Anisotropic surface properties of micro/nanostructured a-C:H:F thin films with self-assembly applications

The singular properties of hydrogenated amorphous carbon (a-C:H) thin filmsdeposited by pulsed DC plasma enhanced chemical vapor deposition (PECVD), such as hardness and wear resistance, make it suitable as protective coating with low surface energy for self-assembly applications. In this paper, we designed fluorine-containing a-C:H (a-C:H:F) nanostructured surfaces and we characterized them for self-assembly applications. Sub-micron patterns were generated on silicon through laser lithography while contact angle measurements, nanotribometer, atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to characterize the surface. a-C:H:F properties on lithographied surfaces such as hydrophobicity and friction were improved with the proper relative quantity of CH4 and CHF3 during deposition, resulting in ultrahydrophobic samples and low friction coefficients. Furthermore, these properties were enhanced along the direction of the lithographypatterns (in-plane anisotropy). Finally, self-assembly properties were tested with silicananoparticles, which were successfully assembled in linear arrays following the generated patterns. Among the main applications, these surfaces could be suitable as particle filter selector and cell colony substrate.

Use of thin films obtained by plasma polymerization for grain protection and germination enhancement

In this work, preliminary results of the use of hydrophobic thin films obtained by plasma deposition to protect grains and seeds are presented: grains coated by the films did not present biological degradation when stored in a saturated water vapor environment, but had their germination accelerated in the presence of water. A model that explains the difference of behavior of the films when exposed to water in vapor form or in liquid form, based on the formation of microchannels within the film that lead to water uptake in seeds, is presented. The model was successfully tested using quartz crystal measurements, which showed that the microchannels within the films can favor the adsorption and permeation of water when the films are immersed in water.

Magnetic Perovskites Sr2FeMoO6 and La(1-x)Ca(x)MnO3: Synthesis, Fabrication and Characterization of Nanosized Powders and Thin Films

Due to font problem on the tilte field the titlte of the thesis is corrected here. The title of the thesis is: Magnetic Perovskites Sr₂FeMoO₆ and La_(1-x)Ca_(x)MnO₃: Synthesis, Fabrication and Characterization of Nanosized Powders and Thin Films

Micro- and nanostructuring of poly(ethylene-2,6-naphthalate) surfaces, for biomedical applications, using polymer replication techniques

Here we investigate the formation of superficial micro- and nanostructures in poly(ethylene-2,6-naphthalate) (PEN), with a view to their use in biomedical device applications, and compare its performance with a polymer commonly used for the fabrication of these devices, poly(methyl methacrylate) (PMMA). The PEN is found to replicate both micro- and nanostructures in its surface, albeit requiring more forceful replication conditions than PMMA, producing a slight increase in surface hydrophilicity. This ability to form micro/nanostructures, allied to biocompatibility and good optical transparency, suggests that PEN could be a useful material for production of, or for incorporation into, transparent devices for biomedical applications. Such devices will be able to be autoclaved, due to the polymer's high temperature stability, and will be useful for applications where forceful experimental conditions are required, due to a superior chemical resistance over PMMA.

Superconducting properties and their enhancement in ReBa2Cu3O7-delta (RE = Y and Gd) films prepared by pulsed laser deposition

Due to font problem on the tilte field the titlte of the thesis is corrected here. The title of the thesis is: Superconducting properties and their enhancement in ReBa₂Cu₃O₇-delta (RE = Y and Gd) films prepared by pulsed laser deposition

