Fumed silica filler has long been used to structurally reinforce silicone elastomers. Unfortunately, the combination of as little as a few weight percent of untreated fumed silica nanoparticles [uFSN] with a siloxane polymer, such as PDMS, forms a difficult to process waxy solid admixture that even long periods of high shear mixing will not thin. In the course of the current work it was noted that after a period of storage certain solid admixtures would become viscous liquids when subjected to additional high shear mixing. It was further found that the required aging period could be decreased if the admixture storage temperature were increased. The only known interaction of PDMS and uFSN at moderate conditions is the adsorption of polymer on filler, and this interaction is also known to occur more quickly at higher temperature. This study examines the relationship between polymer adsorption and admixture liquefaction. Further, the mechanical properties of cured elastomers containing liquefied admixtures are examined to assess the degree of reinforcement that these materials afford.

Les matériaux viscoélastiques sont utilisés dans tous les domaines de l'ingénierie et des systèmes mécaniques, de l'électroménager, spatial, l'automobile, l'aéronautique ou le génie civil (ponts...) grâce à leur capacité d’amortir les chocs ou de filtrer les vibrations. Ce travail constitue une contribution à l’étude du comportement dynamique non linéaire des composants viscoélastiques notamment les élastomères. Dans ce mémoire, on introduit, d’abord, les propriétés mécaniques des élastomères, pour les aspects viscoélasticité et friction. Un rappel des différents phénomènes physiques et une liste non-exhaustive des modèles existants dans la littérature sont présentés. Ensuite, on propose des techniques expérimentales afin de décrire le comportement dynamique sous sollicitations uniaxiales d’un élastomère. Une description des bancs d’essais, des chaines d’analyse vibratoire, des méthodes de traitement des données des essais et d’analyse des mesures expérimentales est détaillée dans ce manuscrit. Une nouvelle approche du modèle de Maxwell généralisé a été proposée pour décrire le comportement dynamique du composant viscoélastique. Ce modèle permet une description précise et une bonne connaissance du comportement dynamique des composants viscoélastiques en fonction de l’amplitude, de la précharge et de la fréquence. La dissipation d'énergie identifiée sous forme d'amortissement peut être issue de l'amortissement intrinsèque des matériaux polymère comme de la friction aux interfaces dans le cas de composants caoutchoucs non adhérisés sur les pièces, dans ce travail, un nouveau modèle visco-tribologique a été développé en couplant les propriétés rhéologiques linéaires du modèle de Maxwell généralisé et le modèle de frottement de Dahl pour la description du comportement de frottement hystérétique des liaisons viscoélastiques non adhérisées. / Viscoelastic materials are used in all areas of engineering and mechanical systems, appliances, aerospace, automotive, aerospace and civil engineering (bridges...) through their ability to absorb shock and vibration filtering. This work is a contribution to the study of nonlinear dynamic behavior of viscoelastic components particularly elastomers. In this dissertation, we introduced the mechanical properties of elastomers, for both viscoelasticity and friction aspects. A review of the different physical phenomena and a non-exhaustive list of existing models in the literature are presented. Then, we propose experimental techniques to describe the dynamic behavior under uniaxial stress of an elastomer. A description of test benches, vibration analysis chains, methods of processing data and analysis of experimental measurements is detailed in this manuscript. A new approach of generalized Maxwell model was proposed to describe the dynamic behavior of viscoelastic component. This model allows an accurate description and a good knowledge of the dynamic behavior of viscoelastic components depending on amplitude, frequency and preload. Energy dissipation identified as damping can be from intrinsic damping of the polymer as friction at the interfaces in case of not bonded rubber component to mechanical part, a new viscoelastic model tribological was developed by combining the rheological properties of linear generalized Maxwell model and the Dahl friction model for describing the behavior of viscoelastic hysteretic friction of not bonded connections.

