Ce travail se situe dans un contexte de développement de matériaux barrières pour l'emballage alimentaire papier-carton utilisant des microfibrilles de cellulose (MFC), ce qui donne une dimension renouvelable, recyclable, et biodégradable. Pour cela, deux stratégies ont été étudiées : l'utilisation des MFC pour la formation d'une couche barrière laminée à l'état humide sur carton, et en tant qu'additif dans une sauce de couchage barrière base aqueuse. Il a été montré que l'utilisation des MFC pour la production de couches barrières est prometteuse dans les deux cas. La lamination de MFC sur carton a permis d'obtenir de bonnes propriétés barrières à l'oxygène et à la graisse en utilisant des MFC hautement fibrillées. L'association carton-MFC a présenté une forte adhésion après séchage, permettant d'éviter l'utilisation de colle. Dans le cas du couchage composite, en vue de diminuer la viscosité et améliorer la barrière, il a été trouvé préférable d'utiliser un faible taux de MFC dans un alcool polyvinylique (PVOH) complètement hydrolysé ayant un faible degré de polymérisation. L'ajout de MFC dans une sauce de couchage composite a montré leur capacité à améliorer la cinétique de séchage du PVOH. L’utilisation combinée de MFC et de charges lamellaires a présenté un effet de synergie sur leurs états de dispersions dans une solution de PVOH, permettant leur utilisation pour l'amélioration de la barrière à la vapeur d'eau en conditions humides, tout en évitant la formation d'agrégats qui détérioreraient la barrière à l'oxygène. Ce travail a contribué à démontrer le potentiel des MFC pour la formation de couches barrières, ouvrant la voie au développement de nouveaux matériaux d'emballages plus responsables. / This study takes place in a context of development of paper-based barrier packaging materials, using of microfibrillated cellulose (MFC) that brings renewability, recyclability, and biodegradability. Two strategies have been investigated: the wet lamination of a MFC barrier layer on board, and the use of MFC as additive in a water-based barrier coating colour. The promising use of MFC for the formation of barrier layers has been demonstrated in both cases. The wet lamination of MFC on board led to good oxygen and grease barrier properties, using highly fibrillated MFC. The board-MFC complex presented a strong adhesion after drying, without requiring glue. In the case of barrier coating, in order to obtain a low viscosity suspensions leading to high barrier layers, the use of highly fibrillated MFC mixed with a fully-hydrolysed poly(vinyl alcohol (PVOH) of low degree of polymerisation has been preferred. The addition of MFC in PVOH demonstrated its potential for improving the drying behaviour of water-barrier barrier coating colours. The combined use of MFC and layered silicates evidenced a synergistic effect on their dispersion in a PVOH solution, leading to an improved water vapour barrier while avoiding the formation of aggregates that otherwise damage the oxygen barrier. The work contributed to demonstrate the potential of MFC to be used for the formation of barrier layers, paving the way for the development of more sustainable barrier packaging materials.

The objective of this study is to investigate the feasibility of depositing 1.5 mm thick titanium coatings, as a repair method for aerospace Ti-6Al-4V substrates, using two new commercially available processes: Low Pressure Cold Spray (LPCS) and Pulsed Gas Dynamic Spray (PGDS). The coatings produced were examined and characterized by their porosity level, microhardness, adhesion strength, particle flattening ratio, wipe tests, fracture surface type and wear tests. Phases and chemical composition were determined using X-Ray diffraction analysis and energy dispersive spectroscopy, respectively. It was found that both spraying processes are capable of producing dense, hard and oxide-free coatings using specific parameters. Finally, as a first step towards repair implementation of these processes, damages were simulated on Ti-6Al-4V samples, which were successfully repaired with low porosity and high hardness levels. The feasibility of repairs was confirmed, the next step will consist in qualification testing to assess coating performances under real life application.

