Industries (food, beverage, petrochemical, etc.) normally use various gravitational separation echniques in their processes. Such separation processes often suffer from the deposition of undesirable material on the active surfaces of the process equipment, e.g. a high-speed separator or decanter, causing a slew of problems with the process or product quality. To restore operational efficiencies, additional cleaning steps using both water and chemicals are required, making the process more expensive and less environmentally friendly. Other than operating time and concentration of the process fluid there are several factors such as surface nature, surface roughness, type of material, surface charge, etc which influence the fouling deposition of surfaces. Fouling on the surfaces can grow following different mechanisms. The goal of this research work is to learn more about the nature of foulant interactions with stainless steel surfaces and eventually design some antifouling methodology. It is too difficult to study foulingfor all kinds of solutions and industries, so we tried to investigate the organic deposition in dairy and brewery industries by using lab-scale synthesized milk and beer solutions, For quantitative and statistical examination of these characteristics, several experimental approaches (FTIR, percent weight change, surface roughness, surface energy) were used. It was confirmed that fouling grows on the surfaces in a non-linear fashion irrespective of the time and concentration of the solution. The fouling of surfaces can be improved by producing more hydrophilic surfaces or by reducing surface roughness. Steric hindrance, electrostatic charge, and water barrier or hydration layer theories can be used to modify the surface nature and hence the fouling deposition. For antifouling purposes, PMMA (organic) and tungsten oxide (inorganic) coatings were employed. The PMMA was deposited using a dip-coating technique using (6%,10%, and 12%) PMMA solution, and the tungsten oxide coating was carried out by using a standard two electrode electrochemical system under different voltage (3.5V and 4.5V) and time (5min, 10 min, and 20 min) conditions. The coatings were characterized by using different techniques and their antifouling effects were studied in model milk and model beer solutions / Vid industriella processer (livsmedel, petrokemisk etc.) används ofta olika tekniker för separation med hjälp av gravitation. Sådana separationsprocesser drabbas ofta av oönskade beläggningar och påväxt på processutrustningens aktiva ytor så som t.ex. i en separator eller en dekanter, vilket orsakar problem med processen eller produktkvaliteten. För att återställa driftseffektivitet krävs särskilda rengöringssteg med både vatten och kemikalier vilket gör processen dyrare och mindre miljövänlig. Förutom drifttid och processvätskans sammansättning finns det flera faktorer såsom ytbeskaffenhet, ytjämnhet, materialtyp, ytladdning m.m. som påverkar mängden oönskade beläggningar på ytor. Föroreningarna på ytor kan tillväxa med olika mekanismer. Målet med detta forskningsarbete är att studera interaktionen mellan olika former av påväxt och ytan på rostfritt stål och senare utforma metoder för att förhindra bildandet av sådana oönskade beläggningar. Det är en stor utmaning att studera olika typer av påväxt för alla typer av flöden och industrier. I studien undersöktes organisk påväxt inom mejeri- och bryggeriindustrin genom att använda syntetiserade mjölk- och ölprodukter i laboratorieskala, för kvantitativa och statistiska undersökningar av dessa egenskaper. Flera olika experimentella metoder användes (FTIR, viktförändring, ytjämnhet, ytenergi). Det bekräftades att tillväxten på ytorna var olinjärt oavsett tid och lösningens koncentration. Bildandet och tillväxt av oönskade beläggningar kan minskas med hjälp av mera hydrofila ytor eller genom att minska ytans ojämnhet. Steriska hinder, elektrostatisk laddning och vattenbarriär eller hydratiseringsskal kan användas för att modifiera ytan och därmed fördröja bildandet av oönskade beläggningar. För att förhindra påväxt belades ytan med PMMA (organisk) och volframoxid (oorganisk). PMMA deponerades genom en doppbeläggningsteknik med användning av (6%, 10% och 12%) PMMA-lösning och volframoxidbeläggningen utfördes med ett elektrokemiskt tvåelektrodssystem med olika spänningar (3,5V och 4,5V) och tider (5min, 10min och 20min). Ytbeläggningarna karakteriserades genom att använda olika tekniker och deras förmåga att förhindra snabb påväxt studerades i modellösningar av mjölk och öl.

