Atualmente, os adesivos de contato de policloropreno base aquosa, possuem capacidade de adesão, variando entre 1,15 até 2,75 kgf/cm2. Em contrapartida, os adesivos de policloropreno base solvente, suportam tensões médias de cisalhamento de 3,8 kgf/cm2. Esta pesquisa apresenta uma proposta inovadora de condicionamento magnético do adesivo de contato de policloropreno base aquosa com o objetivo de aumentar a capacidade de aderência entre o adesivo e o substrato. Para promover um incremento na capacidade de adesão do adesivo de policloropreno base aquosa, formulou-se um adesivo utilizando um nanoaditivo, o gás carbônico como catalisador e um processo de condicionamento magnético precedente à etapa de aplicação sobre os substratos. Os resultados obtidos demonstraram aumento médio de 292 % na tensão de cisalhamento do adesivo condicionado magneticamente quando comparado com o adesivo de mesma formulação sem o condicionamento magnético, e quando comparado com um adesivo comercial de policloropreno base aquosa, o aumento foi de 122 %. / Currently, the aqueous based polychloroprene contact adhesive presents an adhesion capacity variation between 1,15 and up to 2,75 kgf/cm2. However, the solvent based polychloroprene adhesives support average tensions of shearing of 3,8 kgf/cm2. This research is an innovative proposal for magnetic conditioning of the aqueous based polychloroprene contact adhesive with the purpose of increasing the adherence capacity between the adhesive and the substrate. To promote an increase of adhesion to the aqueous based polychloroprene contact adhesive, we formulated one adhesive using a nano-additive, carbon dioxide as catalyst, and a magnetic conditioning process before the phase of application on the substrates. The results obtained show an average increase of 292 % in the shearing tension of the adhesive magnetically conditioned when compared with an adhesive of the same formulation without the magnetic conditioning and 122 % increase when compared to the commercial aqueous based polichloroprene adhesive.

The goal of the dissertation was to investigate the peculiarity of morphological changes of the modified polychloroprene adhesive in the aim to predict the mechanical and adhesive behaviour and to produce composition with useful and essential properties.

Atualmente, os adesivos de contato de policloropreno base aquosa, possuem capacidade de adesão, variando entre 1,15 até 2,75 kgf/cm2. Em contrapartida, os adesivos de policloropreno base solvente, suportam tensões médias de cisalhamento de 3,8 kgf/cm2. Esta pesquisa apresenta uma proposta inovadora de condicionamento magnético do adesivo de contato de policloropreno base aquosa com o objetivo de aumentar a capacidade de aderência entre o adesivo e o substrato. Para promover um incremento na capacidade de adesão do adesivo de policloropreno base aquosa, formulou-se um adesivo utilizando um nanoaditivo, o gás carbônico como catalisador e um processo de condicionamento magnético precedente à etapa de aplicação sobre os substratos. Os resultados obtidos demonstraram aumento médio de 292 % na tensão de cisalhamento do adesivo condicionado magneticamente quando comparado com o adesivo de mesma formulação sem o condicionamento magnético, e quando comparado com um adesivo comercial de policloropreno base aquosa, o aumento foi de 122 %. / Currently, the aqueous based polychloroprene contact adhesive presents an adhesion capacity variation between 1,15 and up to 2,75 kgf/cm2. However, the solvent based polychloroprene adhesives support average tensions of shearing of 3,8 kgf/cm2. This research is an innovative proposal for magnetic conditioning of the aqueous based polychloroprene contact adhesive with the purpose of increasing the adherence capacity between the adhesive and the substrate. To promote an increase of adhesion to the aqueous based polychloroprene contact adhesive, we formulated one adhesive using a nano-additive, carbon dioxide as catalyst, and a magnetic conditioning process before the phase of application on the substrates. The results obtained show an average increase of 292 % in the shearing tension of the adhesive magnetically conditioned when compared with an adhesive of the same formulation without the magnetic conditioning and 122 % increase when compared to the commercial aqueous based polichloroprene adhesive.