Cette thèse a plusieurs objectifs différents. La première est de concevoir de nouveaux composites élastomères charge renforcée sur la base de mélange de deux types d'élastomères différents vulcanisés dans des conditions différentes (température de vulcanisation, système de vulcanisation etc.) afin d'obtenir de meilleures performances de traitement et de propriétés. La deuxième est de caractériser les mélanges nouvellement créées en utilisant différentes méthodes et différentes conditions de fonctionnement. Le troisième est d'étudier la possibilité de remplacer une partie de la charge conventionnelle (noir de carbone) avec de la résine époxy ou l'utilisation de particules fines comme le SiC et Al2O3. Au stade final de la thèse, nous avons proposé des conditions de travail optimales et les applications industrielles. Une proposition très pratique a été donnée pour l'optimisation de la composition pour différentes applications industrielles. À la suite de la recherche à l’échelle industrielle qui est l'objet de cette thèse, nous avons proposé des compositions originales de haute qualité adaptés pour différentes applications. / This thesis has several different aims. First one is to design new filler-reinforced elastomeric composites based on mixing together of two different types of elastomers vulcanized under different conditions (vulcanization temperature, vulcanization system, etc.) in order to obtain better processing and performance properties. Second one is to characterize the newly created mixtures by using variety of methods and different operating conditions. The third one is to investigate the possibility to replace part of the conventional filler (carbon black) with epoxy resin or the use of fine particles as SiC and Al2O3. At the final stage of the thesis, we have suggested the optimal working conditions and industrial applications. A very practical proposal was given for the optimization of the composition for different industrial applications. As a result of the full scale investigation which is the object of this thesis, we have proposed original high quality compositions suitable for different engineering applications.

Este trabalho visa o estudo de elastômeros de uretano/uréia (PU/PBDO) e elastômeros de acetoxipropilcelulose (APC). No caso dos elastômeros de PU/PBDO, sintetizamos filmes com e sem a presença de grãos magnéticos orientados ou não na matriz elastomérica. Após o processo de síntese, algumas amostras de PU/PBDO com e sem as nanopartículas foram expostas à radiação ultravioleta por algumas horas. Diferentes técnicas foram utilizadas na análise estrutural e comportamento óptico e mecânico destes filmes, tais como, a técnica de ressonância magnética nuclear (RMN) convencional e de campo cíclico rápido, difração de raios X, ensaios de tensão x deformação, birrefringência óptica e microscopias óptica, de força atômica e de força magnética. Os resultados de RMN mostraram que a presença das nanopartículas na estrutura dos filmes de PU/PBDO enfraquece a dependência de T1 com a frequência de Larmor na região de interações inter-segmentos da curva de dispersão. Os módulos de Young das amostras de PU/PBDO não dopadas são maiores que os obtidos para as diferentes situações de amostras dopadas. O filme de APC é mais resistente e flexível que os diferentes filmes de PU/PBDO. Os resultados de raios X mostraram que ambos os filmes são compostos por uma rede reticulada e que o cisalhamento aplicado durante a síntese do filme, assim como, diferentes estiramentos aplicados em determinada direção da amostra, podem induzir uma certa orientação das moléculas em sua direção. Padrões de escala µm são observados em amostras de PU/PBDO, com e sem as nanopartículas magnéticas, quando suas superfícies são irradiadas com luz UV e depois aplicado um estiramento em qualquer direção da amostra. Isso indica que as ligações cruzadas induzidas pela luz UV ocorrem na presença das nanopartículas. Nas amostras de APC, o próprio cisalhamento aplicado ao filme, durante sua preparação, produz um padrão de escala µm em sua superfície. Além deste padrão de escala micrométrica, há formação de padrões de escala macroscópica que aparecem somente durante ou após o estiramento do filme ao longo da direção perpendicular ao cisalhamento. / This work aims the study of the urethane/urea (PU/PBDO) elastomerers and acetoxypropylcellulose (APC) elastomers. In the case of PU/PBDO elastomers, we synthesized films with and without the presence of oriented or not magnetic grains in the elastomeric matrix. After the synthesis process, some PU/PBDO samples with and without the nanoparticles were exposed to ultraviolet radiation for several hours. Different techniques were used in the structural analysis and mechanical and optical behavior of these films, such as, the technique of conventional and fast field cycling nuclear magnetic resonance (NMR), X-ray diffraction, stress x strain tests, optical birefringence and optical, atomic force and magnetic force microscopy. The NMR results showed that the presence of nanoparticles in the PU/PBDO film structure weakens the T1 dependence with the Larmor frequency in the region of inter-segment interactions of the dispersion curve. Young modules of the PU/PBDO undoped samples are larger than those obtained for the different situations of the doped samples. APC film is more resistant and flexible then different PU/PBDO films. The X-rays results showed that both films are composed of a cross-linked network and that the casting applied during the film synthesis, as different stretches applied in a given direction in the sample can induce a certain orientation of the molecules in their direction. Patterns of the µm are observed in PU/PBDO samples, with and without the magnetic nanoparticles, when their surfaces are irradiated with UV light and then applied a stretch in any direction of the sample. This indicates that cross-links induced by UV light occur in the nanoparticles presence. In APC samples, the actual casting applied to the film during its preparation, produces a pattern of µm scale on its surface. Besides this micron-scale pattern, there is formation of macroscopic patterns that appear only during or after film stretching along the direction perpendicular to the casting.