Cutting tool inserts are often coated with thin layers either through chemical vapor deposition (CVD) or physical vapor deposition (PVD) processes. In order to have a better wear resistance cutting tools are mostly subjected to post-coating treatment processes. Shot peening is one of the processes that is used to improve the fatigue life of metallic components. In this study, the finite element (FE) method is employed to model the elastic-plastic deformation and development of residual stress distributions in a cutting tool after the impact of a shot medium. To carry out the work, CVD coated cemented carbide has been chosen to be the workpiece (insert), and the coatings of the chosen insert are Titanium Carbo Nitride (TiCN)  and Aluminum Oxide (Al2O3). Aim of the study is to model a single impact in the shot peening process on a surface of a coated cemented carbide insert while simulating the plastic deformation of the materials. In addition, the objective of the study is also to understand and explain the mechanics of shot peening process and find applicable mechanical properties of the materials for FE modeling. Conjugately, the influence of shot peening process parameters (e.g. velocity, diameter or shape of the peening media) on residual stress distribution has been investigated and the results obtained were compared to the one observed from experiment. The modeling in the study is carried out both with and without initial residual stresses in the materials. The initial residual stresses are estimated by applying a thermal load to the model. The results show that the compressive residual stresses achieved while shot peening by an edge-shaped medium are significantly higher at the surface (i.e. in a coated layer) than compared to a globular medium. In contrast, it is observed that the compressive residual stresses in the cemented carbide are significantly higher and deeper when shot peened with globular medium than the edge-shaped medium. Furthermore, the results of parameteric study demonstrate that the smaller medium induces higher residual stresses at the surface (i.e. in a coated layer) than in the cemented carbide. In contrast, it is observed that the bigger medium induces less residual stresses at the surface (i.e. in a coated layer) and higher residual stresses deeper in the cemented carbide. Whereas, it is observed that the higher residual stresses at the surface (i.e. in a coated layer) and in the cemeneted carbide can be achieved simultaneously by shot peens having a  higher velocity. Residual stress profiles modelled in this report correlate with data from previous studies.   This study has been carried out at Sandvik Coromant, Edge and Surfaces department in Stockholm, Sweden.

>Magister Scientiae - MSc / The efficiency of organic photovoltaics is influenced by the structure of the polymer, the morphology of the film, the interfaces between the layers, the choice of electron acceptor material and the ratio between the electron acceptor material and the polymer. In this project, we have used regioregular poly (3-hexylthiophene) (rr-P3HT) as the electron donor material and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), a derivative of the C60 fullerene, as the acceptor material. Different weight-ratios of rr-P3HT to PCBM were prepared by stirring for several hours in a chloroform solution and subsequently spin coated onto crystalline silicon and transparent conductive oxide/glass substrates. The effect of the PCBM concentration on the photo-induced optical emission and absorption properties of rr-P3HT was investigated by photoluminescence and ultraviolet-visible spectroscopy, respectively. Changes in the structural properties, as a function of the weight-ratio, were probed by high-resolution transmission electron microscopy, x-ray diffraction, Fourier transform infrared spectroscopy and Raman spectroscopy. Results show that the structural integrity and crystallinity of rr-P3HT is compromised with the addition of excessive amounts of PCBM, which has a negative impact on the optical absorption of rr-P3HT and the photo-induced charge transfer mechanism between the rr-P3HT and PCBM. This work illustrates that blending rr-P3HT with an equal weight of PCBM results in an optimum configuration for improved performance in organic photovoltaic devices.

Développement de nouveaux matériaux d'emballage à base de micro- et nano-fibrilles de cellulose. Les micro- et nano-fibrilles de cellulose (MFC/NFC) sont des nanomatériaux issus de ressources renouvelables présentant un fort intérêt notamment pour le domaine de l'emballage. En plus des avantages naturels de la cellulose, ces matériaux offrent des propriétés barrières prometteuses (Oxygen, graisse), de bonnes propriétés de résistance mécanique ainsi que la possibilité de produire des films transparents. L'objectif de cette thèse était de développer par des procédés d'endution un carton barrière au gaz et aux graisses en utilisant les MFC/NFC. Différentes suspensions de MFC/NFC ont été premièrement characterisées puis utilisées pour la production de films afin de déterminer leurs propriétés intrinsèques. Des films modèles ont ensuite été développés avec la production de composites matrice/MFC. Une dernière partie était focalisée sur l'introduction de MFC/NFC dans des sauces de couchage afin de développer une couche barrière à la surface d'un carton. Un démonstrateur a ainsi été validé à l'échelle pilote. Le potentiel des MFC/NFC a été démontré comme agent de séchage et comme composant principale d'une couche barrière. Mots clès: Micro- et nano-fibrilles de cellulose, couche barrières, procédés d'enduction / Development of new packaging materials based on micro- and nano-fibrillated cellulose. The micro- and nanofibrillated cellulose (MFC/NFC) are nanomaterials from revewable resource with a high interest and partly for the packaging development. MFC combined both interesting properties (high tensile strength, good barrier to oxygen and grease, good transparency) and the advantages of natural cellulose source. The objective of this thesis was to develop a barrier packaging board based on MFC/NFC by coating processes. Firstly, the study focussed on the characterisation of the MFC suspensions, on the manufacturing of MFC self-standing films and on the determination of their properties. Secondly, the development of MFC based composites was studied as model films. The last part was devoted to the introduction of MFC in coating colours in order to develop a barrier layer at the board surface. Trials at pilot scale demonstrated the industrial feasibility of this product. The potential of the use of MFC/NFC was demonstrated to be used as a drying additive and a main composant of barrier layer. Keywords: Micro- and nanofibrillated cellulose, barrier layer, coating processes