La prédiction de la durée de vie des polymères en milieu marin est devenue, ces dernières années, indispensable afin de limiter les coûts de maintenance des structures utilisées en mer. Le polychloroprène est un élastomère très employé en milieu marin en raison de ses propriétés intrinsèques proches de celles du caoutchouc naturel, avec une durabilité supérieure. Ce travail de thèse a pour objectif de caractériser, comprendre et prédire l'évolution des propriétés mécaniques (module et rupture) au cours du vieillissement et plus particulièrement de l'oxydation, l'un des mécanismes de dégradation majeurs pour ce type de matériaux. Cette prédiction est basée sur l'utilisation d'une description mécanistique de l'oxydation couplée à l'utilisation de relations structure/propriétés issues de la théorie caoutchoutique. Dans un premier temps, un modèle cinétique d'oxydation a été mis en place sur le polychloroprène cru et les constantes associées déterminées par méthode inverse. L'effet de la vulcanisation est, par la suite, intégré au modèle cinétique permettant ainsi une prédiction du module au cours de l'oxydation, ce type de dégradation conduisant à une forte augmentation du module dans le CR en raison de la présence de doubles liaisons dans le matériau. Afin de proposer une prédiction basée sur les propriétés à rupture, l'influence de l'oxydation sur l'énergie de propagation de fissure en mode I (GIC) a été étudiée en détail avec notamment une comparaison entre différents types d'élastomère. Cette étude a permis de mettre en évidence une chute importante de GIC en raison d'une inhibition de la cristallisation induite au cours de l'oxydation. La dernière partie de ce travail est dédiée à la diffusion de l'eau dans le polychloroprène et plus particulièrement les mécanismes de formation d'agrégat d'eau dans le matériau qui se traduit par une forte absorption et donc une perte de propriétés mécaniques à la rupture. / The prediction of the lifetime of polymers in a marine environment is becoming increasingly important in order to limit maintenance costs for structures at sea. Polychloroprene is an elastomer which is widely used in marine structures due to its properties which are similar to natural rubber but with improved durability. The aim of the work described in this thesis is to characterize, understand and predict the evolution of mechanical properties (modulus and rupture) during aging, and in particular during oxidation, one of the main degradation mechanisms in this type of material. The prediction is based on the use of a mechanistic description of oxidation coupled with the use of theoretical structure/property relationships. First a kinetic model of oxidation has been set up for raw polychloroprene, and the associated rate constants have been found by an inverse method. The effect of vulcanization was then included in the model, enabling modulus to be predicted during oxidation. As a result of the presence of double bonds oxidation causes a significant increase in modulus of CR. Then, in order to predict fracture properties, the influence of oxidation on the mode I crack propagation energy (GIc) has been studied in detail, with a comparison between different types of elastomer. This study has revealed a strong drop in GIc due to inhibition of induced crystallization during oxidation. In the last part of the document the diffusion of water in polychloroprene has been examined, and the mechanisms of cluster formation have been described: These lead to large water absorption and a loss of mechanical properties.