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Tratamentos de superfície são técnicas amplamente utilizadas com a finalidade de aumentar a resistência à corrosão de materiais metálicos. No caso específico do alumínio e ligas de alumínio, o tratamento com cromo hexavalente é um dos processos mais utilizados. Isso, em razão da eficiência e da facilidade de aplicação desse processo. Entretanto, em virtude de restrições ambientais e do elevado custo de tratamento de resíduos gerados neste processo, métodos alternativos para sua substituição vêm sendo avaliados. Neste contexto, o presente estudo investigou o processo de formação e proteção à corrosão fornecida por filmes de moléculas autoorganizáveis de compostos à base de fosfonatos sobre a liga de alumínio 1050. Para definir as condições do tratamento foram utilizadas medidas de condutividade e de ângulo de contato, juntamente com ensaios eletroquímicos. Técnicas eletroquímicas, especificamente: medidas de variação do potencial a circuito aberto (PCA), espectroscopia de impedância eletroquímica (EIE) e polarização potenciodinâmica foram utilizadas para avaliar a proteção à corrosão. Os diagramas experimentais de impedância foram interpretados utilizando circuitos elétricos equivalentes que simulam modelos do filme de óxido que se forma na superfície da liga. Os resultados fornecidos com a liga tratada com moléculas auto-organizáveis foram comparados com resultados obtidos em iguais condições com amostras da liga sem qualquer tratamento ou cromatizada com Cr(VI) e mostraram que o tratamento com moléculas auto-organizáveis aumenta significativamente a resistência à corrosão da liga e apresenta, em determinadas condições, desempenho próximo ao fornecido pelo processo de cromatização. / Surface treatments are widely used to increase the corrosion resistance of metallic materials. Specifically for aluminum and aluminum alloys, treatment with hexavalent chromium is one of the most used, due to its efficiency and ease of application. However, because of environmental restrictions and the high cost involved in the treatments of waste generated in this process, alternative methods for its replacement are necessary. In this context, this study investigated the effect of the surface treatment with self-assembling molecules (SAM) based on phosphonate compounds on the corrosion of the 1050 aluminum alloy. The conditions adopted for the SAM treatment were determined by conductivity and contact angle measurements, besides electrochemical experiments. Electrochemical techniques, specifically: measurement of the open circuit potential (OCP) variation with time, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves were used to evaluate the corrosion resistance of the 1050 aluminum alloy exposed to SAM treatment The experimental impedance diagrams were interpreted using equivalent electrical circuit models that simulate film that is formed on the alloy surface. The results of the samples treated with SAM were compared with those of samples either without any treatment or treated with chromatizing conversion coating with Cr(VI) and showed that the first treatment significantly increased the corrosion resistance of the aluminum alloy and approached that of chromatizing with Cr(VI) process.

Atualmente, quando se tem a necessidade de nitretar peças produzidas pela metalurgia do pó, usa-se a nitretação a plasma. Apesar de ser um processo de alto custo, com diversas dificuldades operacionais e de ajuste de processo, a nitretação a plasma é o único processo viável para nitretar esses materiais por ter uma ação apenas superficial, não apresentando ação nitretante no interior dos poros. Nos processos de nitretação a gás e banho de sais, o meio nitretante penetra na porosidade (interconectada) dos materiais sinterizados, havendo assim a formação de camada branca em uma grande profundidade da peça (ou mesmo na peça toda), gerando problemas de deformação e fragilização do componente. Este trabalho teve por objetivo a aplicação do processo shot peening em peças sinterizadas com a finalidade de fechar a porosidade superficial das peças e estudar seu comportamento sob o processo de nitretação a gás. O estudo verifica que o material sinterizado submetido à nitretação gasosa permitiu a entrada do meio nitretante pelos poros abertos e interconectados promovendo a formação de camada branca no interior dos poros de praticamente todo o volume da peça. Essa camada branca no interior do material fragiliza o componente e inviabiliza sua utilização como componente em praticamente qualquer aplicação industrial. As peças sinterizadas jateadas com granalhas de aço antes da nitretação também permitiram o acesso do meio nitretante no interior do componente, porém, sem potencial suficiente para a formação de camada branca. As amostras jateadas apresentaram apenas agulhas de nitretos formados durante a nitretação. / Plasma nitriding is the process used to nitriding components produced by powder metallurgy. Although its high coast and operational difficulties, this is the best process for this kind of materials because the nitring occurs only in the surface. In gas and liquid nitriding processes the nitriding atmosphere goes through interconnected porous and the white layer forms not only on the surface but around internal porous resulting in embrittlement and deformation of the component. The aim of this work was evaluate the gas nitriding behavior of iron samples as received and previously submitted to shot peening process in order to close superficial porosities in a gas nitriding process. The results have shown that during gas nitriding the samples as received, did not present white layer at the surface but around the porous in the bulk of the sample. This fact suggested that the gaseous atmosphere goes through interconnected porous. This white layer causes the embrittlement of the component and its use in industrial application is not recommended. Otherwise, samples previously submitted to shot peening process before nitriding showed an external white layer but also permitted the access of nitriding atmosphere to the bulk of the sample, but in this case the nitriding potential was not sufficient to form white layer around internal porous.