O objetivo deste trabalho é o de caracterizar o processo de condução do EPDM e de formulações deste material quando nele se incorpora diferentes concentrações de trihidróxido de alumínio (alumina trihidratada). Dois procedimentos experimentais foram utilizados para se obter os resultados: o primeiro utilizando medidas de corrente no estado estacionário variando-se a espessura das amostras, o potencial, o material do eletrodo e a temperatura e o segundo através de medidas da distribuição de cargas elétricas no interior do material empregando o método de propagação de um pulso de pressão. Na análise dos resultados experimentais encontrou-se presença de polarização elétrica e de condução, a qual apresenta dependência linear do logaritmo da condutividade com a raiz do campo, na região de altos campos elétricos. Estudo comparativo de alguns modelos foi realizado sem que nenhum deles explicasse os nossos resultados. Propusemos tentativamente a combinação de efeitos de superfície e de volume. Para o material com crescente concentração de alumina também se encontrou dependência da condutividade com a raiz do campo, mas a interpretação dos resultados ficou mais incerta. Além disto, um efeito quadrático com a concentração de alumina foi encontrado para a polarização e para a condução um efeito linear / This work attempts to characterize the processes of electric conduction in the EPDM copolymer and its composites with several contents of alumina trihydrate filler. Two different experimental procedures were employed: (i) measurements of the steady state electric current for several sample thicknesses, applied voltages, temperatures, and different types of electrode (ii) charge distribution measurements using the pressure wave propagation method. The results showed that there is an electric polarization superimposed to an electric conduction. For high electric fields a linear dependence of the log of the conductivity versus the square root of the electric field was found. Several theoretical models were employed aimed at explaining the experimental results but none gave satisfactory results. It seems that the most adequate model is one in which both surface and bulk processes are considered. When the content of alumina trihydrate filler was increased, a linear dependence between the logs of conductivity against the square root of the electric field was again observed, though the results could not be readily interpreted. It was also found that the electric polarization and the electric conductivity show a quadratic and a linear dependence on the alumina trihydrate content, respectively

Dielectric elastomers are electroactive polymers, which change size and shape in response to an electrical field. Dielectric elastomer actuators (DEAs) are highly promising new technologies in optical applications such as tuneable optical lenses, diffraction gratings and active camouflage. This thesis aims to develop a new approach to create a strain actuated compliant colour changing device that is controlled using DEAs as they offer stretchability, low weight, high efficiency, low cost and the possibility for miniaturisation. Conventional DEAs use transparent elastomeric materials with no significant colour change with strain. Conversely, liquid crystal materials are known to display dynamic colour changing behaviour, thereby making them good candidate materials. The thesis examines both the potential for colour changing soft actuators and the upcoming challenges in this field as well as the key concepts around liquid crystals that exhibit colour change. An initial approach was aimed at creating colour changes using dielectric elastomer actuators that drove a masked positioner. This method showed colour change since the mask changes the colour visualisation. The second approach used polymer dispersed liquid crystals, such as a nematic liquid crystal within a reactive silicone resin. The immiscibility of these compounds resulted in a dispersion of the liquid crystal droplets in the silicone matrix. However, the optical properties could not be controlled through mechanical deformation alone and the alignment of resulting LC droplets in the PDLC films was sensitive to the substrate used to perform the actuation. The next approach used reactive cholesteric liquid crystals (CLC) instead. A thin film coating process was preferred to carefully control the film's thickness by stretching. In free standing films a planar cholesteric alignment was obtained with mesogens aligned parallel to the substrate and colour was achieved based on the selective reflection of light. A transfer print technique was introduced to combine CLC coatings with elastomeric substrates that can be stretched. However, no colour change was achieved in response to mechanical deformation primarily due to the modulus and strength mismatch between the thin film and the elastomeric susbstrate material. Finally, lightly crosslinked liquid crystal elastomers using a combination of reactive and non-reactive liquid crystals were produced that were compatible with elastomer substrate materials. In free standing films planar cholesteric alignment was obtained with mesogens aligned parallel to the substrate. Successfully a reversible colour change based on selective reflection of light was achieved in response to a mechanical deformation.