La pyrolyse et la gazéification sont les deux procédés les plus prometteurs pour une valorisation thermique des déchets organiques solides en réponse aux objectifs énergétiques environnementaux actuels et futurs. Si pour la pyrolyse, les déchets traités sont aussi synthétiques (plastiques, composites) que naturels (biomasse), pour la gazéification c'est la biomasse qui est la matière première la plus rencontrée. Les travaux expérimentaux de cette thèse ont été réalisés dans deux types d'installations : une installation à échelle laboratoire (analyseur thermique : TG, ATD, EGA) et une installation à échelle pilote (nommée four « Aubry »). Les traitements thermiques ont été effectués dans les conditions spécifiques pour la pyrolyse (atmosphère d'azote) et la gazéification (vapeurs d'eau). Les matériaux testés ont été le polychloroprène, les composés de la biomasse (hémicellulose, lignine, cellulose), seuls où en mélange, ainsi qu'un bois naturel (le bouleau) et son « modèle » (mélange en proportions équivalents de ses constituants). Deux modèles cinétiques pour la pyrolyse du polychloroprène ont été choisis de littérature et testés. La différence primordiale entre les deux modèles est leur degré de complexité. Le premier est un modèle empirique simplifié, tandis que le deuxième, très détaillé, est un modèle radicalaire Le modèle cinétique utilisé pour modéliser le processus de pyrolyse de la cellulose, pris aussi de la littérature, a montré une concordance très bonne avec nos résultats expérimentaux. L'étude hôte de la gazéification à la vapeur d'eau a nécessité des modifications de nos installations expérimentales, tout particulièrement à l'échelle pilote, pour assurer une atmosphère confinée en vapeur d'eau. Les expériences réalisées en conditions expérimentales spécifiques ont données des résultats excellents pour la composition finale du gaz de synthèse. La simulation, à l'échelle pilote, de la gazéification a été obtenue par adaptation d'un modèle existant, à la réalisation de nos conditions opératoires, prenant en compte les transferts matières et basé sur l'évolution de la porosité d'une particule sphérique équivalente. Le modèle a montré une concordance raisonnable avec nos données expérimentales. La dernière partie de cette thèse présente une étude dans lequel on compare les analyses thermiques pour les constituants purs, un modèle de bois et un bois naturel afin d'établir les interactions possibles entre ces composants lors de la dégradation thermique du bois naturel. Les résultats ont montré que pour les mélanges cellulose-lignine et lignine-hémicellulose, le premier composé inhibe la dégradation du dernier tandis que, pour les mélanges cellulose-hémicellulose, cet effet se manifeste à l'inverse. Tous les modèles testés et les résultats enregistrés dans cette thèse représentent des instruments très utiles pour l'aide au dimensionnement des installations de pyrolyse à échelle laboratoire ainsi que pour des installations de gazéification à la vapeur d'eau à échelle pilote. / The pyrolysis and gasification are the most actual techniques used for valorization of organic wastes. If for pyrolysis the raw materials are both synthetic (plastics) and natural (biomass), in the case of gasification mainly the biomass is used. The experiments presented in this thesis were carried out in two type of plants: a laboratory scale plant (thermal analyses: TGA, DTA, EGA) and a pilot scale plant (so-called “Aubry” furnace). The thermal treatments implemented both the conditions of pyrolysis (nitrogen atmosphere) and gasification (water vapors). The materials tested in the experimental part were: polychloroprene, biomass constituents (hemicelluloses, lignin and cellulose), alones and in mixture, and a natural wood (the birch) with it's “model” (a mixture of it's components in different proportions). For the polychloroprene pyrolysis, two kinetic models chosen from the published literature were tested. The difference in the two models is given by their degree of complexity. The first one was a simplified empirical model. The second one was a free-radical model. For the cellulose pyrolysis was also tested a model proposed in the literature and the model showed a good accuracy in representing our experimental data. The study of gasification at pilot scale needed an appropriate modification of the experimental set-up to create a saturated atmosphere in water vapor inside the Aubry furnace. The experimental work concerning the gasification followed a specific protocol and gave excellent results for the syngas composition. A gasification mathematical model for pilot scale was proposed and tested. This model, based on the evolution of equivalent spherical particles porosity, take supplementary into account the mass transfer. The results given by the last model were in reasonable agreement with our experimental results. The last part of this thesis presents a comparative study of the thermal analyses of pure biomass components, of a wood model and also of a natural wood. The goal is to identify the interactions that could take place between these compounds during the thermal degradation of the natural wood. Our results showed that for the mixtures cellulose-lignin and lignin-hemicelluloses the first compound inhibits the second one. For the mixtures cellulose-hemicelluloses this effect is inverse. All the kinetic models tested in this thesis are useful tools for dimensioning laboratory scale pyrolysis plants and pilot scale set-up for water vapors gasification.