O objetivo deste estudo foi investigar o efeito de filmes finos depositados por plasma nas propriedades de superfície, ópticas, microbiológicas e mecânicas de materiais restauradores indiretos. Utilizou-se discos de porcelana (PC) (VM9, VITA, Zahnfabrik) e compósitos indiretos (Enamic (EN) e Lava Ultimate (LU) ) (12 x 1,1 mm). Diferentes metodologias de deposição dos filmes foram estabelecidas: polimerização a plasma (PECVD) com 70%HMDSO/30%argônio (PAr); PECVD com 70%HMDSO/30%oxigênio (PO2); implantação iônica e deposição por imersão em plasma usando 70%HMDSO/30%argônio (PIDP). Um grupo sem filme foi usado como grupo controle (CTL) O reator de plasma foi bombeado até 2,0 Pa e HMDSO, oxigênio ou argônio foram admitidos no reator estabelecendo a pressão de 20 e 24 Pa. O plasma foi estabelecido pela aplicação de radiofrequência (13,56 MHz, 50-150 W, 30 ou 10 min) à um porta amostra em um sistema capacitivamente acoplado. A rugosidade e a espessura do filme foram determinadas por perfilometria; a molhabilidade foi medida pelo ângulo de contato. A morfologia foi avaliada utilizando microscopia eletrônica de varredura e de força atômica e a composição química foi investigada por espectroscopia de energia dispersiva (EDS), de fotoelétrons excitados por raios-x (XPS) e espectroscopia de infravermelho com transformada de Fourier. A razão de contraste e diferenças de cor foram estudadas pela espectrofotometria no visível. As propriedades mecânicas e tribológicas dos filmes foram determinadas por nanoindentação e nanoriscos. O crescimento do biofilme foi avaliado por microscopia confocal de varredura a laser. As propriedades mecânicas foram determinadas pela resistência à flexão biaxial e fadiga. Todos os dados foram analisados estatisticamente (?=0,05). A rugosidade não foi alterada para a maioria dos grupos com filme, exceto para PC-PAr (p=0,023) e EN-PIDP (p=0,001), que tiveram uma diminuição e aumento, respectivamente. As espessuras dos filmes foram de 620 nm (PAr), 540 nm (PO2) e 70 nm (PIDP). A molhabilidade para todos os grupos com filmes diminuiu, exceto o grupo LU-PIDP (p<0,001). A análise morfológica demonstrou que os filmes revestiram os substratos uniformemente sem descontinuidades. Os filmes PO2 apresentaram estruturas granulares que se apresentaram em menor tamanho e quantidade para PAr e PIDP. A composição química dos filmes revelou três elementos principais: silício, oxigênio e carbono. PAr apresentou uma composição mais orgânica, enquanto PO2 e PIDP mostraram uma natureza mais inorgânica. A razão de contraste diminuiu apenas em LU-PIDP (p<0.001) e os valores de ?E ficaram abaixo de 3,3 para todos os grupos com filme. As propriedades mecânicas e tribológicas foram alteradas com a presença dos filmes, de acordo com cada substrato. Os filmes PAr demonstraram a menor dureza e o maior coeficiente de atrito. Os filmes PO2 e PIDP apresentaram maior dureza e menor coeficiente de atrito. Os filmes alteraram o biofilme formado e a viabilidade das colônias em parâmetros específicos. Não houve mudança na resistência e probabilidade de falha dos materiais com filmes. Conclui-se que os filmes finos depositados alteraram as propriedades de superfície e a formação do biofilme, mantendo a cor e rugosidade abaixo de valores críticos e não influenciaram na resistência mecânica ou probabilidade de falha dos materiais restauradores. / The aim of this study was to investigate the effect of plasma deposited thin films on surface, optical, microbiological and mechanical properties of indirect restorative materials. A porcelain (VM9, VITA, Zahnfabrik) and indirect composite disks (Enamic, VITA; Lava Ultimate, 3M ESPE), were used (12 x 1.1 mm). Different methodologies of film deposition were established: plasma-enhanced chemical vapor deposition (PECVD) with 70%HMDSO/30%argon (PAr); PECVD with 70%HMDSO/30%oxygen (PO2); plasma immersion ion implantation and deposition using 70%HMDSO/30%argon (PIDP). Samples with no films were used as control group (CTL). The plasma reactor was pumped down to 2.0 Pa and HMDSO, oxygen or argon were admitted to the reactor establishing the pressure of 20 and 24 Pa. The plasma was ignited by the application of radiofrequency power (13.56 MHz, 50-150 W, 30 or 10 min) to the lowermost sample holder of a capacitivelly-coupled system. Surface roughness and film thickness were determined by perfilometry. Wettability was measured with a goniometer. Morphological analysis was evaluated using scanning electron microscopy and atomic force microscopy. Surface chemical composition was investigated by energy-dispersive and x-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy. Optical properties were studied by contrast ratio and color differences. Mechanical and tribological properties of the coatings were determined by nanoindentation and scratching test. Biofilm growth was evaluated by confocal laser scanning microscopy. Mechanical properties were determined by biaxial flexural strength and fatigue test. Data were analyzed by statistically (alpha=0.05). Surface roughness was not changed for most of groups after film deposition, PC-PAr and EN-PIDP groups, showed a decrease (p=0.023) and an increase (p=0.001), respectively. The films\' thicknesses were 620 nm (PAr), 540 nm (PO2) and 70 nm (PIDP). A decrease in wettability for all film groups was detected, except LU-PIDP (p<0.001). Morphological analysis demonstrated that films coated the substrates uniformly without any discontinuities. For all materials in PO2, granular structures covered the surface. For PAr and PIDP, these structures decreased. The films\' chemical composition revealed three main elements: silicon, oxygen and carbon. PAr presented a more organic behavior. PO2 and PIDP showed an inorganic nature. For contrast ratio there was only a decrease for LU-PIDP (p<0.001) and color differences continued below 3.3. Mechanical and tribological properties were changed with the presence of the coatings, according to each substrate. PAr films demonstrated the lowest hardness and highest friction coefficient. PO2 and PIDP films had higher hardness and lower friction coefficient values. The films, in different parameters, altered biofilm structure and colony viability. There was no change in strength and failure probability for all coated groups. It can be concluded that plasma-deposited thin films altered specific surface characteristics and biofilm growth, maintaining color properties and surface roughness below established thresholds and strength and failure probability didn\'t differ with the presence of the thin films.

