Orientador: Carlos Roberto Grandini / Banca: Alfredo Gonçalves Cunha / Banca: Paulo Noronha Lisboa Filho / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: Desde a descoberta dos supercondutores com alta Tc, vários trabalhos têm sido efetuados sobre as diferentes propriedades destes materiais. As cerâmicas Y'BA IND.2' "C IND.U 'IND.3' 'O IND. 7-'delta' mostraram que tem suas propriedades supercondutoras fortemente afetadas pela quantidade de oxigênio. Mais recentemente, medidas de relaxações anelásticas em 'LA IND.2'CU 'O IND. 4+'delta' mostraram que a remoção deste elemento pode ser relacionada com dois eventos. Um deles é o decréscimo na mobilidade entre dois planos adjacentes CuO e o outro, é o aumento no número de padrões de mobilidade para os octaedros CU 'O IND. 6'. Para SM'BA IND.2' "C IND.U 'IND.3' 'O IND. 7-'delta' (SBCO), a possibilidade de uma estequiometria de oxigênio variável e sua alta mobilidade nos planos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Since the discovery of the high Tc superconductors, several works have been made about the different propoerties of these materials. Y'BA IND.2' "C IND.U 'IND.3' 'O IND. 7-'delta' ceramic showed to have its superconducting properties strongly affected by the oxygen content. More recently, anelastic relaxation measurements in 'LA IND.2'CU 'O IND. 4+'delta', showed that the remotion of this element can be related to two events. One is the decrease in mobility between two adjacent CuO planes, and the other is the increase in the number of tilting patterns of the Cu 'O IND. 6' octahedra. For SM'BA IND.2' "C IND.U 'IND.3' 'O IND. 7-'delta' (SBCO), the possibility of variable stoichiometry and the high mobility of oxygen in the... (Complete abstract, click electronic access below) / Mestre

Friction on ice is important for many different fields such as winter sports and vehicle traction. In vehicle handling, maximising the friction coefficient between tyres and the ice surface is key to safety. The friction coefficient between tyre rubber and ice has been observed to be as high as unity at low temperatures and as little as 0.05 close to the ice melting temperature. The observed low friction is due to thin water films generated through frictional heating. Little is known about the formation and behaviour of this fluid film and its thickness has been difficult to measure. Previous attempts included techniques such as capacitance, conductivity and fluorescence spectroscopy, however results have been inconsistent. The primary aim of this study was to develop a measurement technique for this lubricating layer, establishing its thickness and the conditions under which its presence results in low friction. This was done by designing a micro-scale linear tribometer (microtribometer) to measure the friction coefficient (μ) on ice under a microscope. Clear ice, and ice with fluorescent particles of various sizes were created. The two ice types were then joined and tested on. During a friction test on the microtribometer, the particles displaced in the direction of sliding due to melt water presence. Images of the ice surface were taken before and after a friction measurement was made, and the amount of particle movement was assessed. The size and displacement of particles were correlated to the range of melt water thickness for a given sliding condition. This study is the first direct measurement method for the melt water layer on ice. Frictional heating is generated through the physical contact of rubber and ice asperities. By conducting friction measurements with rubbers of varying shear modulus (G*) and surface roughness (Ra) on both the microtribometer and on our large–scale tribometer, FRIMA, analysis of the contact can be made over a range of length scales. Further insight into the interfacial effects was provided by surface roughness measurements of both ice and rubber before and ice after microtribometer tests and in FRIMA. Finally, the use of differential interference contrast in reflected light microscopy with ice friction measurements provided visual evidence of the melt water presence. It was found that the melt water thickness based on particle displacement was between 0.1 to 2μm, for a velocity of 4.3 ⇥ 10−4 ms−1 and 0.5MPa nominal load, between –6°C to 0°C. A decreasing film thickness was found with decreasing temperature and the friction coefficient increased with decreasing temperature. At higher temperatures, the differences between the rubbers on both FRIMA and the microtribometer were found to be negligible because of the lubricating layer. Increasing the rubber surface roughness was found to increase at high and decrease friction significantly at low temperatures. These phenomena can be explained by the decreasing amount of solid-solid contact. A simple analytical approach to interpret the results suggests that the rubber compresses significantly and the surface roughness is smoothened upon contact with ice. Furthermore, simple hydrodynamic shear calculations show that pure liquid shear is insufficient to account for the measured low μ values close to melting temperatures. The combined effect of the increasing melt water presence reducing the real contact area and the significant deformation of the rubber asperities failing to compensate for this reduced contact area can account for the results. It is anticipated that these results provide direction for finding ways to improve solid-solid contact between rubber and ice, as there is some viscoelastic dissipation even at conditions close to the melting temperature. Some topics for example are: improving the thermal conductivity of tyre compounds or further investigating the surface roughness of rubber and ice separately and with the thin liquid film in between.