O conhecimento do comportamento mecânico do material é vital para a previsão da durabilidade e atendimento aos requisitos iniciais de projeto. Por meio de ensaios experimentais é possível mensurar esse comportamento e utilizar como parâmetro de entrada em simulações numéricas. Nesse ponto a temperatura altera significativamente as propriedades mecânicas estáticas e dinâmicas do material. Testes de fadiga devem ser considerados na caracterização do material mesmo que um alto custo e tempo sejam necessários. Assim o objetivo deste trabalho é avaliar o comportamento termo-mecânico do policloropreno em tração e fadiga. Este estudo se fez necessário para prever a durabilidade em diversas temperaturas em mancais de rolamento de cardans que exigem rigidez e durabilidade. A abordagem proposta consiste em formular equações constitutivas que considerem as constantes dependentes da temperatura para a situação estática (ensaio de tração) e dinâmica (ensaio de fadiga). Foram estudados 4 modelos constitutivos já consagrados na literatura. Corpos de prova normatizados foram utilizados para a avaliação experimental do material tanto em tração quanto em fadiga. Pode-se concluir que esta abordagem conseguiu modelar adequadamente o comportamento mecânico em ambas as situações estudadas. / Mechanical behavior of materials is vital for predicting durability and compliance with initial requirements of the project. Through experimental tests can measure this behavior and use as an input parameter in numerical simulations. At this point temperature significantly changes static and dynamic mechanical properties of the material. Fatigue tests should be considered in material characterization even if a high-cost and time are required. So the aim of this study is evaluate the thermo-mechanical behavior of polychloroprene in tension and fatigue. This study was necessary to predict durability in various temperatures in driveshafts of rolling bearings that requires rigidity and durability. The proposed approach is formulating constitutive equations to consider the dependent constant temperature for static situation (tensile test) and dynamic (fatigue test). Four constitutive models already established in literature were studied. Standardized test specimens were used for the experimental evaluation of the material both in tension and in fatigue. It can be concluded that this approach could adequately model the mechanical behavior in both cases studied.

O conhecimento do comportamento mecânico do material é vital para a previsão da durabilidade e atendimento aos requisitos iniciais de projeto. Por meio de ensaios experimentais é possível mensurar esse comportamento e utilizar como parâmetro de entrada em simulações numéricas. Nesse ponto a temperatura altera significativamente as propriedades mecânicas estáticas e dinâmicas do material. Testes de fadiga devem ser considerados na caracterização do material mesmo que um alto custo e tempo sejam necessários. Assim o objetivo deste trabalho é avaliar o comportamento termo-mecânico do policloropreno em tração e fadiga. Este estudo se fez necessário para prever a durabilidade em diversas temperaturas em mancais de rolamento de cardans que exigem rigidez e durabilidade. A abordagem proposta consiste em formular equações constitutivas que considerem as constantes dependentes da temperatura para a situação estática (ensaio de tração) e dinâmica (ensaio de fadiga). Foram estudados 4 modelos constitutivos já consagrados na literatura. Corpos de prova normatizados foram utilizados para a avaliação experimental do material tanto em tração quanto em fadiga. Pode-se concluir que esta abordagem conseguiu modelar adequadamente o comportamento mecânico em ambas as situações estudadas. / Mechanical behavior of materials is vital for predicting durability and compliance with initial requirements of the project. Through experimental tests can measure this behavior and use as an input parameter in numerical simulations. At this point temperature significantly changes static and dynamic mechanical properties of the material. Fatigue tests should be considered in material characterization even if a high-cost and time are required. So the aim of this study is evaluate the thermo-mechanical behavior of polychloroprene in tension and fatigue. This study was necessary to predict durability in various temperatures in driveshafts of rolling bearings that requires rigidity and durability. The proposed approach is formulating constitutive equations to consider the dependent constant temperature for static situation (tensile test) and dynamic (fatigue test). Four constitutive models already established in literature were studied. Standardized test specimens were used for the experimental evaluation of the material both in tension and in fatigue. It can be concluded that this approach could adequately model the mechanical behavior in both cases studied.

