it was found that it arises (reproducibly) whenever four interconnected conditions are simultaneously fulfilled: (1) CO adsorption at potentials lower than about 0.2 V; (2) on surfaces saturated with COads; (3) in the presence of traces of CO in solution; (4) in the presence of surface steps. If any of these four conditions is not satisfied, the CO preoxidation pathway does not appear, even though the steps on the electrode surface are completely covered by CO. By controlling the removal of the CO adlayer (voltammetrically), we show that once the CO adlayer has been partially oxidized, the (111) terrace sites of stepped surfaces are released earlier than the (110) step sites. Moreover, if (110) steps are selectively decorated with CO, its oxidation occurs only at potentials ∼150 mV higher than the CO preoxidation peak. Our results systematically demonstrate that step sites are less active to oxidize CO than those ones responsible for the CO preoxidation process. Once the sites responsible for the CO preoxidation are made free, there is no apparent motion of the remaining adsorbed CO layer, suggesting that the activation of the surface controls the whole process, rather than the diffusion of COads toward hypothetically “most active sites”. Voltammetric and chronoamperometric experiments performed on partially covered CO adlayers suggest that adsorbed CO behave as a motionless species during its oxidation, in which the CO adlayer is removed piece by piece. By means of in situ FTIR experiments, the stretching frequency of CO selectively adsorbed on (110) step sites was examined. Band frequency results confirm that those molecules adsorbed on steps are fully coupled with the adsorbed CO on (111) terraces when the surface reaches full coverage.

Influence of alkylphosphonic acid grafting on the electronic and magnetic properties of La2/3Sr1/3MnO3 surfaces

Self-assembled monolayers (SAMs) are highly promising materials for molecular engineering of electronic and spintronics devices thanks to their surface functionalization properties. In this direction, alkylphosphonic acids have been used to functionalize the most common ferromagnetic electrode in organic spintronics: La2/3Sr1/3MnO3 (LSMO). However, a study on the influence of SAMs grafting on LSMO electronic and magnetic properties is still missing. In this letter, we probe the influence of alkylphosphonic acids-based SAMs on the electronic and magnetic properties of the LSMO surface using different spectroscopies. We observe by X-ray photoemission and X-ray absorption that the grafting of the molecules on the LSMO surface induces a reduction of the Mn oxidation state. Ultraviolet photoelectron spectroscopy measurements also show that the LSMO work function can be modified by surface dipoles opening the door to both tune the charge and spin injection efficiencies in organic devices such as organic light-emitting diodes.

Les grandes surfaces suivi de La logique du seuil ou la problématique de l’altérité dans Autoportraits de Marie Uguay et Nombreux seront nos ennemis de Geneviève Desrosiers

Les recueils de poésie Autoportraits de Marie Uguay et Nombreux seront nos ennemis de Geneviève Desrosiers appartiennent tous deux au genre de l’intimisme. Celui-ci est principalement caractérisé par une observation rapprochée du quotidien. Mon projet est constitué de deux volets : une recherche sur l’intimisme chez Uguay et Desrosiers, ainsi qu’un projet de création inspiré de leur poésie. Dans le volet recherche de mon mémoire, je me penche sur la logique du seuil et les rapports problématiques à l’altérité dans ces deux recueils. Dans Autoportraits et Nombreux seront nos ennemis, la position en retrait ou sur le seuil du « Je » permet d’observer ce qui l’entoure en conservant une perspective intime confortable où il ne se retrouve pas confronté à l’altérité. Les poèmes de la partie création de mon mémoire témoignent de l’inventivité dont le « Je » fait preuve afin d’échapper à son quotidien et sont empreints d’une perméabilité entre rêve et réalité. Le quotidien statique se présente comme un piège, un enfermement. La tension entre l’ici et l’ailleurs est exprimée dans les textes par une logique de l’attente; celle d’un nouveau départ et de la réalisation du rêve. Par cette pratique, je souhaite jouer avec les dangers de l’intimisme : ceux d’un narcissisme ou d’un sentimentalisme exacerbés.