Doctor of Philosophy (PhD) / This thesis aims to establish a sound scientific methodology for the effective and efficient polishing of thermally stable PCD composites (consisting of diamond and SiC) for cutting tools applications. The surface roughness of industrial PCD cutting tools, 0.06 μm Ra is currently achieved by mechanical polishing which is time consuming and costly because it takes about three hours to polish a 12.7 mm diameter PCD surface. An alternative technique, dynamic friction polishing (DFP) which utilizes the thermo-chemical reactions between the PCD surfaces and a catalytic metal disk rotating at high peripheral speed has been comprehensively investigated for highly efficient abrasive-free polishing of PCD composites. A special polishing machine was designed and manufactured in-house to carry out the DFP of PCD composites efficiently and in a controllable manner according to the requirements of DFP. The PCD polishing process and material removal mechanism were comprehensively investigated by using a combination of the various characterization techniques: optical microscopy, SEM and EDX, AFM, XRD, Raman spectroscopy, TEM, STEM and EELS, etc. A theoretical model was developed to predict temperature rise at the interface of the polishing disk and PCD asperities. On-line temperature measurements were carried out to determine subsurface temperatures for a range of polishing conditions. A method was also developed to extrapolate these measured temperatures to the PCD surface, which were compared with the theoretical results. The material removal mechanism was further explored by theoretical study of the interface reactions under these polishing conditions, with particular emphasis on temperature, contact with catalytic metals and polishing environment. Based on the experimental results and theoretical analyses, the material removal mechanism of dynamic friction polishing can be described as follows: conversion of diamond into non-diamond carbon takes place due to the frictional heating and the interaction of diamond with catalyst metal disk; then a part of the transformed material is detached from the PCD surface as it is weakly bonded; another part of the non-diamond carbon oxidizes and escapes as CO or CO2 gas and the rest diffuses into the metal disk. Meanwhile, another component of PCD, SiC also chemically reacted and transformed to amorphous silicon oxide/carbide, which is then mechanically or chemically removed. Finally an attempt was made to optimise the polishing process by investigating the effect of polishing parameters on material removal rate, surface characteristics and cracking /fracture of PCD to achieve the surface roughness requirement. It was found that combining dynamic friction polishing and mechanical abrasive polishing, a very high polishing rate and good quality surface could be obtained. The final surface roughness could be reduced to 50 nm Ra for two types of PCD specimens considered from pre-polishing value of 0.7 or 1.5 μm Ra. The polishing time required was 18 minutes, a ten fold reduction compared with the mechanical abrasive polishing currently used in industry.