L’originalité de ce travail est d’utiliser de la lignine, une macromolécule aromatique extraite de la biomasse lignocellulosique, en remplacement de résines pétrosourcées pour la formulation d’encres à destination de l’emballage alimentaire. Différentes modifications chimiques ont été réalisées sur des lignines commerciales afin de les rendre compatibles avec les composants utilisés dans la formulation des encres. Les réactifs et les procédés mis en place ont été choisis afin de limiter l’impact environnemental sur l’ensemble de la chaîne de valeur. Les modifications chimiques ont été mesurées par différentes techniques analytiques telles que la GPC SEC pour la distribution des masses molaires et la spectrométrie RMN et FTIR pour la mesure des groupements fonctionnels de la lignine. Les propriétés des encres obtenues ont été caractérisées par des mesures rhéologiques et colorimétriques (système CIE L*a*b*) sur des essais d’impression. Parmi les résultats notables, des changements au niveau de l’équilibre hydrophile/hydrophobe ont été particulièrement remarqués. Qui plus est, les encres à base de lignines modifiées chimiquement ont permis une amélioration du gamut de couleur par rapport à celles contenant de la lignine brute. A l’issue de ces travaux, deux applications ont été proposées Des encres biosourcées à base de lignine qui répondent à la majorité des exigences industrielles ont été formulées. De plus, une formule d’enduction à base de lignine modifiée améliorant les propriétés barrières des papiers recyclés a été développée avec succès. / The originality of this work is to use lignin, an aromatic macromolecule from lignocellulosic biomass, in replacement of petroleum-based resins for the formulation of inks for food contact packaging applications. Different chemical modifications were carried out on commercial lignins, in order to make them compatible with the ink components. Used reagents and processes were chosen in order to limit the environmental impact of the whole value chain. Chemical modifications were monitored by several analytical techniques such as GPC SEC for the molar mass distribution and NMR and FTIR spectrometry for the monitoring of lignin functional groups. Ink properties were characterized by rheological and colorimetric (CIE L*a*b* system) measurements on printed samples. Among the significant results, changes in hydrophilic/hydrophobic balance were particularly noticed. Furthermore, the colour gamut of modified lignin-based inks was enhanced, compared to the one of unmodified lignin-based inks. Two applications emerged from this work: (1) formulation of lignin-based bio-sourced inks, which meet most of the industrial requirements, and (2), development of a modified lignin-based coating which improved barrier properties of recycled paperboard.