Les grandes surfaces suivi de La logique du seuil ou la problématique de l’altérité dans Autoportraits de Marie Uguay et Nombreux seront nos ennemis de Geneviève Desrosiers

Les recueils de poésie Autoportraits de Marie Uguay et Nombreux seront nos ennemis de Geneviève Desrosiers appartiennent tous deux au genre de l’intimisme. Celui-ci est principalement caractérisé par une observation rapprochée du quotidien. Mon projet est constitué de deux volets : une recherche sur l’intimisme chez Uguay et Desrosiers, ainsi qu’un projet de création inspiré de leur poésie. Dans le volet recherche de mon mémoire, je me penche sur la logique du seuil et les rapports problématiques à l’altérité dans ces deux recueils. Dans Autoportraits et Nombreux seront nos ennemis, la position en retrait ou sur le seuil du « Je » permet d’observer ce qui l’entoure en conservant une perspective intime confortable où il ne se retrouve pas confronté à l’altérité. Les poèmes de la partie création de mon mémoire témoignent de l’inventivité dont le « Je » fait preuve afin d’échapper à son quotidien et sont empreints d’une perméabilité entre rêve et réalité. Le quotidien statique se présente comme un piège, un enfermement. La tension entre l’ici et l’ailleurs est exprimée dans les textes par une logique de l’attente; celle d’un nouveau départ et de la réalisation du rêve. Par cette pratique, je souhaite jouer avec les dangers de l’intimisme : ceux d’un narcissisme ou d’un sentimentalisme exacerbés.

3D-form metrology of arbitrary optical surfaces by absorption in fluids

We present an imaging technique for the 3D-form metrology of optical surfaces. It is based on the optical absorption in fluids situated between the surface and a reference. An improved setup with a bi-chromatic light source is fundamental to obtain reliable topographic maps. It is able to measure any surface finish (rough or polished), form and slope and independently of scale. We present results focused on flat and spherical optical surfaces, arrays of lenses and with different surface finish (rough-polished). We achieve form accuracies from several nanometers to sub-lambda for sag departures from tens to hundred of microns. Therefore, it seems suitable for the quality control in the production of precision aspheric, freeform lenses and other complex shapes on transparent substrates, independently of the surface finish.

Étude des phénomènes d'entartrage de la gibbsite sur les surfaces métalliques

Le procédé Bayer est cyclique et il permet d'extraire les hydrates d'alumine, contenu dans le minerai de bauxite. L'alumine est la matière première nécessaire pour la production de l'aluminium métallique par le procédé d'électrolyse. La solubilisation des hydrates d'alumine est effectuée dans une solution d'hydroxyde de sodium concentrée, liqueur Bayer, à haute température et pression. Il existe deux types de procédé : un procédé dit à basse température (150ÀC) et un procédé dit haute température (250ÀC). Selon la température utilisée, certaines impuretés présentes dans la bauxite vont être solubilisées comme par exemple la silice, le fer ou le titane. Comme le procédé est basé sur la solubilisation puis sur la précipitation des hydrates d'alumine, la solution est chauffée puis refroidie par une série d'échangeurs de chaleur. Ces changements de température impliquent des variations dans les conditions de saturation et sursaturation ce qui va conséquemment causer la formation de tartre dans le procédé. Selon la température du procédé utilisé, la composition chimique du tartre formé peut être différente. Dans le but d'inhiber partiellement ou totalement la cristallisation de la gibbsite, ou hydrate d'alumine, sur les surfaces métalliques, la compréhension des paramètres influençant sa formation est nécessaire. L'un des moyens de réduire ou d'inhiber la formation du tartre est de modifier les énergies de surface entre les surfaces métalliques et la solution de liqueur Bayer. Pour ce faire, des métaux ayant des propriétés différentes seront étudiés en entartrage et des composés organiques seront ajoutées à la solution d'hydroxyde de sodium afin de modifier l'interface entre ces métaux et la solution. L'influence des hydrates d'alumine et des différents composés organiques sur les métaux sera déterminer [i.e. déterminée] par des mesures d'isothermes d'adsorption, de potentiels zêta et d'angles de contact, dans le but d'établir une corrélation entre l'interface métal/solution et les temps de nucléation mesurés en entartrage. Un deuxième volet consiste en la fabrication d'un montage en laboratoire permettant d'effectuer la formation reproductible du tartre de freudenbergite. La freudenbergite est un tartre à base de titane qui se forme dans le procédé à haute température. Cette étude démontre que la formation du tartre dans le procédé Bayer est un phénomène de formation de cristaux de gibbsite en solution qui vont adhérer aux défauts de surfaces des surfaces métalliques. En ce sens, la rugosité de surface des métaux est le facteur déterminant pour la formation du tartre dans le procédé Bayer. Des tests d'entartrage réalisés au laboratoire sur cinq métaux différents démontrent une corrélation évidente entre la rugosité de surface, mesurée par microscope à force atomique, et les temps de nucléation obtenus en entartrage. Les mesures d'interactions interfaciales des aluminates de sodium sur les métaux étudiés, en présence ou non de composés organiques, ne permettent pas d'établir de corrélation avec les temps de nucléation obtenus en entartrage. Par contre, l'allongement de l'entartrage en présence de gluconate et de tartrate de sodium, des composés inhibiteurs de croissance des cristaux de gibbsite, confirme le phénomène de formation du tartre par des cristaux formés en solution. La croissance des cristaux de tartre étant partiellement inhibée, les temps de nucléation vont être allongés lors des tests d'entartrage. À l'inverse, l'EDTA favorise la formation de plusieurs cristaux en solution, ce qui diminue significativement la vitesse d'entartrage lorsqu'elle est ajoutée dans la liqueur Bayer. Afin de confirmer que la rugosité de surface est le facteur prédominant dans la formation du tartre dans le procédé Bayer, dans nos conditions de laboratoire, des tests d'entartrage sont effectués sur une surface d'or recouverte d'une monocouche d'alcane thiols. Ces tests démontrent que le changement de nature de la surface d'or ne permet pas de changer significativement le temps de nucléation de l'or dans nos conditions d'entartrage. Un montage expérimental comportant un four et quatre autoclaves, contrôlé par un système informatique a permis d'effectuer la formation de tartre de freudenbergite de façon reproductible au laboratoire.