First principles modeling of metallic alloys and alloy surfaces

By alloying metals with other materials, one can modify the metal’s characteristics or compose an alloy which has certain desired characteristics that no pure metal has. The field is vast and complex, and phenomena that govern the behaviour of alloys are numerous. Theories cannot penetrate such complexity, and the scope of experiments is also limited. This is why the relatively new field of ab initio computational methods has much to give to this field. With these methods, one can extend the understanding given by theories, predict how some systems might behave, and be able to obtain information that is not there to see in physical experiments. This thesis pursues to contribute to the collective knowledge of this field in the light of two cases. The first part examines the oxidation of Ag/Cu, namely, the adsorption dynamics and oxygen induced segregation of the surface. Our results demonstrate that the presence of Ag on the Cu(100) surface layer strongly inhibits dissociative adsorption. Our results also confirmed that surface reconstruction does happen, as experiments predicted. Our studies indicate that 0.25 ML of oxygen is enough for Ag to diffuse towards the bulk, under the copper oxide layer. The other part elucidates the complex interplay of various energy and entropy contributions to the phase stability of paramagnetic duplex steel alloys. We were able to produce a phase stability map from first principles, and it agrees with experiments rather well. Our results also show that entropy contributions play a very important role on defining the phase stability. This is, to the author’s knowledge, the first ab initio study upon this subject.

Influence of topography and surface chemistry on the wetting properties of TiO2-based ceramic coatings

Vätning av fasta ytor är ett viktigt fenomen i såväl naturen som i en lång rad av industriella tillämpningar. Det är allmänt känt att vätningen av en fast yta styrs av ytans kemi samt struktur. Målsättningen med avhandlingen var att studera hur kemisk heterogenitet och ytråhet på nanometernivå påverkar vätningsegenskaperna hos en fast yta. Ytorna som studerades var titandioxid-baserade kerama ytor som framställdes med hjälp av en sol-gel process. Vätningstudierna utfördes genom kontaktvinkelmätningar, vilket innebär att man mäter vinkeln som vätska/luft-gränsskiktet hos en vätskedroppe bildar mot en fast yta. Ytråheten hos materialen studerades främst genom atomkraftsmikroskopi (AFM). I AFM detekteras ytans struktur av en mycket skarp nål som skannar ytan. Resultaten i avhandlingen kunde framgångsrikt modelleras med existerande teorier för vätning av heterogena ytor.

Annual evolution of global, direct and diffuse radiation and fractions in tilted surfaces

It was evaluated the annual evolution of global, direct and diffuse components of incident solar radiation on tilted surfaces to 12.85, 22.85 and 32.85º, facing north, in Botucatu, state of São Paulo, Brazil. The radiometric fractions were obtained for each component of the radiation in the aforementioned surfaces, through the ratio with the global and top of the atmosphere radiations. Seasonality was evaluated based on monthly averages of daily values. The measures occurred between 04/1998 and 07/2001 at 22.85º; 08/2001 and 02/2003 at 12.85º; and from 03/2003 to 12/2007 at 32.85º, with concomitant measures in the horizontal surface (reference). The levels of global and direct radiation on tilted surfaces were lower in summer and higher in the equinoxes when compared with the horizontal. The diffuse radiation on tilted surfaces was lower in most months, with losses of up to 65%. A trend of increasing differences occurred between horizontal and tilted surfaces with the increase of the angle in all the components and fractions of incident radiation. The annual evolution of rainfall and cloud cover ratio directly affected the atmospheric transmissivity of direct and diffuse components in the region.

Outlining precision boundaries among areas with different variability standards using magnetic susceptibility and geomorphic surfaces

There is an increasing demand for detailed maps that represent in a simplified way the knowledge of the variability of a particular area or region maps. The objective was to outline precision boundaries among areas with different accuracy variability standards using magnetic susceptibility and geomorphic surfaces. The study was conducted in an area of 110 ha, which identified three compartment landscapes based on the geomorphic surfaces model. To determinate pH, organic matter, phosphorus, potassium and magnesium, the total sand and clay, 514 soil samples were collected at depths of 0-0.20 m and 0.60-0.80 m. The sum of base, cationic exchange capacity and base saturation were calculated and the magnetic susceptibility was evaluated in the laboratory using a system based on a balance of analytical precision method. Geomorphic surfaces identification allowed setting specific management areas (locations with maximum homogeneity of soil attributes). The map of spatial variability of magnetic susceptibility can be used to validate the precise boundaries among geomorphic surfaces identified in the field and infer the variability of clay content and soil base saturation.