In considering the concept of surface-immobilised liposomes as a drug release system, two factors need to addressed, the interfacial surface density of the liposomes for maximum drug loading and the stability of these liposomes to allow for controlled drug release. This thesis investigates a multilayer system for the affinity immobilisation of liposomes and their stability to various applied stresses. In the work presented here an allylamine monomer was used to create plasma coatings that were stable, thin and amine-rich. The aging studies using AFM showed these films to rapidly oxidise on exposure to water. The freshly deposited films were used for further surface modifications, by the covalent grafting of PEG layers of different interfacial densities under the conditions of varying polymer solvation. The AFM was used to measure the interaction forces between the grafted PEG layers and modified silica interfaces. It was found that the polydispersity of the PEG species resulted in bridging interactions of ???brush???-like PEG layers with the silica surface. These interactions were screened minimised by increasing the ionic strength of the solution. Although the densely grafted PEG layers were found to be highly protein-resistant by the XPS and QCM-D some minor protein-polymer adhesions were observed by the AFM. The densely anchored biotinylated PEG chains served as an optimum affinity platform for affinity-docking of NeutrAvidinTM molecules, which assembled in a rigid, 2-D layer as confirmed by the QCM-D. The submonolayer surface density of NeutrAvidin, as determined by Europium-labelling, was attributed to steric hindrance of the immobilised molecules. The final protein layer enabled specific binding of biotin-PEG-liposomes as a highly dissipative, dense and stable layer verified by tapping mode AFM and QCM-D. We found that these liposomes were also stable under a range of stresses induced by the shearing effects of water, silica probe and HSA layer at increased loads and velocities. The frictional response of the liposome layer also demonstrated the viscoelasticity and stability of these surface immobilised liposomes. Finally, the minimal adhesive interaction forces, as measured by the AFM, demonstrated the repellency of these liposomes to commonly found proteins, such as HSA.

L'étude du mouvement d'un patin, glissant à la surface libre d'une couche de grains, permet de tester la réponse d'un matériau granulaire immergé à un cisaillement simple. Il existe une force seuil, proportionnelle au poids du patin et indépendante de sa surface, en deçà de laquelle le patin reste immobile. Au-delà du seuil, la force de cisaillement, qui permet de déplacer le patin à vitesse constante, est proportionnelle à son poids, indépendante de sa surface et de sa vitesse. La taille des grains ne joue pas de rôle significatif dans la valeur des forces mesurées mais apparaît comme seule longueur caractéristique dans ces systèmes; d'une part, l'écoulement induit sous le patin en mouvement n'affecte que quelques couches de grains. D'autre part, pendant le régime transitoire, la couche se dilate sur une distance de glissement égale au rayon d'un grain. L'extension de ce travail à des mélanges secs de grains de deux tailles différentes montre que les coefficients de friction dépendent, de manière complexe, du taux de mélange mais que la longueur caractéristique à considérer dans ce cas est la moyenne, en masse, des diamètres des deux constituants. Par ailleurs, la contrainte seuil dépend du temps pendant lequel la couche de matériau est restée au repos avant la mesure. La condensation capillaire de ponts liquides entre les grains explique, au moins en partie, le vieillissement des propriétés mécaniques des matériaux granulaires secs en atmosphère humide. Des mesures d'angle limite d'avalanche montrent que le vieillissement des propriétés mécaniques de billes de verre immergées dans de l'eau est dû à des réactions chimiques de surface. Les propriétés mécaniques des matériaux granulaires immergés ne dépendent pas du temps en l'absence de réactivité chimique et de sollicitations extérieures (vibrations mécaniques, variations de température, etc. . . ). Cependant, les variations de la température ambiante, qui induisent une compaction lente du matériau, peuvent conduire à une augmentation des seuils d'écoulement. Les matériaux granulaires se comportent comme des fluides à seuil. L'étude du passage forcé d'un débit constant d'air au travers d'une fine couche d'un matériau granulaire immergé montre qu'il existe une surpression seuil, indépendante de l'épaisseur de la couche, en deçà de laquelle le gaz reste piégé sous la couche. à faible débit imposé, le gaz s'échappe périodiquement du système sous forme de bulles. à fort débit, l'air s'échappe continûment du système après avoir formé un canal stable au sein du matériau. Entre ces deux régimes limite, on observe un régime intermittent; le système oscille, sans périodicité apparente, entre les émissions de bulles successives et l'émission d'un jet continu d'air. Nous poursuivrons, dans un premier temps, l'étude des propriétés de friction des matériaux granulaires immergés. Nous montrerons ensuite que l'étude du passage d'un gaz au travers d'un fluide à seuil (matériau granulaire immergé, gel, mousse,. . . ), peut apporter des informations importantes pour la compréhension de systèmes géophysiques et, en particulier, de certains volcans.

