Yes / This study examines experimentally and for the first time the effect of reduced air pressure on dynamic wetting. The purpose is to assess the role of air viscosity on dynamic wetting failure which hitherto has been speculated on but not measured. In this paper we used dip coating as the model experimental flow and report data on air entrainment velocity Vae we measured with a series of silicone oils in a range of viscosities in a vacuum chamber where the pressure can be reduced from atmospheric down to a few mbar when the mean molecular free path of air is large and air ceases to have a viscosity. To complement earlier work, we carried out the experiments with a range of substrates of varying roughness. The substrates were chosen so that for each one, their two sides differ in roughness. This enables simultaneous comparative observation of their wetting performance and reduces the experimental error in assessing the role of roughness. The data presented here capture the effects of viscosity, roughness and air pressure but the important result of this study is that Vae can be increased considerably (exponentially) when the pressure is reduced with the suggestion that Vae approaches infinity as pressure approaches zero. In other words, the role of the surrounding air viscosity is important in dynamic wetting. The data from this study have significant implication to the fundamental understanding of dynamic wetting. Indeed they form the missing data link to fully understand this phenomenon. The data presented in this work also confirm the complex role of roughness, in that it can increase or decrease the air entrainment speed depending on the value on the viscosity of the coating solution. The results presented in this paper are very useful in practice as they imply that if one chooses carefully roughness one can coat viscous formulation at unexpectedly very high speeds with a moderate vacuum (50 mbar typically).

Yes / The coating flow examined here, labelled angled dip coating, is that where a substrate enters a pool of liquid forming an angle ß with the vertical so that it intersects the liquid along a wetting line which is not perpendicular to the direction of its motion. This flow situation is distinctly different from that where the substrate, inclined in the other dimension by the so-called angle of entry ¿, intersects the liquid surface perpendicularly to its motion. Experiments were carried out with various liquids to determine the effect of ß on the substrate velocity at which air is entrained into the liquid. It was observed that as this angle departs from zero, air entrainment is delayed to higher speeds. The data show that the speed which is relevant to air entrainment is not the velocity of the substrate itself but its component normal to the wetting line. This result has important practical implications and suggests that this fundamental principle is also applicable to other coating flows.

Yes / This study assesses experimentally the role of gas viscosity in controlling the minimum film thickness in slot coating in both the slot over roll and tensioned web modes. The minimum film thickness here is defined with respect to the onset of air entrainment rather than rivulets, the reason being that rivulets are an extreme form of instabilities occurring at much higher speeds. The gas viscosity effects are simulated experimentally by encasing the coaters in a sealed gas chamber in which various gases can be admitted. An appropriate choice of two gases was used to compare performances: air at atmospheric pressure and helium at sub-ambient pressure (25mbar), which we establish has a significantly lower “thin film” viscosity than atmospheric air. A capacitance sensor was used to continuously measure the film thickness on the web, which was ramped up in speed at a fixed acceleration whilst visualizations of the film stability were recorded through a viewing port in the chamber. The data collected show clearly that by coating in rarefied helium rather that atmospheric air we can reduce the minimum film thickness or air/gas entrainment low-flow limit. We attribute this widening of the stable coating window to the enhancement of dynamic wetting that results when the thin film gas viscosity is reduced. These results have evident practical significance for slot coating, the coating method of choice in many new technological applications, but it is their fundamental merit which is new and one that should be followed with further data and theoretical underpinning.

<p>This thesis describes the current status and novel aspects of the analysis of the molecules of life, i.e. peptides and proteins, using capillary electrophoresis (CE) coupled to mass spectrometry (MS) via (sheathless) electrospray ionization (ESI). Early reports of sheathless CE-ESI-MS were plagued by limited lifetimes of the electrospray emitter. In this thesis, two new approaches, the Black Dust and the Black Jack methods, utilizing polymer-embedded graphite instead of noble metals are presented. These emitters have shown improved long-term stability and proven excellent for sheathless electrospray operation. Failure of an emitter is often caused by electrochemical reactions occurring at the emitter-liquid interface. The electrochemical properties of the graphite coated emitters were therefore evaluated by classical electrochemical methods, such as cyclic voltammetry and chronoamperometry. The graphite coated emitters showed excellent electrochemical stability and properties compared to noble metal and polymer configurations.</p><p>Analyte-wall interactions have long been known to cause problems in the CE analysis of biomolecules. This can be circumvented by internal modification of the capillary walls. Additionally, it is of outermost importance to have a stable and sufficiently high electroosmotic flow (EOF) to sustain the electrospray, when using a sheathless approach. New monomer and polymer coatings are presented for rapid and high-efficient CE-ESI-MS separations of peptides and proteins.</p><p>Furthermore, the use of CE-ESI coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) shows great potential for rapid proteomic probing of human cerebrospinal fluid. The results are comparable with more established techniques, such as liquid chromatography and two-dimensional gel electrophoresis coupled to MS. However, the CE-ESI-FTICRMS analysis has significantly lower sample consumption and faster analysis time compared to the other techniques. The applications and use of CE-ESI-MS is expected to have a bright future with continued growth as current trends of multidimensional hyphenation and microfabricated devices are further developed and explored.</p>