This thesis focuses on designing thermoplastic composites with high mechanical properties and a low processing temperature. Thermoplastic composites, which are used in this work, are composed of thermoplastic polyurethane (TPU) matrices and plain woven E-glass fabrics (GFs). TPUs were synthesised with large quantities of hard segments (HS), including 70% and 90%wt HS. The GF-TPU composites manufactured in this study have a melting point of around 175oC. As such, 180oC represents the processing temperature, which was used to produce GF-TPU composites. The influences of HS content and annealing treatment at 80oC on the thermal, dynamic mechanical and mechanical properties of TPU samples and GF-TPU composites with 25% fibre volume fraction (Vf) have been investigated. The highest crystallinity, storage modulus, Tg, yield strength, tensile strength and tensile modulus of all the TPU samples are seen in the TPU/90 samples annealed for 4 days. The TPU/90 samples display higher tensile properties than the TPU/70 and polypropylene (PP) samples, while the PP samples show the greatest elongation at break point. Furthermore, the tensile properties of the TPU/70 and TPU/90 samples are much higher than those of commercial TPUs. As such, annealed GF-TPU/90 composites with 25% Vf present the greatest dynamic mechanical, flexural, and tensile properties. GF-TPU/90 composites with 25% Vf show higher flexural strength than GF-PP composites or GF-polyamide 6 (PA6) composites with the same Vf. The effects of fibre surface treatments on the mechanical properties of GF and GF-TPU/70 composites with 25% Vf have also been studied in this investigation. GF treated with burn-off treatment is found to exhibit the lowest tensile properties. The interfacial adhesion between GF treated by NaOH for 0.5hrs and a TPU/70 matrix is greater than between GF treated by acetone for 5hrs and a TPU/70 matrix. Silanised GF presents greater tensile properties than desized GF. Thus, enhanced interfacial adhesion and tensile, flexural, ILSS and GIC properties are observed in the silanised GF-TPU/70 composites than in the desized GF-TPU/70 composites. GF-TPU/70 composites based on GFs treated by NaOH for 0.5hrs then sized with 0.15%wt. aminosilane display the greatest interfacial adhesion, flexural properties, ILSS and GIC, damage tolerance and impact-damage resistance. Conversely, the lowest interfacial adhesion, GIC, damage tolerance and impact-damage resistance are seen in the GF-PP composites based on 25% Vf as-received GF. There is a significant increase in the tensile and flexural properties of GF-TPU/90 composites with increasing the Vf from 25% to 50%. Moreover, the flexural strength of GF-TPU/90 composites with 50% Vf is not only higher than that of GF-EP composites or GF-vinyl ester composites with normalised 50% Vf, but is also much higher than that of GF-PP composites with 50% Vf. Despite this result, GF-TPU/90 composites with 50% Vf show the lowest fracture toughness, impact-damage resistance and damage tolerance, which are improved by adding 25% and 50%wt. of TPU/70 to the TPU/90 matrix. GF-TPU/90 composites based on a modified matrix have higher GIC, GIIC, impact-damage resistance and damage tolerance than GF-TPU/90 composites based on an unmodified matrix. The GIC, GIIC, impact-damage resistance and damage tolerance of GF-TPU/90 composites based on a modified matrix increase with increasing the percentage of TPU/70. Hence, the highest GIC, GIIC, impact-damage resistance and damage tolerance are seen in the GF-TPU/90 composites based on a modified matrix with 50%wt. of TPU/70.

