La famille des élastomères silicones LSR (Liquid Silicone Rubber) de haute technicité est identifiée comme celle possédant les plus forts arguments de développement au cours des prochaines décennies en raison de leurs propriétés spécifiques et de leurs facilités de mise en forme en grande série. Notamment, le moulage par injection du LSR sur d’autres matières telles que les thermoplastiques ou les métaux est aujourd’hui possible, ce qui ouvre la possibilité d’obtenir des composants multi-matières, multi-couleurs et de nouvelles fonctionnalités. Cette thèse se concentre sur la transformation des élastomères silicones LSR dans le but de mieux appréhender les phénomènes impliqués, afin d’améliorer les procédés d’élaboration et d’optimiser les conditions de transformation des composants élastométriques mono ou bi-matières à géométrie et propriété fonctionnelle bien définie. Les comportements rhéologique, cinétique et thermique des élastomères silicones ont été étudiés et caractérisés sous des conditions réelles de mise en œuvre par différentes méthodes associées. Un modèle thermo-rhéo-cinétique a été développé et ensuite implémenté dans un code de calcul de remplissage Cadmould® pour simuler le moulage par injection des élastomères silicones LSR ou encore le surmoulage de thermoplastiques. Pour la validation des modèles choisis et des paramètres identifiés, les essais d’injection sur l’outillage industrielle instrumenté ont été réalisés et confrontés à des résultats numériques obtenus. Enfin, la caractérisation de l’adhésion et l’adhérence interfaciale entre les thermoplastiques et les élastomères silicones a été réalisé sous différentes sollicitations complexes. De plus, l’évolution d’adhérence interfaciale des assemblages collés au cours de la vulcanisation des élastomères silicones a été caractérisée par l’essai de traction en utilisant un rhéomètre rotatif sous différentes modes de chauffage. / The family of high technology silicone elastomers LSR (Liquid Silicone Rubber) is identified as having the strongest arguments for development in the coming decades due to their unique properties and easy forming in large series. In particular, the injection molding of LSR on other materials such as thermoplastics or metals is possible today, which opens the possibility of obtaining multi-material, multi-color and new features components. The work presented in this thesis focuses on the transformation of silicone elastomers in order to better understand the phenomena involved, as to improve production processes and optimize processing conditions for mono or bi-material components in geometry and property functional well defined. The rheological, curing kinetic and thermal behaviors of silicone elastomers have been studied and characterized under real conditions of production by different methods combined. A thermo-rheo-kinetic model was then developed and implemented in commercial computer software Cadmould® to simulate the injection molding process of LSR or the overmolding process of LSR on to thermoplastics. For the validation of the models chosen and the parameters identified, the injection molding tests on industrial instrumented tools were performed and compared to numerical results. Finally, the characterization of interfacial adhesion between the thermoplastic and silicone elastomers was carried out under various adhesion tests. Moreover, the evolution of interfacial adhesion in thermoplastic/silicone components during the vulcanization of silicone elastomers has been characterized by the tensile test using a rotating rheometer in different heating cycles

Cette étude vise à mieux comprendre les mécanismes physiques à l'origine des propriétés mécaniques et des propriétés ultimes des caoutchoucs renforcés. Des échantillons de caoutchouc naturel dans lequel sont dispersés des agrégats de Silice précipitée ou de Noir de Carbone et vulcanisés au Soufre ont étés mis en oeuvre. Les principaux paramètres étudiés sont la densité de réticulation et l'interface charge-caoutchouc modifiée au moyen de différents traitements de surface de silice. L'impact des charges et du type d'interface sur les propriétés mécaniques dans le domaine des faibles déformations (effet Payne) et des grandes déformations est présenté. Le phénomène de cristallisation sous étirement dans le caoutchouc naturel est étudié par diffraction des rayons X in-situ au cours d'essais de traction quasi-statiques ou d'essais dynamiques couplés à un système d'acquisition stroboscopique. Nous montrons une corrélation des mesures du module, du degré de gonflement à l'équilibre, de l'orientation des chaînes mesurée par diffusion de rayons X et de la densité de réticulation mesurée par RMN dans le caoutchouc naturel non chargé. Dans le caoutchouc naturel renforcé, les corrélations établies à l'aide de ces mêmes mesures permettent de