Angioplasty over the years has proven to be an excellent substitute for open heart surgery where an artery/vien, blocked by atherosclerosis, is expanded using a stent. Metallic and coated metallic stents have been used for angioplasty. Metal stents might induce blood clotting, release cytotoxic heavy metal ions which are potential inducers of allergies, clotting, immune reactions and hyperproliferation of smooth muscle cells and also lead to protein absorption which activates clotting factors. Biodegradable polymers have also been tried as stent materials, but the loss of radial strength over time is a big problem associated with them. The use of a hybrid stent, consisting of biodegradable polymer and biocompatible stainless steel, is proposed. The use of such a system would require excellent adhesion between the stent metal and the biodegradable polymer. This study presents the electrochemically induced micromechanical interlocking to enhance adhesion between 304 stainless steel and high density polyethylene. High density polyethylene was used instead of biodegradable polymer for initial investigation. Electrochemical etching on the stainless steel wire was accomplished by immersing a stainless steel wire in a sodium carbonate electrolyte while applying a known voltage through the wire. The electrochemical etching of the stainless steel wire resulted in pitting under suitable conditions. The etching time, voltage and electrolyte concentration were varied to achieve different pit sizes and pit distributions on the stainless steel wire. An image analysis was conducted using an image analysis software to find the exact pit size and pit distribution on the stainless steel wire from electrochemical etching. A statistical model based on design of engineering experiments was derived. Etched and the unetched wires were molded with high density polyethylene and a mechanical test was conducted to measure the force required to pull the wire out of the polymer and verified using calculations based on the pit size and pit distribution of the pits on the surface of the wire. Electrochemical etching produced burr free surface features. It was observed that the pH level in the electrolyte contributes to the pit size and pit distribution. The results of the statistical model were consistent with the experimental values and it was possible to optimize the electrochemical etching parameters for maximum pit size and pit distribution. It was also observed that while voltage and etching time contribute to pit size and pit distribution, the electrolyte concentration does not have significant effect on the pit size and pit distribution. The calculated pull out force and measured values were off by 22.7%. The lower value of calculated force could result from neglecting some of the smaller pits while performing the image analysis. The average adhesive strength of the etched samples was 276% higher than that of the unetched samples.

Este trabalho objetivou a manufatura de laminados híbridos metal-fibra (LMF) empregando-se chapas com 0,5 mm de espessura de liga-\'TI\'6\'AL\'4\'V\' com superfícies modificadas por laser de fibra de modo a otimizar a sua adesão com polímero termoplástico poli-sulfeto de fenileno (PPS). Observou-se que a microtextura superficial da liga metálica dependeu fortemente da potência do feixe laser, quando potências mais baixas levaram à verdadeira texturização da superfície metálica, enquanto que potências mais elevadas conduziram à ablação da mesma. A texturização superficial metálica sob laser de baixa potência aparentou ser a condição mais apropriada para a adesão metal-polímero por ancoragem mecânica de macromoléculas, o que foi contrabalanceado por elevados níveis de tensão residual das chapas metálicas, gerando grande distorção das mesmas e inviabilizando sua utilização. O emprego de uma potência intermediária (160 W) mostrou-se propício à otimização entre a adesão física entre metal-polímero e o nível de tensões residuais criado nas chapas metálicas. Concluiu-se que os espécimes extraídos do centro dos laminados metal-fibra exibem uma tensão limite média para falha por cisalhamento interlaminar consideravelmente superior à dos espécimes usinados a partir da borda dos LMF. O LMF manufaturado sob maiores pressão e temperatura exibiu uma maior compactação e melhor consolidação, culminando num máximo desempenho médio sob carga de cisalhamento interlaminar. Evidências de uma correlação entre o mecanismo de falha por cisalhamento interlaminar do corpo de prova e o seu nível de resistência a este tipo de carregamento mecânico foram documentadas e discutidas. / This work aimed at manufacturing hybrid fiber-metal laminates (FML) by employing 0,5 mm-thick \'TI\'6\'AL\'4\'V\'-alloy plaques with fiber laser modified surface in order to optimize metal adhesion with poli-phenylene sulfide (PPS) thermoplastic polymer. The surface microtexture of metallic alloy strongly depended upon the laser power, inasmuch as low-power laser led to true texturization of metal surface, whereas high-power laser light drove to its ablation. Surface metal texturization under low-power laser apparently was the most appropriate condition to metal-polymer adhesion via mechanical entanglement of macromolecules, which was offset by high levels of residual stresses on metallic plaques, bringing them quite warped and useless. The use of an intermediate laser power (160 W) has been shown benign to the optimization between metal-polymer physical adhesion and the residual stress level created in the metal plates. It has been concluded that testpieces machined from the FML central position exhibited average ultimate interlaminar shear strenght considerably higher than those extracted from the FML borders. The FML manufactured under higher pressure and temperature was more compacted and better consolidated, so that it displayed the greatest average performance under interlaminar shear loading. Evidences of a correlation between the failure mechanism by interlaminar shearing of test coupon and its allowance to this type of mechanical loading were documented and discussed.