Neste trabalho investigamos os efeitos de superfícies de contorno e de confinamento na ordem orientacional de cristais líquidos, onde utilizamos cristais líquidos termotrópicos e liotrópicos. A importância deste estudo deve-se à aspectos tanto de interesse tecnológico (formas de alinhamento) como de pesquisa básica. Com relação aos cristais líquidos termotrópicos, determinamos que cargas eletrostáticas superficiais induzidas por esfregamento influenciam as propriedades orientacionais do cristal líquido, essas cargas foram medidas com a técnica de microscopia de força eletrostática (EFM). Estudamos novas formas de alinhamento ao tratar a superfície com polímeros fotosensíveis, onde foi possível introduzir uma competição entre dois potenciais superficiais de alinhamento (grades de relevo e fotoalinhamento) e geramos padrões microtexturizados com diferentes direções de alinhamento, o que pode ser aplicado na elaboração de dispositivos biestáveis. Em ambos os casos, uma forma de alinhamento local pode ser obtida com o uso de um microscópio óptico de campo próximo (SNOM). Com o uso de um surfactante (OTE) produzimos um perfil periódico de alinhamento homeotrópico e planar para tentar observar estados orientacionais esperados teoricamente, além de propor novos tratamentos superficiais. As análises topográficas foram feitas com medidas de microscopia de força atômica (AFM) e as análises de textura do cristal líquido com um microscópio óptico de luz polarizada. O efeito do confinamento de uma amostra de cristal líquido liotrópico foi investigado através do comportamento dinâmico induzido por campos magnéticos externos, dando evidências de uma transição de fase induzida apenas pelo confinamento da amostra. A ocorrência desta transição de fase foi confirmada através de medidas diretas com o uso de técnicas ópticas não-lineares, como a geração de segundo harmônico e Varredura-Z. / In this work we investigated the boundary surface and confinement effects on the orientational order of liquid crystals, where we used thermotropic and lyotropic liquid crystals. The importance of these studies refers to technological and fundamental research aspects. Regarding to the thermotropic liquid crystals, we determined that the electrostatic charges induced by rubbing of polymeric surfaces influence the liquid crystal orientational properties, these charges were measured with the electrostatic force microscopy technique (EFM). We studied new liquid crystal aligning forms with photosensitive polymers, where it was possible to impose a competition between two surface aligning potentials (surface relief gratings and photoalingment) and we created microtextured patterns of diferent alignment directions, which favors the use in bistable devices. In both cases, a local treatment can be achieved with a scaning near-field optical microscope (SNOM). With a surfactant (OTE) we produced periodic patterns of homeotropic and planar states to investigate the possibility of new orientational states induced to the liquid crystal, which are expected theoretically. The topographic analysis were done by atomic force microscopy (AFM) measurements and the liquid crystal texture was investigated with a polarized microscope. The confinement effect on a lyotropic liquid cristal was investigated according to theoretical approches of the dynamical behavior induced by external magnetic fields, giving evidences of a phase transition induced only due to the sample confinement. This phase transition was confirmed with direct measurements of the transition by using nonlinear optical techniques, as second harmonic generation and Z-scan.