préciser les mécanismes de renforcement aux faibles et aux grandes déformations. Enfin, la résistance à la déchirure est évaluée en géométrie cisaillement pur sur les matériaux non-renforcés et renforcés. Les effets du type d'interface, de la densité de réticulation et de la vitesse d'essai sur la résistance à la déchirure sont présentés. Nous discutons également les profils de déformation locale obtenus par corrélation d'image / This study aims at better understanding the physical mechanisms responsible for the mechanical and ultimate properties in reinforced rubber materials. Sulfur vulcanized samples made of a Natural Rubber matrix in which aggregates of precipitated Silica or Carbon Black are dispersed have been manufactured. The main control parameters are the crosslink density and the filler/rubber interactions through different silica surface treatments. The effect of fillers and interface type on the mechanical properties in the small strain regime (Payne effect) and large strain regime is presented. X-ray diffraction experiments have been performed to study the phenomenon of strain-induced crystallization (SIC) both during quasi-static tensile tests and dynamical tests coupled to a stroboscopic acquisition device. Mechanical measurements have proved to correlate fairly well to the crosslink density measured by NMR, to equilibrium swelling degree and to the average chain segment orientation measured by X-ray scattering in unfilled natural rubber in agreement with the rubber elasticity theory. In reinforced materials, the correlation of those different measurements of local chain stretching give new insights on the reinforcement mechanisms at small and large strain. Tear experiments have been performed on Pure Shear pre-notched unfilled and filled samples. The influence of interface type, crosslink density and test drawing speed on tear resistance are presented. Local strain profiles obtained from digital image correlation and the crystallized fraction profiles from in-situ X-ray diffraction are also discussed

Orientador: Prof. Dr. Renato Altobelli Antunes / Coorientador: Prof. Dr. Everaldo Carlos Venancio / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, Santo André, 2018. / Neste trabalho foram preparados nanocompósitos funcionais de polianilina (PANI) reforçada com negro de fumo (NF) (PANI/NF) e um elastômero termoplástico sulfonado (SEBSS) para aplicação em recobrimentos a base de tinta epóxi, visando uma melhor proteção contra a corrosão. Os resultados mostraram que a morfologia do nanocompósito depende das condições de síntese e processamento utilizadas. A morfologia obtida para os nanocompósitos varia de estruturas granulares (para síntese realizada com baixas concentrações de monômero e iniciador) a uma mistura de estruturas fibrilares e granulares (para síntese realizada com altas concentrações de monômero e iniciador). As estruturas granulares observadas para os nanocompósitos de PANI/NF são as estruturas caroço-casca, onde o caroço é o negro de fumo e a casca é a polianilina. Os resultados de XPS confirmam quimicamente a presença de polianilina na superfície do negro de fumo, dando indícios de que pode ter ocorrido à formação de estruturas casca-caroço, tendo sido observado o aumento progressivo da quantidade de nitrogênio na superfície do negro de fumo Os resultados de polimerização obtidos diferem do que normalmente se encontra para a polimerização da anilina em baixas e altas concentrações de monômero e iniciador (por exemplo, persulfato de amônio, APS), refletindo assim a importância do processo de adsorção da anilina na superfície do negro de fumo (NF). Na ausência de negro de fumo, a morfologia da polianilina variou de nanofibras longas, com diâmetro médio ~ 40 nm, para baixas concentrações de monômero e iniciador (0,1-0,2 mol.L-1 e 0,025-0,050 mol.L-1, respectivamente), para fibras curtas com diâmetro médio da ordem de ~80 nm, para altas concentrações de monômero e iniciador (0,40 mol.L-1 e 0,1 mol.L-1, respectivamente). Os resultados de caracterização espectroscópica (FTIR e UV-VIS) mostraram que a polianilina foi obtida no estado de oxidação esmeraldina, na ausência e na presença do negro de fumo. Também mostram a sulfonação do SEBS e sua interação com o nanocompósito, resultando na protonação da PANI/NF pelos grupos sulfônicos presentes no elastômero termoplástico. Os resultados de caracterização térmica (TGA e DSC) mostraram que a estabilidade térmica e o processo de isomerização irreversível das nanofibras de PANI dependem de sua dimensão (diâmetro e comprimento da fibra). Os resultados de DSC mostraram a presença de dois picos exotérmicos (170 oC < T < 350 oC) para o processo de isomerização irreversível para nanofibras de PANI obtidas com baixas concentrações de monômero e iniciador, 0,10 e 0,025 mol.L-1, respectivamente, e um único pico para