Physical characteristics of oily spraying liquids and droplets formed on coffee leaves and glass surfaces

The physical characteristics of a spray liquid are important in getting a good droplet formation and control efficiency over a particular target. As a function of these characteristics, it is possible to decipher which is the best adjuvant based on the respective concentration used during the spray. Therefore, ten spraying liquids were prepared, which varied in concentrations of pesticide lufenuron + profenofos, mineral oil, water and manganese sulfate. Pendant droplets formed from these mixtures were measured to examine their impact on surface tension. Droplets were applied to the surface of coffee leaves and the surface tension, contact angle formed and the leaf area wetted by the droplet, were measured. A smooth glass surface was taken as a comparative to the coffee leaves. The highest concentrations of oil resulted in lower surface tension, smaller contact angles of droplets on leaf surfaces and larger areas wetted by the droplets. Both surfaces showed hydrophilic behavior.

Liquid transportation and distribution during (re)wetting : impact on coated papers in printing

In many industrial applications, such as the printing and coatings industry, wetting of porous materials by liquids includes not only imbibition and permeation into the bulk but also surface spreading and evaporation. By understanding these phenomena, valuable information can be obtained for improved process control, runnability and printability, in which liquid penetration and subsequent drying play important quality and economic roles. Knowledge of the position of the wetting front and the distribution/degree of pore filling within the structure is crucial in describing the transport phenomena involved. Although exemplifying paper as a porous medium in this work, the generalisation to dynamic liquid transfer onto a surface, including permeation and imbibition into porous media, is of importance to many industrial and naturally occurring environmental processes. This thesis explains the phenomena in the field of heatset web offset printing but the content and the analyses are applicable in many other printing methods and also other technologies where water/moisture monitoring is crucial in order to have a stable process and achieve high quality end products. The use of near-infrared technology to study the water and moisture response of porous pigmented structures is presented. The use of sensitive surface chemical and structural analysis, as well as the internal structure investigation of a porous structure, to inspect liquid wetting and distribution, complements the information obtained by spectroscopic techniques. Strong emphasis has been put on the scale of measurement, to filter irrelevant information and to understand the relationship between interactions involved. The near-infrared spectroscopic technique, presented here, samples directly the changes in signal absorbance and its variation in the process at multiple locations in a print production line. The in-line non-contact measurements are facilitated by using several diffuse reflectance probes, giving the absolute water/moisture content from a defined position in the dynamic process in real-time. The nearinfrared measurement data illustrate the changes in moisture content as the paper is passing through the printing nips and dryer, respectively, and the analysis of the mechanisms involved highlight the roles of the contacting surfaces and the relative liquid carrier properties of both non-image and printed image areas. The thesis includes laboratory studies on wetting of porous media in the form of coated paper and compressed pigment tablets by mono-, dual-, and multi-component liquids, and paper water/moisture content analysis in both offline and online conditions, thus also enabling direct sampling of temporal water/moisture profiles from multiple locations. One main focus in this thesis was to establish a measurement system which is able to monitor rapid changes in moisture content of paper. The study suggests that near-infrared diffuse reflectance spectroscopy can be used as a moisture sensitive system and to provide accurate online qualitative indicators, but, also, when accurately calibrated, can provide quantification of water/moisture levels, its distribution and dynamic liquid transfer. Due to the high sensitivity, samples can be measured with excellent reproducibility and good signal to noise ratio. Another focus of this thesis was on the evolution of the moisture content, i.e. changes in moisture content referred to (re)wetting, and liquid distribution during printing of coated paper. The study confirmed different wetting phases together with the factors affecting each phase both for a single droplet and a liquid film applied on a porous substrate. For a single droplet, initial capillary driven imbibition is followed by equilibrium pore filling and liquid retreat by evaporation. In the case of a liquid film applied on paper, the controlling factors defining the transportation were concluded to be the applied liquid volume in relation to surface roughness, capillarity and permeability of the coating giving the liquid uptake capacity. The printing trials confirmed moisture gradients in the printed sheet depending on process parameters such as speed, fountain solution dosage and drying conditions as well as the printed layout itself. Uneven moisture distribution in the printed sheet was identified to be one of the sources for waving appearance and the magnitude of waving was influenced by the drying conditions.