Este trabalho objetivou a manufatura de laminados híbridos metal-fibra (LMF) empregando-se chapas com 0,5 mm de espessura de liga-\'TI\'6\'AL\'4\'V\' com superfícies modificadas por laser de fibra de modo a otimizar a sua adesão com polímero termoplástico poli-sulfeto de fenileno (PPS). Observou-se que a microtextura superficial da liga metálica dependeu fortemente da potência do feixe laser, quando potências mais baixas levaram à verdadeira texturização da superfície metálica, enquanto que potências mais elevadas conduziram à ablação da mesma. A texturização superficial metálica sob laser de baixa potência aparentou ser a condição mais apropriada para a adesão metal-polímero por ancoragem mecânica de macromoléculas, o que foi contrabalanceado por elevados níveis de tensão residual das chapas metálicas, gerando grande distorção das mesmas e inviabilizando sua utilização. O emprego de uma potência intermediária (160 W) mostrou-se propício à otimização entre a adesão física entre metal-polímero e o nível de tensões residuais criado nas chapas metálicas. Concluiu-se que os espécimes extraídos do centro dos laminados metal-fibra exibem uma tensão limite média para falha por cisalhamento interlaminar consideravelmente superior à dos espécimes usinados a partir da borda dos LMF. O LMF manufaturado sob maiores pressão e temperatura exibiu uma maior compactação e melhor consolidação, culminando num máximo desempenho médio sob carga de cisalhamento interlaminar. Evidências de uma correlação entre o mecanismo de falha por cisalhamento interlaminar do corpo de prova e o seu nível de resistência a este tipo de carregamento mecânico foram documentadas e discutidas. / This work aimed at manufacturing hybrid fiber-metal laminates (FML) by employing 0,5 mm-thick \'TI\'6\'AL\'4\'V\'-alloy plaques with fiber laser modified surface in order to optimize metal adhesion with poli-phenylene sulfide (PPS) thermoplastic polymer. The surface microtexture of metallic alloy strongly depended upon the laser power, inasmuch as low-power laser led to true texturization of metal surface, whereas high-power laser light drove to its ablation. Surface metal texturization under low-power laser apparently was the most appropriate condition to metal-polymer adhesion via mechanical entanglement of macromolecules, which was offset by high levels of residual stresses on metallic plaques, bringing them quite warped and useless. The use of an intermediate laser power (160 W) has been shown benign to the optimization between metal-polymer physical adhesion and the residual stress level created in the metal plates. It has been concluded that testpieces machined from the FML central position exhibited average ultimate interlaminar shear strenght considerably higher than those extracted from the FML borders. The FML manufactured under higher pressure and temperature was more compacted and better consolidated, so that it displayed the greatest average performance under interlaminar shear loading. Evidences of a correlation between the failure mechanism by interlaminar shearing of test coupon and its allowance to this type of mechanical loading were documented and discussed.

L'objectif de la présente thèse est d'améliorer les propriétés barrières du MetPET en conditions sévères. Plus précisément d'établir les corrélations structure-propriétés : structure du primaire d'accroche déposé en ligne sur le film PET avant métallisation et propriétés barrières et d'adhésion métal en condition sèche et humide du composite final obtenu (MetPET). L'approche choisie est la polymérisation en émulsion en régime semi-continu. Cette approche permettra d'apporter un caractère hydrophobe (phase 1-Coeur) favorisant la barrière à l'humidité et un caractère hydrophile (phase 2-Ecorce) en surface présentant des groupes fonctionnels favorables à l'adhésion métal en condition humide. De plus nous avons aussi investigué l'influences de divers additifs de formulations afin d'optimiser les propriétés du primaire d'accroche. Les latex présentant une structure de type cœur/écorce est très favorable pour la barrière à l'humidité. En effet ces latex présentent une perméabilité à l'eau sensiblement plus faible que les latex sans structure (100% composition de l'écorce). Concernant la perméabilité à l'oxygène celle-ci est principalement assurée par la couche métallique. La formulation de nos latex cœur/écorce par des agents mouillants s'est révélé indispensable pour assurer un bon étalement de nos latex sur le substrat PET. En effet nos latex issus de la synthèse ont été synthétisés avec un minimum de tensio-actif, ce qui a eu pour effet négatif d'obtenir une tension de surface trop élevée pour assurer leur mouillabilité sur le film PET. De plus cet agent mouillant a aussi montré une influence positive sur les performances d'adhésion de la couche métal sur le film PET traité avec le primaire d'accroche. La formulation de nos latex cœur/écorce par un réticulant a montré un influence positive sur les propriétés barrières aux gaz et sur les performances d'adhésion métal. Cet agent réticulant tend à favoriser la réticulation entre particule et ainsi favoriser la formation d'un film continu barrière à l'eau. De plus celui-ci apporte des fonctions de type azoté favorable aux interactions avec les atomes métallique (aluminium) / The proposition of this work is to improve the barrier property of a laminate aimed to be applied in the field of packaging for foodstuffs. This laminate is constituted by a PET substrate metallized with aluminum deposited under vacuum. Given that PET is not a strongly polar polymer it is necessary to improve its adhesion to metals. This study was carried out in order to understand if there is a way to make sure that the polar groups will be bonded to the metal without being disturbed by the conditions of the environment. Our approach was the semi-batch emulsion polymerization, followed by the restructuration of the initial system (regular spherical polymeric nanoparticles) by changing its original morphology. Finally, the latexes were formulated by using variable amounts of compounds that were expected to improve the properties of the final material in terms of barrier and metallic adhesion. A part of the latexes synthesized in the scope of this work was submitted to pilot trials in an industrial line of PET extrusion. The latexes were used to coat the PET inline. The core-shell nanoparticles presented a lower permeability to water than the particles synthesized in the absence of the seed. This was related to the tortuosity promoted by the core, which increases the pathway of a diffusing molecule. The permeability to oxygen was found to be mainly related to the metallic layer. Given that the latexes were synthesized with the minimum amount of tensioactive necessary to originate stable dispersions, the wettability agent was found to be indispensable for the proper spreading of the coatings onto the PET. Furthermore, this compound played an important role on the adhesion property of the films. The cure agent, in the correct concentration, promotes the adhesion to metallic substrates. Moreover, this compound helped to prevent the interaction of the wettability agent with the water, decreasing consequently the plasticization of the structure in conditions of high humidity