amostras nanofibras de PANI obtidas com altas concentrações de monômero e iniciador, 0,40 e 0,10 mol.L-1, respectivamente. Nas caracterizações morfológicas realizadas nas amostras de aço revestido com a tinta epóxi e tinta epóxi modificadas, notou-se um aumento da rugosidade das amostras contendo as nanopartículas, o que foi confirmado por meio de MEV, onde foi visualizada a formação de aglomerados de SEBSS. Por meio de ensaio mecânico de nanoindentação foi possível verificar uma diminuição da dureza e do módulo elástico da tinta devido à presença do SEBS sulfonado (SEBSS). Os ensaios eletroquímicos de polarização potenciodinâmica e espectroscopia de impedância eletroquímica demonstraram o efeito de combate frente à corrosão dos nanocompósitos contendo PANI/NF, com a diminuição da densidade de corrente de corrosão e aumento do efeito capacitivo das amostras modificadas, indicando o aumento da resistência do material à corrosão. / In this work, functional nanocomposites (PANI/NF) consisting of polyaniline (PANI) reinforced with carbon black (CB) have been synthesized for application in coatings based on epoxy, aiming at a better protection against corrosion.. The results showed that the morphology of the nanocomposites depends on the synthesis and processing conditions. The obtained morphology for the nanocomposites varies from granular structures (for synthesis carried out with low concentration of monomer and initiator) to a mixture of granular and fibrillar (nanofibers) morphologies (for synthesis carried out with higher monomer and initiator concentrations). The granular structures observed for PANI/NF nanocomposites are the core-shell structures, in which the core is the carbon black and the shell is the polyaniline. The XPS results chemically confirmed the obtainment of the core-shell structures, where it have been observed the progressive increase in the amount of oxygen in the carbon black surface. These results differ from those normally obtained for polyaniline synthesized in the absence of CB with low and high monomer (aniline) and initiator (ammonium peroxydisulfate, APS) concentrations, which shows the effect of the aniline adsorption process on carbon black (CB). In the absence of carbon black, the PANI morphology changed from long fibers, with mean diameter of ~40 nm, for low concentrations of monomer and initiator (0,1-0.20 mol.L-1 e 0.025-0.050 mol.L-1, respectively), to shorter fibers with mean diameter of ~80 nm, for high concentrations of monomer and initiator (0.40 mol.L-1 e 0.10 mol.L-1, respectively). The spectroscopic (FTIR and UV-VIS) characterization results showed that the polyaniline was obtained on its emeraldine oxidation state, both in the absence or presence of the carbon black. They also showed the sulfonation of SEBS and its interaction with the nanocomposite, resulting in the PANI/NF protonation by the sulfonic groups in the thermoplastic elastomer. Thermal characterization studies (TGA and DSC) showed that the thermal stability and the irreversible isomerization process of PANI depend on the nanofiber size (fiber diameter and length). The DSC results showed the presence of two exothermal peaks ( 170 oC < T < 350 oC) for the irreversible isomerization process for PANI nanofibers obtained with low concentration of monomer and initiator, 0.10 and 0.025 mol.L-1, respectively, and only one peak for PANI nanofibers obtained with high concentration of monomer and initiator, 0.40 and 0.10 mol.L-1, respectively. The morphological characterizations carried out in the carbon steel coated with epoxy and modified epoxy, it was observed an increase of the modified epoxy coating roughness, which was confirmed by the SEM results, where it was observed the formation of SEBSS aggregates. From the nanoindentation results it was observed an increase of the hardness and of the elastic modulus of the modified epoxy coating due to the presence of the sulfonated SEBS (SEBSS). The potentiodynamic electrochemical polarization and electrochemical impedance measurments showed the effect of the PANI/NF modified epoxy coating layer against the carbon steel corrosion, where it was observed a decrease of the corrosion current density and an increase of the capacitive effect on the PANI/NF modified epoxy coating layer, which indicates an increase of the resistance against corrosion of the carbon steel susbtrate.