Dans de nombreux domaines, tels que l’aéronautique et l’aérospatial, les matériaux composites sont utilisés par soucis d’allègement des structures. Pour cette même raison, les assemblages mettant en jeu ces matériaux sont préférentiellement réalisés par collage. Ce mode d’assemblage présente aussi l’avantage d’éviter tout risque d’endommagement engendré par des ruptures de fibres. Néanmoins, chacune des opérations de mise en œuvre du collage doit être maîtrisée, en particulier lorsque des élastomères réticulés, réputés peu aptes au collage, sont impliqués. Ainsi, un primaire est généralement utilisé pour assurer l’adhésion entre l’élastomère et le matériau composite. Dans ce travail de thèse, il s’agit de supprimer l'étape d’enduction du primaire à la surface de l’élastomère réticulé avant bobinage des fibres imprégnées de résine. Cette suppression vise à réduire les risques Hygiène Sécurité Environnement (primaire classé Cancérigène, Mutagène et Reprotoxique) et permet de simplifier les cycles de fabrication. Pour assurer l’adhésion entre l’élastomère réticulé à base d’EPDM et le matériau composite à matrice époxyde sans élément intermédiaire, il est essentiel de comprendre les mécanismes de formation de l’assemblage : création de liaisons physiques, influence de la rugosité de surface, diffusion de monomères et réactions chimiques. Cette compréhension permet par la suite de modifier la formulation des matériaux, dans notre cas remplacer le copolymère présent dans l’élastomère, afin d’améliorer l’adhésion et de s’affranchir de tout traitement de surface. / In many fields, in particular in aeronautic and aerospace, assemblies by bonding instead of bolting are used in order to lighten structures involving composite materials. Furthermore chemical bonding minimizes the risk of damage by fibers breaking. In this context, our research work concerns the assembly between a cured elastomer, known to be difficult to be bonded, and a composite material without using adhesives which are classified as carcinogenic, mutagenic and toxic agent. In order to have a good adhesion between cured EPDM elastomer and composite material with epoxy resin without adhesive, it is crucial to understand mechanisms of self assembly of these materials: role of physical bonds, influence of roughness, monomers diffusion and chemical reactions. This good understanding allows us editing material formulations, in our case copolymer in elastomer, to improve adhesion and remove surface treatment.