Acoustic Propagation over Periodic and Quasi-Period Rough Surfaces Proceedings

Numerical techniques such as the Boundary Element Method, Finite Element Method and Finite Difference Time Domain have been used widely to investigate plane and curved wave-front scattering by rough surfaces. For certain shapes of roughness elements (cylinders, semi-cylinders and ellipsoids) there are semi-analytical alternatives. Here, we present a theory for multiple scattering by cylinders on a hard surface to investigate effects due to different roughness shape, the effects of vacancies and variation of roughness element size on the excess attenuation due to a periodically rough surfaces.

Zonage viticole des surfaces potentielles dans la valle centrale de Tarija, Bolivie.

La présente étude de zonage viticole a été faite dans la région de la vallée Central de Tarija(VCT), dans la ville de Tarija, au Sud de la Bolivie; une région avec plus de 400 années de tradition qui présente une vitiviniculture de haute qualité. La Vallée possède une surface total de 332 milles ha.; existant des vignobles entre 1660 y 2300 m.s.n.m. et dans ce rang d?altitude il existe 91 mille ha. avec un haut potentiel pour la culture de la vigne. Pour la détermination des surfaces homogènes de la région ont été considérés les aspects d?environnement avec l?aide d?images satellitaires, des cartes topographiques, des données climatologiques et des cartes géologiques ; pour déterminer les caractéristiques de la région pour la culture de la vigne. Au niveau climatique furent appliqués les indices du Système CCM Géo viticole développés par Tonietto & Carbonneau (2004), lesquelles considèrent des éléments thermiques (Indice Héliothermique), hydriques (Indice de sécheresse) et nictothermiques (Indice de Froid nocturne); nous avons identifié 8 types des climats différents dans toute la région. Dans les particularités du sol furent déterminés la morphologie et il a été géo référencié tous ses caractéristiques (analyses chimique et physique). S?ai fait une classification spécifique des critères de culture de la vigne pour déterminer l?aptitude du sol, en même temps ont été identifié les surfaces avec des limitants pour le conduit des vignobles. L?étude a pour objectif d?identifié les zones potentielles pour la culture de la vigne et de cette façon orienté son élargissement avec le support des politiques d?état et pertinente assistance technique au producteurs de cette région. MOTS CLES: Zonage ? grappe ? viticulture d?altitude ? altitude - Système CCM ? aptitude ? Bolivie

PM and material decay: analysis of dry depositions on horizontal and vertical surrogate surfaces through a Deposition Box system