Nanocompósitos de Al2O3/ZrO2 apresentam-se promissores para serem utilizados como biomateriais, por promoverem melhorias significativas quanto à homogeneidade microestrutural, propriedades mecânicas e serem biologicamente inerte. Dentre as técnicas capazes de tornar seu desempenho biológico mais adequado, o recobrimento biomimético tem se destacado, sendo que sua eficiência pode ser melhorada a partir de prévios tratamentos superficiais. Nesse sentido, o objetivo desse trabalho foi estudar a adesão e a uniformidade do revestimento de fosfato de cálcio em nanocompósitos de Al2O3 contendo 5% em volume de inclusões nanométricas de ZrO2. Para isso, nanocompósitos foram conformados, sinterizados, tratados quimicamente com soluções de H3PO4, HNO3 e NaOH e por plasma em diferentes condições de processo: 20%N2-80%H2, 40%N2-60%H2, 40%N2-40%H2-20%O2, 30%N2-50%H2-20%O2, 100%N2 e 100%O2 e recobertos biomimeticamente com soluções que simulam o plasma sanguíneo (SBF 1,5x e 5,0x) nos tempos de 7, 14, 21 e 28 dias de incubação. A partir dos resultados obtidos pode-se observar que os prévios tratamentos superficiais promoveram variações na rugosidade média superficial (Ra) entre 0,045 e 0,079 &micro;m. Além disso, independentemente do tratamento superficial, observou-se a formação de apenas três fases de fosfatos de cálcio: hidroxiapatita (HA), &alpha;-fosfato tricálcico (&alpha;-TCP) e &beta;-fosfato tricálcico (&beta;-TCP). Observou-se ainda, que o percentual das fases formadas variou de acordo com o tratamento, sugerindo a possibilidade de controlar a razão TCP:HA. Nos resultados obtidos pelo teste de riscamento observou-se que tratamentos realizados com plasma, H3PO4 e HNO3 aumentaram a carga crítica (Lc) entre 2,0 e 2,9N, melhorando assim a aderência da camada de fosfato de cálcio formada. Os testes de proliferação celular utilizando linhagem de células de hamster chinês (CHO) demonstraram que os nanocompósitos tratados com H3PO4, HNO3 e NaOH e recobertos biomimeticamente com SBF 5,0x são biocompatíveis. / Nanocomposite Al2O3/ZrO2 have to be promising to be used as biomaterials for promoting significant improvements in the microstructural homogeneity, mechanical properties and be biologically inert. Among the techniques to make it more useful biological performance, the biomimetic coating has been highlighted, and its efficiency can be improved from previous surface treatments. In this sense, the objective of this work was to study the adhesion and uniformity of calcium phosphate nanocomposite coating of Al2O3 containing 5% by volume of nanometric inclusions of ZrO2. For this nanocomposites were shaped, sintered, chemically treated with solutions of H3PO4, HNO3 and NaOH, and plasma in different process conditions: 20%N2-80%H2, 40%N2-60%H2, 40%N2-40%H2-20%O2, 30%N2-50%H2-20% O2, 100% N2 and 100%O2 and covered with solutions biomimetic that simulate the blood plasma (SBF 1.5x and 5.0x) in the times of 7, 14, 21 and 28 days of incubation. From the results obtained it can be seen that prior surface treatments promoted variations in average surface roughness (Ra) from 0.045 to 0.079 micrometers. Furthermore, regardless of surface treatment, formation of the observed only three-phase calcium phosphate: hydroxyapatite (HA), tricalcium &alpha;-phosphate (&alpha;-TCP) and &beta;-tricalcium phosphate (&beta;-TCP). It was also observed that the percentage of phases formed varied according to the treatment, suggesting the possibility of controlling the ratio TCP:HA. In the results obtained by scratching test was observed that plasma treatments performed, HNO3 and H3PO4 increased the critical load (Lc) between 2.0 and 2,9N, thereby improving the adhesion of the calcium phosphate layer is formed. Cell proliferation assays The strain using chinese hamster cells (CHO) have demonstrated that nanocomposites treated with H3PO4, HNO3 and NaOH, and coated with solution biomimetic SBF 5.0x are biocompatible.