Este trabalho visa o estudo de elastômeros de uretano/uréia (PU/PBDO) e elastômeros de acetoxipropilcelulose (APC). No caso dos elastômeros de PU/PBDO, sintetizamos filmes com e sem a presença de grãos magnéticos orientados ou não na matriz elastomérica. Após o processo de síntese, algumas amostras de PU/PBDO com e sem as nanopartículas foram expostas à radiação ultravioleta por algumas horas. Diferentes técnicas foram utilizadas na análise estrutural e comportamento óptico e mecânico destes filmes, tais como, a técnica de ressonância magnética nuclear (RMN) convencional e de campo cíclico rápido, difração de raios X, ensaios de tensão x deformação, birrefringência óptica e microscopias óptica, de força atômica e de força magnética. Os resultados de RMN mostraram que a presença das nanopartículas na estrutura dos filmes de PU/PBDO enfraquece a dependência de T1 com a frequência de Larmor na região de interações inter-segmentos da curva de dispersão. Os módulos de Young das amostras de PU/PBDO não dopadas são maiores que os obtidos para as diferentes situações de amostras dopadas. O filme de APC é mais resistente e flexível que os diferentes filmes de PU/PBDO. Os resultados de raios X mostraram que ambos os filmes são compostos por uma rede reticulada e que o cisalhamento aplicado durante a síntese do filme, assim como, diferentes estiramentos aplicados em determinada direção da amostra, podem induzir uma certa orientação das moléculas em sua direção. Padrões de escala µm são observados em amostras de PU/PBDO, com e sem as nanopartículas magnéticas, quando suas superfícies são irradiadas com luz UV e depois aplicado um estiramento em qualquer direção da amostra. Isso indica que as ligações cruzadas induzidas pela luz UV ocorrem na presença das nanopartículas. Nas amostras de APC, o próprio cisalhamento aplicado ao filme, durante sua preparação, produz um padrão de escala µm em sua superfície. Além deste padrão de escala micrométrica, há formação de padrões de escala macroscópica que aparecem somente durante ou após o estiramento do filme ao longo da direção perpendicular ao cisalhamento. / This work aims the study of the urethane/urea (PU/PBDO) elastomerers and acetoxypropylcellulose (APC) elastomers. In the case of PU/PBDO elastomers, we synthesized films with and without the presence of oriented or not magnetic grains in the elastomeric matrix. After the synthesis process, some PU/PBDO samples with and without the nanoparticles were exposed to ultraviolet radiation for several hours. Different techniques were used in the structural analysis and mechanical and optical behavior of these films, such as, the technique of conventional and fast field cycling nuclear magnetic resonance (NMR), X-ray diffraction, stress x strain tests, optical birefringence and optical, atomic force and magnetic force microscopy. The NMR results showed that the presence of nanoparticles in the PU/PBDO film structure weakens the T1 dependence with the Larmor frequency in the region of inter-segment interactions of the dispersion curve. Young modules of the PU/PBDO undoped samples are larger than those obtained for the different situations of the doped samples. APC film is more resistant and flexible then different PU/PBDO films. The X-rays results showed that both films are composed of a cross-linked network and that the casting applied during the film synthesis, as different stretches applied in a given direction in the sample can induce a certain orientation of the molecules in their direction. Patterns of the µm are observed in PU/PBDO samples, with and without the magnetic nanoparticles, when their surfaces are irradiated with UV light and then applied a stretch in any direction of the sample. This indicates that cross-links induced by UV light occur in the nanoparticles presence. In APC samples, the actual casting applied to the film during its preparation, produces a pattern of µm scale on its surface. Besides this micron-scale pattern, there is formation of macroscopic patterns that appear only during or after film stretching along the direction perpendicular to the casting.

This thesis is an investigation of the TPE filament for Fused Deposition Modelling (FDM) manufacturing method. All the investigations aim to optimize the quality of the filament in order to make Thermoplastic Elastomer (TPE) material possible for FDM manufacturing method. Optimization experiments were made to find out key parameters in the extrusion process that determine the quality of the filament. With the optimal parameters, further investigation of the additive content in the TPE granulate was made to solve the current problem of the filament in practical 3D printing, which the high surface friction massively affects the FDM manufacturing feasibility. The filaments were manufactured by the desktop extruder 3devo filament extruder and the surface friction tests were performed on TribotesterTM. Additionally, discussion was made to summarize the pros and cons of TPE material as well as the significance of 3D printing TPE. Potential application and benefits are mentioned for combining the property of TPE and the advantage of FDM manufacturing. Current state-of-art extrusion equipment and FDM technology are also summarized.

Composites are multiphasic materials with individual constituent parts that work cooperatively to produce some desired result. For the common case of structural composites, the use of nanoscale additives does not always yield a predictable outcome due to the complex interactions that occur in the interfacial region where a reinforcing filler meets the supporting matrix. It stands to reason, however, that the thoughtful and deliberate exploitation of unusual effects in this region could lead to the development of nanocomposite materials with extraordinary properties. In this thesis work, I will introduce two such responses in a compliant nanocomposite consisting of highly-aligned carbon nanotubes (CNTs) encased within a poly(dimethylsiloxane) (PDMS) matrix. It is first demonstrated that the material exhibits extremely anisotropic dynamic mechanical behavior. The composite will behave in a way that is evocative of the neat polymer when deformed orthogonal to the CNT alignment direction, yet will exhibit strain softening when cyclically compressed along their axis due to the collective buckling of the nanotube struts. Next, it is shown that this nanocomposite material has the ability to respond and adapt to applied loads. Independent, yet complimentary tests reveal that the structure of the polymer in the presence of nanoscale interstitials will evolve during dynamic stressing, an effect that was predicted nearly 50 years ago. With support from both recent and established literature, an updated mechanism is proposed. Collectively, these results provide insight into the complicated mechanics between polymer matrices and embedded nanoparticles, and assist in the design of advanced synthetic materials with unique physical properties.