Airborne Particulate Matter (PM), can get removed from the atmosphere through wet and dry mechanisms, and physically/chemically interact with materials and induce premature decay. The effect of dry depositions is a complex issue, especially for outdoor materials, because of the difficulties to collect atmospheric deposits repeatable in terms of mass and homogeneously distributed on the entire investigated substrate. In this work, to overcome these problems by eliminating the variability induced by outdoor removal mechanisms (e.g. winds and rainfalls), a new sampling system called ‘Deposition Box’, was used for PM sampling. Four surrogate materials (Cellulose Acetate, Regenerated Cellulose, Cellulose Nitrate and Aluminum) with different surfaces features were exposed in the urban-marine site of Rimini (Italy), in vertical and horizontal orientations. Homogeneous and reproducible PM deposits were obtained and different analytical techniques (IC, AAS, TOC, VP-SEM-EDX, Vis-Spectrophotometry) were employed to characterize their mass, dimension and composition. Results allowed to discriminate the mechanisms responsible of the dry deposition of atmospheric particles on surfaces with different nature and orientation and to determine which chemical species, and in which amount, tend to preferentially deposit on them. This work demonstrated that “Deposition Box” can represent an affordable tool to study dry deposition fluxes on materials and results obtained will be fundamental in order to extend this kind of exposure to actual building and heritage materials, to investigate the PM contribution in their decay.

Excited state energy surfaces of flexible emitters for thermally activated delayed fluorescence

Organic Light-Emitting Diodes (OLEDs) technology has matured over recent years, reaching the commercialization level and being used in various applications. The required efficiency can be achieved by transforming triplet excitons into singlet states via Reverse InterSystem Crossing (RISC), which a general mechanism called thermally activated delayed fluorescence (TADF). Two prototypical molecules in the field, 2CzBN and 4CzBN, Carbazole Benzonitrile (donor-acceptor) derivatives, possess similar energy gap between singlet and triplet (∆EST, a key parameter in the RISC rate), but different TADF performance. In this sense, other parameter must be considered to explain these different behaviors. In this work, we theoretically investigate 2CzBN and 4CzBN and address the problem of how flexible donor-acceptor (D-A) or donor-acceptor-donor (D-A-D) molecular architectures affect the nature of excited state, and the oscillator strength. Furthermore, we analyze the RISC rates as a function of the conformation of the carbazole side groups, considering the S0, S1, T1 and T2 states. The oscillator strength of 4CzBN is higher than of 2CzBN, which, in turn, is almost vanishing, resulting in only 4CzBN being a TADF active molecule. We also note the presence of a second triplet state T2 lower in energy than S1, and that the reorganization energies, associated to the RISC processes involving T1 and T2, are both important factor in differentiating the rates in 2CzBN and 4CzBN. However, the 4CzBN RISC rate from T2 to S1 is surprisingly high with respect to the one from T1 to S1, although, according to EL-Sayed rules, since T2 (CT/LE) is more similar to S1 (CT) than in 2CzBN (LE, CT), this transition should be less favored. These insights are important to understand the photophysics of the TADF process and to design novel TADF emitters based on the benzo-carbazole architecture.

Biomimetic surfaces for greener coastal infrastructures: an analysis of factors that contribute to make artificial structures more “natural”

The growing ecological awareness of Ocean Sprawl impacts is promoting the adoption of eco-engineering strategies to enhance the ecological performance of coastal infrastructures. Biomimicry, as an eco-engineering tool, aims to design infrastructure more suitable for wildlife by manipulating structural factors to mimic natural habitats. However, little is known about the extent to which natural and artificial substrates differ in their structure and to what extent such differences affect the biota. To fill these knowledge gaps and consequently design biomimetic surfaces, I initially explored how much physical structure diverges between various types of natural and artificial substrates and tested to what extent differences in physical structure and material composition affect the epibenthic communities. By mean of an in-field mensurative experiment and a systematic review coupled with a meta-analysis, I found that, although communities tended to differ between natural and artificial coastal habitats, both physical structure and material composition reported an overall mild effect on epibenthic communities. However, an informed choice of building material and an appropriate combination of multiple structural manipulations can promote ecological benefits at multiple levels, from increasing the ecological performance in situ to reducing the impacts during the production process. Thus, I combined my findings in a final experiment, still in progress, where I am testing the combined role of shape, brightness and inclination of biomimetic surfaces I have designed in producing benefits at multiple levels. Overall, I suggest that biomimicry has the potential to increase the ecological value of artificial habitats especially when a wide range of aspects is simultaneously considered. Indeed, none of the structural factors, individually, can fully mimic the “natural conditions” to effectively improve the ecological performance of the artificial substrates. This emphasizes the need to include in future works a multi-level perspective to fully achieve the great potential of biomimicry.