O conhecimento do comportamento mecânico do material é vital para a previsão da durabilidade e atendimento aos requisitos iniciais de projeto. Por meio de ensaios experimentais é possível mensurar esse comportamento e utilizar como parâmetro de entrada em simulações numéricas. Nesse ponto a temperatura altera significativamente as propriedades mecânicas estáticas e dinâmicas do material. Testes de fadiga devem ser considerados na caracterização do material mesmo que um alto custo e tempo sejam necessários. Assim o objetivo deste trabalho é avaliar o comportamento termo-mecânico do policloropreno em tração e fadiga. Este estudo se fez necessário para prever a durabilidade em diversas temperaturas em mancais de rolamento de cardans que exigem rigidez e durabilidade. A abordagem proposta consiste em formular equações constitutivas que considerem as constantes dependentes da temperatura para a situação estática (ensaio de tração) e dinâmica (ensaio de fadiga). Foram estudados 4 modelos constitutivos já consagrados na literatura. Corpos de prova normatizados foram utilizados para a avaliação experimental do material tanto em tração quanto em fadiga. Pode-se concluir que esta abordagem conseguiu modelar adequadamente o comportamento mecânico em ambas as situações estudadas. / Mechanical behavior of materials is vital for predicting durability and compliance with initial requirements of the project. Through experimental tests can measure this behavior and use as an input parameter in numerical simulations. At this point temperature significantly changes static and dynamic mechanical properties of the material. Fatigue tests should be considered in material characterization even if a high-cost and time are required. So the aim of this study is evaluate the thermo-mechanical behavior of polychloroprene in tension and fatigue. This study was necessary to predict durability in various temperatures in driveshafts of rolling bearings that requires rigidity and durability. The proposed approach is formulating constitutive equations to consider the dependent constant temperature for static situation (tensile test) and dynamic (fatigue test). Four constitutive models already established in literature were studied. Standardized test specimens were used for the experimental evaluation of the material both in tension and in fatigue. It can be concluded that this approach could adequately model the mechanical behavior in both cases studied.

Dans des contextes industriels spécifiques, coller un revêtement épais élastomère à des canalisations en acier constitue le meilleur moyen de les protéger de la corrosion en milieu marin. Ce travail de thèse a principalement pour objectif de mieux appréhender le comportement à long terme de ces assemblages acier/colle/revêtement en milieu marin. Deux approches complémentaires ont été définies. La première se base sur des outils statistiques pour traiter les données de caractérisations physico-chimiques des matériaux issus des assemblages utilisés en service depuis plus de trente ans. A partir de ces données hétérogènes (les assemblages sont différents en termes de formulations des matériaux, de procédé de collage et de conditions de vieillissement); des groupes homogènes présentant des scénarios de vieillissement identiques ont été identifiés et les mécanismes majeurs de dégradation du revêtement ont été établis. La seconde approche se focalise sur les assemblages actuellement utilisés dans les opérations de rénovation. Une démarche expérimentale a donc été mise en place en laboratoire afin d’accélérer de manière contrôlée le vieillissement des matériaux et assemblages. Les objectifs sont multiples. Pour chaque matériau (revêtement et colle), il s’agissait de comprendre les mécanismes de dégradation et les cinétiques d’absorption d’eau qui expliquent les évolutions de propriétés mécaniques et physico-chimiques observées au cours du vieillissement. De même, les interfaces ont été caractérisées et les paramètres de procédé qui influent sur la tenue de l’interface métallique ont été identifiés. Cette approche découplée a permis de mieux comprendre le comportement en milieu marin de l’assemblage d’étude à partir de celui des matériaux et interfaces présentes. / In some industrial applications, bonding rubber coatings to metallic pipelines is a suitable solution to protect them from marine corrosion. This study deals with the long term behavior of such metallic coated pipelines in a marine environment. Two different approaches have been developed. The first focuses on degradation data of pipelines used for around thirty years in normal service conditions. As these bonded assemblies are different in terms of material formulations, manufacturing processes and aging conditions, statistical tools were used to identify homogeneous groups with identical aging mechanisms. Also, based on these results, the main degradation mechanisms of the rubber coating were established. The second approach focused on pipelines used currently in renovation operations. An experimental methodology was developed in the laboratory to accelerate aging processes. The bulk materials, surfaces and interfaces were characterized physically, chemically and mechanically before and after natural sea water ageing. This enabled an understanding of the mechanisms and kinetics governing adhesion and degradation to be developed. It also allowed the influence of sea water aging on the failure strength of the assembly of interest to be investigated.