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2015-12-03T16:47:38Z No. of bitstreams: 1 jaianebandolimonteiro.pdf: 2039791 bytes, checksum: c3f28c1a95fdef73d0cc0190a9dfa169 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2015-12-03T21:29:38Z (GMT) No. of bitstreams: 1 jaianebandolimonteiro.pdf: 2039791 bytes, checksum: c3f28c1a95fdef73d0cc0190a9dfa169 (MD5) / Made available in DSpace on 2015-12-03T21:29:38Z (GMT). No. of bitstreams: 1 jaianebandolimonteiro.pdf: 2039791 bytes, checksum: c3f28c1a95fdef73d0cc0190a9dfa169 (MD5) Previous issue date: 2015-04-30 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O objetivo foi avaliar a alteração dimensional dos moldes de silicona por condensação imediatamente, 30min, 1h e 7 dias após a moldagem, com o auxílio da máquina de medição tridimensional por coordenadas. Os grupos foram divididos em: G1: Speedex Putty/Speedex Light Body (Coltene/Vigodent AS Indústria e Comércio), G2: Optosil P Plus/Xantopren L Blue (Heraeus Kulzer GmbH), G3: Zetaplus Putty/Oranwash L (Zhermack SpA) e G4: Precise SX (Dentsply Indústria e Comércio Ltda). Para a obtenção das 80 medições dos 4 materiais (n=20), foi usado um dispositivo composto por uma moldeira perfurada e uma outra parte com 3 edentações pré-estabelecidas. Para a avaliação dimensional, a máquina Crysta-Plus M 574 (Mitutoyo) realizou cada medida 3 vezes nos tempos estabelecidos e obteve-se a média aritmética. A média final das 4 distâncias I, II, III e IV do dispositivo edentado foi novamente aplicada. A análise estatística foi realizada com o teste de Kolmogorov-Smirnov que rejeitou a hipótese nula de distribuição assimétrica. Posteriormente, foi feita a ANOVA para comparar os 4 materiais simultaneamente e o teste paramétrico t de Student para comparar os materiais 2 a 2. O nível de significância global foi de p≤0,05. A maior contração linear foi observada na Speedex, mas não foi significante (p=0,08). A Zetaplus Putty/Oranwash L parece ser a mais estável (p=0,99), mas não foi significante. Não houve diferença estatisticamente significante entre nenhuma silicona por condensação quando comparadas simultaneamente nos 4 tempos ou quando comparadas 2 a 2, à exceção, Precise SX e a Speedex (p=0,05) no tempo T3. Todas as siliconas por condensação testadas apresentam alteração dimensional clinicamente aceitável e podem ser vazadas imediatamente, 30min, 1h e 7 dias após a moldagem. / The purpose was to evaluate the dimensional changes of condensation silicone impressions by immediately, 30min, 1h and 7 days after impression, with the help of threedimensional measuring coordinate machine. The groups were divided in: G1: Speedex Putty/Speedex Light Body (Coltène/Vigodent S/A Ind and Com), G2: Optosil P Plus/Xantopren L Blue (Heraeus Kulzer GmbH), G3: Zetaplus Putty/Oranwash L (Zhermack SpA) and G4: Precise SX (Dentsply Ind and Com Ltda). To obtain 80 measurements of 4 material (n=20) was used a device consisting of a perforated tray and one another part with 3 pre-established indentations. For dimensional evaluation, the Crysta-Plus M574 machine (Mitutoyo) held each measurement 3 times at the established times and obtained the arithmetic mean. The final average of the 4 distances of I, II, III and IV the edentulous device was again applied. Statistical analysis was performed using the Kolmogorov-Smirnov test to reject the null hypothesis of asymmetric distribution. Subsequently, ANOVA was performed to compare the four materials simultaneously and Student's t parametric test to compare the 2 by 2 materials. The overall significance level of p≤0,05. The higher linear contraction was observed in Speedex, but was not significant (p=0,08). The Zetaplus Putty/Oranwash L seems to be more stable (p=0,99) but was not significant. There was no significant difference between any silicone condensation compared simultaneously in 4 times or compared 2 by 2, except, Precise SX and Speedex (p=0,05) in T3 time. All tested condensation silicones exhibit clinically acceptable dimensional change and can be leaked immediately, 30min, 1h and 7 days after impression.

The first magnetization loop and the first stress–strain cycle of magnetoactive elastomers (MAEs) in a magnetic field differ considerably from the following loops and cycles, possibly due to the internal restructuring of the magnetic filler particles and the matrix polymer chains. In the present study, the irreversible magnetization processes during the first magnetization of MAEs with different filler compositions and tensile moduli of the matrix are studied by first-order reversal curve (FORC) measurements. For MAEs with mixed magnetic NdFeB/Fe fillers the FORC distributions and magnetization distributions of the first major loop reveal a complex irreversible magnetization behavior at interaction fields Hu < −50 kA m−1 due to the magnetostatic coupling between the magnetically hard NdFeB and the magnetically soft Fe particles. This coupling is enhanced either if the interparticle distance is reduced by particle motion and restructuring or by an increase in the particle densities. If the stiffness of the matrix is increased, the structuring and thus the interparticle interactions are suppressed and the magnetization reversal is dominated by domain processes in the NdFeB particles at high coercive fields of Hc > 600 kA m−1.