Active control of sound radiated by vibrating surfaces on a McLaren supercar

Sound radiators based on forced vibrations of plates are becoming widely employed, mainly for active sound enhancement and noise cancelling systems, both in music and automotive environment. Active sound enhancement solutions based on electromagnetic shakers hence find increasing interest. Mostly diffused applications deal with active noise control (ANC) and active vibration control systems for improving the acoustic experience inside or outside the vehicle. This requires investigating vibrational and, consequently, vibro-acoustic characteristics of vehicles. Therefore, simulation and processing methods capable of reducing the calculation time and providing high-accuracy results, are strongly demanded. In this work, an ideal case study on rectangular plates in fully clamped conditions preceded a real case analysis on vehicle panels. The sound radiation generated by a vibrating flat or shallow surface can be calculated by means of Rayleigh’s integral. The analytical solution of the problem is here calculated implementing the equations in MATLAB. Then, the results are compared with a numerical model developed in COMSOL Multiphysics, employing Finite Element Method (FEM). A very good matching between analytical and numerical solutions is shown, thus the cross validation of the two methods is achieved. The shift to the real case study, on a McLaren super car, led to the development of a mixed analytical-numerical method. Optimum results were obtained with mini shakers excitement, showing good matching of the recorded SPL with the calculated one over all the selected frequency band. In addition, a set of directivity measurements of the hood were realized, to start studying the spatiality of sound, which is fundamental to active noise control systems.

Mitigating non-Lambertian surfaces issues in Stereo Matching with Neural Radiance Fields

Depth estimation from images has long been regarded as a preferable alternative compared to expensive and intrusive active sensors, such as LiDAR and ToF. The topic has attracted the attention of an increasingly wide audience thanks to the great amount of application domains, such as autonomous driving, robotic navigation and 3D reconstruction. Among the various techniques employed for depth estimation, stereo matching is one of the most widespread, owing to its robustness, speed and simplicity in setup. Recent developments has been aided by the abundance of annotated stereo images, which granted to deep learning the opportunity to thrive in a research area where deep networks can reach state-of-the-art sub-pixel precision in most cases. Despite the recent findings, stereo matching still begets many open challenges, two among them being finding pixel correspondences in presence of objects that exhibits a non-Lambertian behaviour and processing high-resolution images. Recently, a novel dataset named Booster, which contains high-resolution stereo pairs featuring a large collection of labeled non-Lambertian objects, has been released. The work shown that training state-of-the-art deep neural network on such data improves the generalization capabilities of these networks also in presence of non-Lambertian surfaces. Regardless being a further step to tackle the aforementioned challenge, Booster includes a rather small number of annotated images, and thus cannot satisfy the intensive training requirements of deep learning. This thesis work aims to investigate novel view synthesis techniques to augment the Booster dataset, with ultimate goal of improving stereo matching reliability in presence of high-resolution images that displays non-Lambertian surfaces.

The Applicability Of Ordered Mesoporous Sba-15 And Its Hydrophobic Glutaraldehyde-bridge Derivative To Improve Ibuprofen-loading In Releasing System.

The mesoporous SBA-15 silica with uniform hexagonal pore, narrow pore size distribution and tuneable pore diameter was organofunctionalized with glutaraldehyde-bridged silylating agent. The precursor and its derivative silicas were ibuprofen-loaded for controlled delivery in simulated biological fluids. The synthesized silicas were characterized by elemental analysis, infrared spectroscopy, (13)C and (29)Si solid state NMR spectroscopy, nitrogen adsorption, X-ray diffractometry, thermogravimetry and scanning electron microscopy. Surface functionalization with amine containing bridged hydrophobic structure resulted in significantly decreased surface area from 802.4 to 63.0 m(2) g(-1) and pore diameter 8.0-6.0 nm, which ultimately increased the drug-loading capacity from 18.0% up to 28.3% and a very slow release rate of ibuprofen over the period of 72.5h. The in vitro drug release demonstrated that SBA-15 presented the fastest release from 25% to 27% and SBA-15GA gave near 10% of drug release in all fluids during 72.5 h. The Korsmeyer-Peppas model better fits the release data with the Fickian diffusion mechanism and zero order kinetics for synthesized mesoporous silicas. Both pore sizes and hydrophobicity influenced the rate of the release process, indicating that the chemically modified silica can be suggested to design formulation of slow and constant release over a defined period, to avoid repeated administration.