La production de poly(chlorure de vinyle) (PVC) sous forme de suspension chez INEOS ChlorVinyls est réalisée en réacteur fermé agité, dont les parois sont en émail ou en acier inoxydable. Il se forme en cours de polymérisation un dépôt de PVC (croûte) sur les parois du réacteur qui génère de nombreux inconvénients. Afin de limiter cet encroûtement, INEOS ChlorVinyls et l’ensemble des producteurs de PVC appliquent à chaque batch (par exemple pour INEOS ChlorVinyls 50 fois par jour pour ses 22 réacteurs) un revêtement organique. L’application systématique du revêtement et la formation de croûtes ont des conséquences économiques non négligeables (arrêts de production, coût de main d’œuvre et matière, coût de traitement des déchets, qualité du PVC contaminé par le revêtement…).La compréhension du phénomène d’encroûtement en vue de développer un revêtement permanent devient donc nécessaire pour améliorer la qualité des produits, diminuer les coûts et dégager un avantage concurrentiel favorable à INEOS vis-à-vis de ses concurrents. Le sujet de thèse a été divisé en deux parties bien distinctes avec premièrement l’étude du mécanisme d’encroûtement et la mise en place d’un scénario permettant d’expliquer de manière physique et chimique la formation de la croûte sur les parois du réacteur. Une seconde partie a été dédiée au développement d’un revêtement polymère avec la sélection d’un système résistant au milieu réactionnel de polymérisation en suspension du chlorure de vinyle puis à l’optimisation de l’adhésion du revêtement polymère sur acier inoxydable afin d’obtenir des performances maximales et durables. / The suspension synthesis of PolyVinyl Chloride (S-PVC) at the INEOS ChlorVinyls facility in Mazingarbe (FRANCE) is realized thanks to a closed-reactor technology with reactor walls made of stainless steel or enamel. One of the major problems during the production of PVC by suspension polymerization is the formation of a deposit (called crust or scale) on the reactor walls. The formation of scale leads to numerous sorts of drawbacks like a decrease of the reactors’ productivity, the need to clean the reactors after each batch, the exposure of the operators to VinylChloride Monomer (VCM) which is classified CMR, some quality issues… At the moment, a coating is applied before each batch (50 times per day for the 22 reactors at Mazingarbe) in order to lower the amount of scale formed during the S-PVC batch. The application of the coating added to the formation of scale leads to important extra costs. The comprehension of the scale formation mechanism with the aim of then developing a durable protective coating becomes a priority in order to increase the final product quality, lower the costs and gain a competitive advantage for INEOS ChlorVinyls. The Ph.D. subject was divided into two parts with the first year dedicated to the comprehension of the scale formation mechanism and the establishment of a complete scenario explaining the formation of scale from a chemical and physical point of view. The second part of this project was dedicated to the development of a polymer coating with the selection of an adapted polymer candidate and then the optimization of its adhesion onto stainless steel in order to obtain the optimal performances and the durability of the coating.