NilsonGroup presenterade uppdraget att undersöka vattenbaserade lim som alternativ till lösningsbaserade lim vid tillverkning av skor, vilket var grunden till det här arbetets ämne och avgränsningar har tagits fram. Vattenbaserade lim är ett alternativ till lösningsbaserade lim som inte är lika hälsofarligt, då lösningsmedelkan orsaka allvarliga hälsoeffekter. Enligt NilsonGroup ligger skobranschen steget efter vad det gäller hållbarhet och i nuläget saknas det en satsning på hållbarutveckling, medan andra branscher är bättre på att leta efter nya möjligheter. Det här arbetet vill lyfta fram på vilka sätt vattenbaserade lim är ett mindre riskfylltalternativ till lösningsbaserade lim och visa att skillnaderna i limfogens egenskaper inte blir så olika. Första delen av resultatet innefattar en definition av lim och limning. Fokus ligger på att reda ut vad som krävs och hur en limfog skapas med ett lim mellan två ytor, för att läsaren ska få en grundlig kunskap om det innan arbetet går in på lim i skor. Det presenteras även vilka egenskaper som är viktiga för en limfog och vilka faktorer det är som vanligtvis vägs in vid val av lim. Andra delen handlar om material, lim och limfogar i skoindustrin. Resultatet visar att det är den övre delen av skon och sulan som är den mest kritiska limfogen att skapa vid tillverkningen av en sko, samt att de mest förekommande lim som används vid skotillverkning är av polymererna polyuretan och polykloropren. De material till den övre delen av skon som främst används av NilsonGroup och generellt hela skoindustrin, är syntetiskt skinn, läder och bomull. Till en skos sula används gummi och polyuretan i störst utsträckning. Resultatet kommer fram till fem olika kombinationer av material och vattenbaserade lim som har bra potential att kunna bilda en hållbar limfog. Resultatet visar även att de egenskaper som vattenbaserade och lösningsbaserade polykloropren- och polyuretanlim ger en limfog är lika, så när det kommer till att välja mellan vattenbaserade lim och lösningsbaserade lim, så är det komponenterna i limmen och riskerna de medför som innefattar den stora skillnaden. I bilaga 1presenteras alla de mest förekommande komponenter som polyuretan- och polykloroprenlim består av, samt vilka hälsoeffekter de kan orsaka vid exponering för ämnet. / NilsonGroup presented the assignment to investigate water-borne adhesives as an alternative to solvent-borne adhesives in shoe production. This represent the purpose of this work and the limitations that have been developed. Water-borne adhesives do not pose as serious health risks as solvent-borne adhesives, mainly because of the solvent that may cause serious health risks. According to NilsonGroup, the shoe industry is a step behind in terms of sustainability and there is no investment in sustainable development. While other industries are stepping forward in terms of sustainability. The purpose of this work is to highlight waterborne adhesives as a less critical alternative to solvent-borne adhesives. And to prove that the characteristics between the two choices are not so different. The first part of this work explains adhesives and adhesive bonding. The part explains the requirements and how an adhesive joint is created from an adhesive between two different surfaces. This is necessary to get the reader to understand the basics about adhesive bonding before the work focus on adhesives in shoes. Important properties related to the adhesive joint and the common factors when choosing adhesives is also a part of this work. Second part of this work deals with material, adhesives and adhesive joints in the shoe industry. The upper part of the shoe and sole bonding process is the most critical joint in the shoe and the most common adhesives in the shoe industry is made of polyurethane and polychloroprene polymers. Some common materials used in the upper part of shoes made by NilsonGroup, and the shoe industry overall, are synthetic leather, leather and cotton. The sole is usually made of rubber or polyurethane. The result presents five different combinations of material and waterborne adhesives that may have the potential to produce a durable joint. The result shows that the properties related to waterborne and solvent-borne adhesives are equivalent. When choosing type of adhesive, the components in the adhesives and the health risk they cause, makes up the big difference. Appendix 1 presents common components in polyurethane and polychloroprene adhesives along with health risks that they may cause when exposed.