Gelatin as an additive in bio-based barrier films

The main objective of the present study was to verify the approach on starch-gelatin blending for the paperboard coating formulations with enhanced barrier and mechanical properties. Based on that, another objective was to find out, how the approach will function with wood-based polysaccharides (CMC, EHEC and HPC) by analyzing their barrier properties and convertibility. The last objective was to find out, if pigments can be used in the composition of polysaccharide-protein blends without causing any negative effect on stated properties. The whole process chain of the barrier coating development was studied in the research. The methodology applied included pilot-scale coating and converting trials for the evaluation of mechanical properties of obtained coatings, namely their exposure to cracking with the loss of barrier properties. The results obtained indicated that the combination of starch with gelatin, in fact, improves the grease barrier properties and flexibility of starch-based coatings, thereby confirming the offered approach. The similar results were obtained for CMC, exhibited elevated barrier properties and surface coverage, proving that the approach also functions with wood-based polysaccharides. The introduction of equal amounts of talc gave various effects at different gelatin dosages on barrier properties of wood-based polysaccharides. Mainly, the elevation of grease barrier properties was observed. The convertibility of talc-filled coatings was not sufficient.

Algorithm to determine the intersection curves between bezier surfaces by the solution of multivariable polynomial system and the differential marching method

The determination of the intersection curve between Bézier Surfaces may be seen as the composition of two separated problems: determining initial points and tracing the intersection curve from these points. The Bézier Surface is represented by a parametric function (polynomial with two variables) that maps a point in the tridimensional space from the bidimensional parametric space. In this article, it is proposed an algorithm to determine the initial points of the intersection curve of Bézier Surfaces, based on the solution of polynomial systems with the Projected Polyhedral Method, followed by a method for tracing the intersection curves (Marching Method with differential equations). In order to allow the use of the Projected Polyhedral Method, the equations of the system must be represented in terms of the Bernstein basis, and towards this goal it is proposed a robust and reliable algorithm to exactly transform a multivariable polynomial in terms of power basis to a polynomial written in terms of Bernstein basis .

Microcracks and Vortices in Superconducting Thin Films

In this work, superconducting YBa₂ Cu₃O_6+x (YBCO) thin films have been studied with the experimental focus on the anisotropy of BaZrO₃ (BZO) doped YBCOthin films and the theoretical focus on modelling flux pinning by numerically solving Ginzburg- Landau equations. Also, the structural properties of undoped YBCO thin films grown on NdGaO₃ (NGO) and MgO substrates were investigated. The thin film samples were made by pulsed laser ablation on single crystal substrates. The structural properties of the thin films were characterized by X-ray diffraction and atomic force microscope measurements. The superconducting properties were investigated with a magnetometer and also with transport measurements in pulsed magnetic field up to 30 T. Flux pinning was modelled by restricting the value of the order parameter inside the columnar pinning sites and then solving the Ginzburg-Landau equations numerically with the restrictions in place. The computations were done with a parallel code on a supercomputer. The YBCO thin films were seen to develop microcracks when grown on NGO or MgO substrates. The microcrack formation was connected to the structure of the YBCO thin films in both cases. Additionally, the microcracks can be avoided by careful optimization of the deposition parameters and the film thickness. The BZO doping of the YBCO thin films was seen to decrease the effective electron mass anisotropy, which was seen by fitting the Blatter scaling to the angle dependence of the upper critical field. The Ginzburg-Landau simulations were able to reproduce the measured magnetic field dependence of the critical current density for BZO doped and undoped YBCO. The simulations showed that in addition to the large density also the large size of the BZO nanorods is a key factor behind the change in the power law behaviour between BZO doped and undoped YBCO. Additionally, the Ginzburg-Landau equations were solved for type I thin films where giant vortices were seen to appear depending on the film thickness. The simulations predicted that singly quantized vortices are stable in type I films up to quite large thicknesses and that the size of the vortices increases with decreasing film thickness, in a way that is similar to the behaviour of the interaction length of Pearl vortices.