De nombreux traitements de surface (sablage, attaques acides…) ont été mis au point sur les implants dentaires afin de favoriser leur ostéointégration. Par ailleurs, depuis plusieurs années des revêtements à base de phosphates de calcium sont également développés dans le même but.L’objectif principal de la thèse est de mettre au point un procédé de revêtement à basse température afin de déposer à la surface de l’implant en titane une couche mince de phosphate de calcium, de structure et de composition analogue au minéral osseux en vue de favoriser l’ostéointégration. Il est aussi souhaité que ce revêtement présente des propriétés antibactériennes afin de lutter contre les infections post-opératoires. Dans un premier temps, un traitement de surface de l’implant en titane composé d’une étape de sablage et d’une attaque acide a été développé. Il permet d’obtenir une rugosité moyenne de surface comprise entre 1,4 et1,8 µm ainsi qu’une texture microporeuse et une mouillabilité de surface améliorée. Puis, les procédés de revêtement d’électrodéposition et d’immersions successives ont été étudiés. L’étapede centrifugation implémentée dans le procédé d’immersions successives s’est révélée cruciale et un revêtement d’environ 2 µm d’épaisseur composé d’apatite biomimétique a été obtenu. La composition et l’épaisseur du revêtement élaboré par électrodéposition est fortement influencée par la durée du dépôt. Ainsi une durée d’électrodéposition de 1 mn menée à un potentiel de -1,6V/ECS permet d’obtenir un revêtement d’environ 1,5 µm d’épaisseur composé d’une couche de phosphate octocalcique et de cristaux de brushite. Un test de vissage/dévissage dans une mâchoire artificielle a démontré la tenue mécanique des revêtements obtenus selon les deux procédés. Enfin, des ions antibactériens tels que l’argent, le cuivre ou le zinc ont été incorporésaux revêtements. Il a été démontré que des taux importants d’incorporation allant jusqu’à 40 %molaire par rapport au calcium peuvent être atteints pour le cuivre et le zinc. Des tests biologiques permettant d’évaluer l’effet de ces revêtements sur l’activité biologique de cellules mésenchymateuses humaines ainsi que sur la formation d’un biofilm (modèle de péri-implantite)en vue de la prévention des infections post-opératoires ont conduit à des résultats prometteurs pour le développement de tels revêtements bioactifs. Ces travaux de thèse s’inscrivent dans le cadre du projet BIOACTISURF, soutenu par la Région Midi-Pyrénées, et réalisé en collaboration avec le Laboratoire de Génie Chimique (LGC) ainsi qu’un partenaire industriel / Numerous surface treatments have been developed in order to improve osseointegration of dentalimplants (sandblasting, acid etching…). Moreover, various strategies involving calcium phosphate coatings have emerged for the same target for a few decades. The main purpose of this work is todevelop a low temperature process allowing the deposition of a thin calcium phosphate layer at the titanium implant surface. The composition and structure of this calcium phosphate coating have to be close to the bone mineral to enable osseointegration improvement. Moreover, thecoating should have antibacterial properties in order to prevent post-operative infections. A surfacetreatment protocol composed of sandblasting and acid etching was firstly developed creating anaverage roughness of 1.4 – 1.8 µm with micropits and improved wettability. Secondly, two processes were studied to produce the calcium phosphate coating: the alternate soaking processand the electrodeposition. It was demonstrated that the centrifugation step implemented in thealternate soaking process is crucial and a coating of about 2 µm thick composed of biomimeticapatite was obtained. Among all the operating parameters of the electrodeposition process, time ofelectrodeposition has the major impact on the composition and the thickness of the coating. An electrodeposition of 1 mn at -1.6 V/SCE leads to a 1.5 µm thick coating composed of a layer ofoctacalcium phosphate and dicalcium phosphate dihydrate crystals. A screw/unscrew test demonstrated the mechanical stability of the coatings obtained by both processes. Finally,antibacterial ions such as silver, copper and zinc were incorporated in the coatings. Highincorporation rate up to 40 mol.% compared to calcium were determined for copper and zinc.Biological tests were conducted to qualify the effect of these coatings on the biological activity ofhuman mesenchymal cells and on the formation of a biofilm (peri-implantitis model) to preventpost-operative infections. They led to promising results for the development of such bioactivecoatings. This work is part of the BIOACTISURF project, supported by the Midi-Pyrénées Region,and carried out in collaboration with the Laboratory of Chemical Engineering (LGC) and an industrial partner