O zinco vem sendo utilizado, já há bastante tempo, como revestimento protetor e decorativo para peças metálicas [1]. No entanto, cada vez mais a indústria busca revestimentos protetores que sejam mais resistentes à corrosão, que tenham boas características de soldabilidade, pintabilidade e, principalmente baixo custo. Os métodos mais comuns pelos quais os revestimentos de zinco são aplicados são imersão a quente, eletrodeposição e aspersão térmica. O presente trabalho tem como objetivo caracterizar a morfologia dos revestimentos Galvanized (GI), Galvannealed (GA) e Zn-55Al de zinco obtidos pelo processo de imersão a quente, verificar o comportamento eletroquímico e analisar o comportamento corrosivo dos revestimentos pelas técnicas de Potenciometria e Eletrodo Vibratório (SVET). Os resultados demonstraram que é possível a análise das fases por voltametria em microcélula no revestimento em que as fases foram crescidas, porém, não é possível aplicar a técnica nas diferentes fases formadas nos revestimentos industriais devido à espessura dos revestimentos. Não foi observado influência da luz Ultravioleta-visível na taxa de corrosão dos revestimentos estudados por SVET e esta técnica mostrou-se satisfatória para grandes aumentos e pequenas áreas. As análises por SVET demonstraram a possibilidade de analisar a corrosão localizada em diferentes fases intermetálicas nos revestimentos. / Zinc has been used for quite some time, as decorative and protective coating for metal parts. However, the industry increasingly seeks protective coatings that are more resistant to corrosion, have good weldability characteristics, and especially low cost. The most common methods by which zinc coatings are applied are hot dipping, electroplating and thermal spraying. The present work aims to characterize the morphology of the coatings Galvanized (GI), galvannealed (GA) and Zn-55Al of zinc obtained by hot dip process, check the electrochemical behavior and analyze the behavior of coatings for corrosion techniques of pots and Vibrating electrode (SVET). The results showed that it is possible to analyze the phases by microcell voltammetry in the coating in which the phases were grown, however, is not possible to apply the technique in the different phases formed in industrial coatings due to the thickness of coatings. There was no influence of UV-VIS in the corrosion rate of the coatings studied by SVET and this technique was satisfactory for large and small areas increases. The analysis by SVET demonstrated the possibility of analyzing the localized corrosion in different intermetalic phases in coatings.

Esta dissertação discute o emprego de técnicas de estabilização de taludes rodoviários de corte e aterros utilizando drenagem superficial e vegetação. Os conceitos de aplicação de vegetação no aumento da resistência do solo, diminuição da poro-pressão e diminuição da erosão superficial do terreno são revisados. O trabalho discute a importância da interação solo-vegetação, sua influência em taludes, a importância da matéria orgânica nos solos, a sucessão vegetal com vegetação nativa. Estes conceitos foram utilizados na análise de um trecho da BR386, entre a entrada para a via de acesso a Progresso até Canoas, atualmente em processo de duplicação. A partir da inspeção de campo foram identificados os principais problemas de instabilidade e erosão da obra. Foram coletadas seis amostras de solos de quatro taludes da obra para caracterização e para melhor descrição dos problemas de ruptura superficial e controle de erosão nos cortes e aterros analisados. Os materiais amostrados envolveram duas amostras com característica de argila de alta plasticidade, uma argila de baixa plasticidade, uma areia siltosa não plástica, uma areia argilosa e uma areia argilosa não plástica. Foram analisados os problemas encontrados em campo, em função do tipo de materiais, tendo sido propostas soluções adaptadas a cada caso, principalmente focando problemas referentes à drenagem e a busca de soluções ambientais eficazes e com preservação do caráter paisagístico. / This work discusses the use of stabilization techniques for road cuttings and embankments using drainage and vegetation. The concepts of increase soil strength due to vegetation, decrease of the pore pressure and reduction in erosion of the ground surface are reviewed. The work also discusses the importance of soil-vegetation interactions, their influence on slopes, the importance of organic matter in soils and plant succession with native vegetation. These concepts were used in the analysis of a length of the BR386 highway, between the entrance to the access route to Progress up to Canoas, currently in the process of duplication. From the field inspection the main problems of instability and erosion of the works were identified. Six soil samples were collected from four slopes for soil characterization and better description of the superficial instabilities and erosion control in the cuts and embankments analyzed. The materials involved two samples with characteristic of high plasticity clay, low plasticity clay, non plastic silty sand and sand clay not plastic. The problems encountered in the field were analyzed, considering the type of soils involved and proposals of solutions have been made adapted for each case, mainly focusing on drainage and the search for effective environmental solutions which preserve the landscape character.