<p>Vehicle simulators are becoming more common in vehicle industries. Company earns lot of money on simulations instead of real tests. Real tests are necessary but not made so extensively as before.</p><p>In this thesis the building of an vehice simulator will be described and a comparison between three different cruise controls. The three cruise controls are PI-regulator, a regulator who regulates after positions in the terrain and a MPC-regulator. The reason for choosing this three is to see the difference between simple regulation and more complex regulation with respect to fuel consumption, travel time and complexity.</p><p>The vehicle simulator is made in Matlab/Simulink, Visual Studio and Open Scene Graph. The facilities needed for runnning the simulator is a relative good computer with a grapics card on at least 128 MB RAM plus a steering wheel and pedals for brake and gas to achieve best feeling. A keyboard can be used but it reduces almost all feeling.</p><p>After several simulations a conclusion was made. The MPC-regulator was the regulator who consumed least fuel and travel time. The regulator who regulates after positions in the terrain was not too far away. It would be interesting to do more research about it. In fact it is only a PI-regulator who makes ``clever'' decisions when a hill with enough slope appears. With enough slope means a downhill where the vehicle can accelerate without the use of fuel and an uphill where the vehicle can not keep its speed with maximum use of fuel.</p><p>A conclusion was stated that the friction and height profile influenced on settings for the PI-regulator and with some adjustments on this settings, fuel could be saved.</p>

<p>Friction Stir Welding (FSW) is a new technology which joins materials by using frictional heat. Inthe first part of this thesis, a profound literature study is performed. The basic principles, therobotic implementation and possibilities to use FSW for high strength titanium alloys areexamined. In the next phase, a FSW-tool is modelled and implemented on an industrial robot in arobot simulation program. Reachability tests are carried out on car body parts and jet engineparts. By using a simulation program with embedded collision detection, all possible weldinglocations are determined on the provided parts. Adaptations like a longer FSW-tool and amodified design are suggested in order to get a better reachability. In different case studies, thenumber of required robots and the reduction of weight and time are investigated and comparedto the current spot welding process.</p>

<p>The general trend in the car body manufacturing industry is towards low-series production and reduction of press lubricants and car weight. The limited use of press lubricants, in combination with the introduction of high and ultra-high strength sheet materials, continuously increases the demands of the forming tools. To provide the means of forming new generations of sheet material, development of new tool materials with improved galling resistance is required, which may include tailored microstructures, introducing of specific(MC, M(C,N))carbides and nitrides, coatings and improved surface finish. In the present work, the wear mechanisms in real forming operations have been studied and emulated on a laboratory scale by developing a test equipment. The wear mechanisms identified in the real forming process, were distinguished into a sequence of events consisting of initial local adhesive wear of the sheets resulting in transfer of sheet material to the tool surfaces. Successive forming operations led to growth of the transfer layer and initiation of scratching of the sheets. Finally, scratching changed into severe adhesive wear, associated with gross macroscopic damage. The wear process was repeated in the laboratory test-equipment in sliding between several tool materials, ranging from cast iron to conventional ingot cast tool steels to advanced powder metallurgy tool steel, against dual-phase carbon steel sheets. By use of the test-equipment, selected tool materials were ranked regarding wear resistance in sliding against ferritic-martensitic steel sheets at different contact pressures.</p><p>Wear in sheet metal forming is mainly determined by adhesion; initially between the tool and sheet surface interaction and subsequently, after initiation of material transfer, between a sheet to sheet contact. Atomic force microscopy force curves showed that adhesion is sensitive to both chemical composition and temperature. By alloying of iron with 18wt.% Cr and 8wt.% Ni, alloying in itself, or changes in crystal structure, led to an increase of 3 times in adhesion at room temperature. Hence, alloying may be assumed a promising way for control of adhesive properties. Additionally, frictional heating should be controlled to avoid high adhesion as, generally, adhesion was found to increase with increasing temperature for all investigated materials.</p>