This thesis describes the current status and novel aspects of the analysis of the molecules of life, i.e. peptides and proteins, using capillary electrophoresis (CE) coupled to mass spectrometry (MS) via (sheathless) electrospray ionization (ESI). Early reports of sheathless CE-ESI-MS were plagued by limited lifetimes of the electrospray emitter. In this thesis, two new approaches, the Black Dust and the Black Jack methods, utilizing polymer-embedded graphite instead of noble metals are presented. These emitters have shown improved long-term stability and proven excellent for sheathless electrospray operation. Failure of an emitter is often caused by electrochemical reactions occurring at the emitter-liquid interface. The electrochemical properties of the graphite coated emitters were therefore evaluated by classical electrochemical methods, such as cyclic voltammetry and chronoamperometry. The graphite coated emitters showed excellent electrochemical stability and properties compared to noble metal and polymer configurations. Analyte-wall interactions have long been known to cause problems in the CE analysis of biomolecules. This can be circumvented by internal modification of the capillary walls. Additionally, it is of outermost importance to have a stable and sufficiently high electroosmotic flow (EOF) to sustain the electrospray, when using a sheathless approach. New monomer and polymer coatings are presented for rapid and high-efficient CE-ESI-MS separations of peptides and proteins. Furthermore, the use of CE-ESI coupled to Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) shows great potential for rapid proteomic probing of human cerebrospinal fluid. The results are comparable with more established techniques, such as liquid chromatography and two-dimensional gel electrophoresis coupled to MS. However, the CE-ESI-FTICRMS analysis has significantly lower sample consumption and faster analysis time compared to the other techniques. The applications and use of CE-ESI-MS is expected to have a bright future with continued growth as current trends of multidimensional hyphenation and microfabricated devices are further developed and explored.

Ce travail s’intéresse a la synthèse et à la caractérisation de revêtements hybrides O/I à base de silice, préparés par voie sol-gel et déposés sur polycarbonate (PC), pour des applications en milieu chaud et humide dans le domaine culinaire. Le PC étant connu pour sa sensibilité à l’hydrolyse dans ce type de milieux (provoquant sa dépolymérisation progressive et ainsi la libération de bisphénol A, molécule suspectée comme étant toxique), le rôle du revêtement est donc de protéger le PC et d’éviter son vieillissement prématuré, tout en améliorant ses propriétés mécaniques. Dans un premier temps, de nombreux sols ont été synthétisés et optimisés, principalement en termes de nature et quantités de précurseurs, et de pH, dans le but d’obtenir des revêtements homogènes et transparents. Un suivi des réactions d’hydrolyse et de condensation des sols a également été réalisé afin de déterminer le temps minimal de maturation de ces derniers. Apres dépôt des revêtements par dip-coating, les propriétés mécaniques des films ont été étudiées par de nombreuses techniques. D’un point de vue général, les propriétés des échantillons revêtus ont été trouvées supérieures à celles du PC nu. L’influence de nombreux paramètres de synthèse comme le ratio organoalcoxysilane(s)/silice colloïdale, l’ajout d’additifs, le type de traitement de surface du PC pré-dépôt ou encore les conditions de recuit, a également été étudiée. L’ensemble de ce travail a permis d’obtenir, à partir de deux systèmes sol-gel différents, des revêtements performants en termes de transparence, d’adhésion au substrat, de non-toxicité, couplés à des valeurs élevées de dureté, de densité et de module de Young / This work deals with the synthesis and the characterization of hybrid O/I silica coatings prepared by the sol-gel route and deposited on polycarbonate (PC), for applications in hot and humid environment in the alimentary field. PC is well-known for undergoing hydrolysis in such conditions (causing its progressive depolymerization and thus leading to the release of bisphenol A, a molecule suspected to be toxic): the function of the coating would thus consist in preventing PC from this kind of premature ageing, along with the enhancement of its mechanical properties. As a first step, a lot of different sols were synthesized and optimized, mainly in terms of type and quantity of precursors, along with the pH, in order to obtain transparent and homogeneous coatings. The hydrolysis and condensation reactions were monitored in order to determine the minimum ageing time to be waited before any film deposition. After deposition by dip-coating, the mechanical properties of the films were assessed by using many different techniques. Basically, the coated-PC samples display higher properties than the uncoated one. The influence of numerous synthesis parameters such as the organoalkoxysilanes/colloidal silica ratio, the presence of additives, the kind of surface treatment of PC before film deposition, or the annealing conditions was also studied. This whole work led to the synthesis, from two different sol-gel systems, of superior quality coatings in terms of transparency, adherence to the substrate, non-toxicity, along with elevated hardness, density and Young’s modulus values