A sobrevivência das organizações em cenários altamente competitivos tem exigido a melhoria da eficiência, flexibilidade e qualidade dos sistemas de produção (DE RON, 1998). Neste âmbito, a programação de tarefas assume grande responsabilidade ao suportar o planejamento e controle da manufatura, garantindo que estes processos estejam alinhados com os objetivos estratégicos das organizações. Esta dissertação aborda a programação de tarefas em sistemas de pintura com tempos de setup dependentes da sequência do processamento. No primeiro artigo é proposta uma sistemática para liberação do tamanho de lote que minimiza a soma dos custos de setup e pintura. Na sequência, os lotes liberados são sequenciados utilizando as regras Apparent Tardiness Cost (ATC) e Apparent Tardiness Cost with Setups (ATCS). Quando aplicado em processo de pintura, o ganho de eficiência da instalação medido através do Overall Equipment Effectiveness (OEE) foi de 32,84%. O segundo artigo propõe uma modificação na regra ATCS através da inclusão de um parâmetro relativo à qualidade de execução do procedimento de pintura. Tal parâmetro é justificado pelo impacto decorrente de falhas no processo de pintura, gerando atrasos de entrega. Esta nova heurística, quando aplicada no mesmo processo de pintura, elevou o OEE em 2,74%, a precisão de entrega em 2,11% e o percentual de embalagens completas ao final do processo de pintura em 8%. / The competitive industrial scenarios required companies to improve efficiency, flexibility and quality of production systems (RON, 1998). In this context, job scheduling is deemed important to support planning and control of manufacturing systems. This dissertation addresses the scheduling problem in painting systems where setups depend on the job sequence. The first paper proposes an approach to release batches aimed at minimizing the sum of setup and painting costs. The released lots are scheduled using the Apparent Tardiness Cost (ATC) and Apparent Tardiness Cost with Setups (ATCS) rules. When applied to a painting process, the proposed approach increased efficiency measured by the Overall Equipment Effectiveness 32.84%. The second article proposes a modification to the ATCS rule by including a quality related parameter. This parameter is tailored to reduce delivery delays due to quality problems. This new heuristic, when applied to the same painting process, increased the OEE 2.74%, the delivery accuracy 2.11% and the percentage of completed packages at the end of the painting process 8%.

Este trabalho de conclusão tem como tema a relação entre as especificações de resinas alquídicas e de tintas preparadas com estas resinas, com foco nas características de teor de sólidos e viscosidade, fazendo uso das técnicas projeto de experimentos, superfície de resposta e análise de regressão. O objetivo principal é o estudo dos limites de especificação ideais para a resina alquídica, de forma que os lotes de tinta apresentem propriedades dentro da especificação já ao final do processamento, reduzindo a incidência de lotes fabris com necessidade de ajuste. Como conseqüência, temos redução de retrabalho e lead time fabril, adequação de custo de produtos, maior qualidade intrínseca e maior confiança na sistemática de desenvolvimento, produção e controle de qualidade. Inicialmente, foi realizada uma revisão bibliográfica sobre a tecnologia de tintas e resinas alquídicas, conceitos de controle de qualidade, planejamento de experimentos, análise por superfície de resposta e análise de regressão. Na seqüência, foi conduzido o estudo de caso, realizado na empresa Killing S.A. Tintas e Adesivos, planta localizada na cidade de Novo Hamburgo. Os resultados experimentais indicaram modelos de regressão polinomial válidos para as propriedades avaliadas. Foram tomadas as propriedades teor de sólidos e viscosidade Copo Ford #2 da mistura A+B como parâmetros para análise dos limites de especificação da resina alquídica, onde se comprovou que a variabilidade atualmente permitida é excessiva. A aplicação dos modelos de regressão indicou novos limites de especificação para a resina alquídica, mais estreitos, viabilizando a obtenção de tintas com propriedades especificadas. / This master thesis presents an analysis of the relationship between specification of alkyd resins and relative coatings, regarding two characteristics: solids value and viscosity. The study was conducted applying the techniques of design of experiments, response surface and regression analysis. The main objective was to study the ideal specification limits to the alkyd resin, so that the coatings batches present properties equivalent to the specification reducing the occurrence of batch adjustments. Reduction in adjustments lead to reduced rework, lead time, and manufacturing costs. It also contributes to higher intrinsic quality and trust in the development, production and quality control system. The first step was a literature review about the coating and alkyd resin technology, control quality concepts, design of experiments, response surface and regression analysis. Then, a case study was developed in the company Killing S.A. Tintas e Adesivos, a producer located in the city of Novo Hamburgo. The experimental results denoted valid polynomial regression models to the evaluated properties.It was studied the properties solids value and viscosity Ford Cup #2 to the mixture A+B as parameters to the specification limits analysis of the alkyd resin, being proved that the actual permitted variability is excessive. The application of the regression models pointed narrower specification limits to the alkyd resin, permitting the production of coatings with specificated properties.