This thesis includes two parts. The first part reviews the history and fundamentals of surface science and tribology. The second part presents the major research outcomes and contributions. This research explores the aspects of friction, wear, and surface modification for tribological augmentation of surfaces. An effort has been made to study these aspects through gaining insights by fundamental studies leading to specific practical applications in railroads. The basic idea was to surface engineer metals for enhanced surface properties. A micro- and nano- scale experimental approach has been used to achieve these objectives. Novel principles of nano technology are incorporated into the experiments. Friction has the potential to generate sufficient energy to cause surface reactions through high flash temperatures at the interface of two materials moving in relative motion. This allows surface modifications which can be tailored to be tribologically beneficial through a controlled process. The present work developed a novel methodology to generate a functional tribofilm that has combined properties of high hardness and high wear resistance. A novel methodology was implemented to distinguish sliding/rolling contact modes during experiments. Using this method, a super hard high-performance functional tribofilm with “regenerative” properties was formed. The main instrument used in this research for laboratory experiments is a tribometer, using which friction, wear and phase transformation characteristics of railroad tribo-pairs have been experimentally studied. A variety of material characterization techniques have been used to study these characteristics at both micro and nano scale. Various characterization tools used include profilometer, scanning electron microscope, transmission electron microscope, atomic force microscope, X-ray diffractometer, nanoindenter, and X-ray photon spectroscope. The regenerative tribofilms promise exciting applications in areas like gas turbines, automotive industry, compressors, and heavy industrial equipment. The outcome of this technology will be an economical and more productive utilization of resources, and a higher end performance.

Teleoperation systems have been used in the operating rooms for more than a decade. However, the lack of force feedback in commercially available systems still raises safety issues and forbids surgical gestures like palpation. Although force feedback has already been implemented in experimental setups, a systematic methodology is still lacking to design the control laws. The approach developed in this thesis is a contribution towards such a systematic methodology: it combines the use of disturbance observers with the use of a structured fixed-order controller. This approach is validated by experiments performed on a one degree of freedom teleoperation system. A physical model of this system is proposed and validated experimentally. Disturbance observers allow to compensate friction, which is responsible for performance degradation in teleoperation. Contrary to alternative approaches,they are based on a model of the frictionless mechanical system. This allows to compensate friction with a time varying behavior, which occurs in laparoscopy. Parametric uncertainties in this model may lead to an unstable closed-loop. A kind of "separation principle" is provided to decouple the design of the closed-loop system from the design of the observer. It relies on a modified problem statement and on the use of available robust design and analysis tools. A new metric is proposed to evaluate the performance of friction compensation systems experimentally. This metric evaluates the ability of a compensation system to linearize a motion system, irrespective of the task and as a function of frequency. The observer-based friction compensation is evaluated with respect to this new metric and to a task-based metric. It correctly attenuates the friction in the bandwidth of interest and significantly improves position and force tracking during a palpation task. Structured fixed-order controllers are optimized numerically to achieve robust closed-loop performance despite modeling uncertainty. The structure is chosen among classical teleoperation structures. An efficient algorithm is selected and implemented to design such a controller, which is evaluated for a palpation task. It is compared to a full-order unstructured controller, representative of the design approach that has been used in the teleoperation literature up to now. The comparison highlights the advantages of our new approach: order-reduction steps and counter-intuitive behaviors are avoided. A structured fixed-order controller combined with a disturbance observer is implemented during a needle insertion experiment and allowed to obtain excellent performance.