Starch in paper coatings is known to increase the risk of print mottle in lithographic offset printing. The objective of this study was to increase the understanding of this behaviour. Four phenomena that could lead to print mottle, where the presence of starch might be important, have been identified: uneven binder migration, uneven coating mass distribution, uneven deformation during calendering and differential shrinkage. The latter three were investigated in this project. Starch-containing coating colours often have high water retention. A relationship between the water retention of the coating colours and the distribution of coating thickness was found in a pilot trial. A theory is proposed, where the surface profile of the base paper beneath the blade, that governs the coat weight distribution in blade coating, is affected by moisture from the dewatering coating colours and the compressive force exerted by the blade. Drying strategies were studied to see whether they would induce porosity variations in the coating layers. There is a strong connection between the rate of evaporation and the shrinkage of the coating layer, but no porosity variations due to the choice of drying strategy were found. Shrinkage is governed by the capillary forces. At the same capillary pressure, the coating shrinks more for some binder systems, which is suggested to be due to a weaker chemical interaction between the binder and the pigment. Oxidized starch/latex coatings, stained with a fluorescent marker, had a greater standard deviation in fluorescence intensity than CMC/latex coatings caused by a difference in either porosity or latex distribution. It was shown that calendering introduces porosity variations into the coating layer that are larger for starch-containing coatings. The drying strategies appeared to have a significant effect on these porosity variations and they correlated positively with print mottle in some cases and in another case negatively. In the case of the negatively correlated, the mottle was probably caused by variations in surface porosity existing prior to the calendering.

The purpose of the thesis was to study chemical and corrosion resistance of selected conversion coatings. The corrosion and the possibilities of corrosion protection with focus on conversion coatings on aluminum and steel surface were described in the theoretical part. In the experimental part corrosion and chemical resistance of samples without the next treatment and samples with polyester powder coating and synthetic coating were tested.

No description available.

Axial piston pumps and motors are widely used in heavy-duty applications and play a fundamental role in hydrostatic and power split drives. The mechanical power losses in hydraulic piston pumps come from the friction between parts in relative motion. The improvement, albeit marginal, in overall efficiency of these components may significantly impact the global efficiency of the machine. The friction between slipper and swash plate is a functional key in an axial piston pump, especially when the pump (at low rotational speed or at partial displacement) works in the critical areas where the efficiency is low. The application of special surface treatments have been exploited in pioneering works in the past, trying different surface finishing or adding ceramic or heterogeneous metallic layers. The potential of structured coatings at nanoscale, with superhydrophobic and oleophobic characteristics, has never been exploited. Due to the difficulty to reproduce the real working conditions of axial piston pump slippers, it has been made a hydraulic test bench properly designed in order to compare the performance of nano-coated slippers with respect to standard ones. The nano-coated and standard slippers have been subjected to the following working conditions: a test at variable pressure and constant rotational speed, a test at constant pressure and variable rotational speed. The comparison between standard and nanocoated slippers, for both working conditions, shows clearly that more than 20% of friction reduction can be achieved using the proposed nano-coating methodology.