Dielectric elastomer actuators (DEAs) are compliant capacitors, which are able to transduce electrical into mechanical energy and vice versa. As they may be applied in different surrounding conditions and in applications with alternating excitations, it is necessary to investigate both, the thermal behavior and the in fluence of the temperature change during operation. Due to mechanical and electrical loss mechanisms during the energy transfer, the DEA is subjected to an intrinsic heating. In detail, the dielectric material, which has viscoelastic properties, shows a mechanical hysteresis under varying mechanical loads. This behavior leads to a viscoelastic loss of energy in the polymer layer, resulting in a heating of the structure. The non-ideal conduction of the electrode provokes a resistive loss when charging and discharging the electrode layer. Operation with frequencies in the kilohertz-range leads to remarkable local heat dissipation. The viscoelastic material behavior and the resistivity are assumed to be dependent on the temperature and/or on the strain of the material. By this, a back-coupling from the thermal field to the mechanical field or the electrical field is observed. In order to provide a thermal equilibrium, also the convective cooling { the structure is subjected to { has to be considered. Depending on the frequency and the type of electrical driving signal and mechanical load, viscoelastic and resistive heating provide different contributions during the dynamic process. In the present study we capture the described effects within our modeling approach. For a given dielectric elastomer actuator, numerical investigations are performed for a given electrical load.

Industrial development processes as well as research in physics, materials and engineering science rely on computer modelling and simulation techniques today. With increasing computer power, computations are carried out on multiple scales and involve the analysis of coupled problems. In this work, continuum modelling is therefore applied at different scales in order to facilitate a prediction of the effective material or structural behaviour based on the local morphology and the properties of the individual constituents. This provides valueable insight into the structure-property relations which are of interest for any design process. In order to obtain reasonable predictions for the effective behaviour, numerical models which capture the essential fine scale features are required. In this context, the efficient representation of discontinuities as they arise at, e.g. material interfaces or cracks, becomes more important than in purely phenomenological macroscopic approaches. In this work, two different approaches to the modelling of discontinuities are discussed: (i) a sharp interface representation which requires the localisation of interfaces by the mesh topology. Since many interesting macroscopic phenomena are related to the temporal evolution of certain microscopic features, (ii) diffuse interface models which regularise the interface in terms of an additional field variable and therefore avoid topological mesh updates are considered as an alternative. With the two combinations (i) Extended Finite Elemente Method (XFEM) + sharp interface model, and (ii) Isogeometric Analysis (IGA) + diffuse interface model, two fundamentally different approaches to the modelling of discontinuities are investigated in this work. XFEM reduces the continuity of the approximation by introducing suitable enrichment functions according to the discontinuity to be modelled. Instead, diffuse models regularise the interface which in many cases requires even an increased continuity that is provided by the spline-based approximation. To further increase the efficiency of isogeometric discretisations of diffuse interfaces, adaptive mesh refinement and coarsening techniques based on hierarchical splines are presented. The adaptive meshes are found to reduce the number of degrees of freedom required for a certain accuracy of the approximation significantly. Selected discretisation techniques are applied to solve a coupled magneto-mechanical problem for particulate microstructures of Magnetorheological Elastomers (MRE). In combination with a computational homogenisation approach, these microscopic models allow for the prediction of the effective coupled magneto-mechanical response of MRE. Moreover, finite element models of generic MRE microstructures are coupled with a BEM domain that represents the surrounding free space in order to take into account finite sample geometries. The macroscopic behaviour is analysed in terms of actuation stresses, magnetostrictive deformations, and magnetorheological effects. The results obtained for different microstructures and various loadings have been found to be in qualitative agreement with experiments on MRE as well as analytical results. / Industrielle Entwicklungsprozesse und die Forschung in Physik, Material- und Ingenieurwissenschaft greifen in einem immer stärkeren Umfang auf rechnergestützte Modellierungs- und Simulationsverfahren zurück. Die ständig steigende Rechenleistung ermöglicht dabei auch die Analyse mehrskaliger und gekoppelter Probleme. In dieser Arbeit kommt daher ein kontinuumsmechanischer Modellierungsansatz auf verschiedenen Skalen zum Einsatz. Das Ziel der Berechnungen ist dabei die Vorhersage des effektiven Material- bzw. Strukturverhaltens auf der Grundlage der lokalen Werkstoffstruktur und der Eigenschafen der konstitutiven Bestandteile. Derartige Simulationen liefern interessante Aussagen zu den Struktur-Eigenschaftsbeziehungen, deren Verständnis entscheidend für das Material- und Strukturdesign ist. Um aussagekräftige Vorhersagen des effektiven Verhaltens zu erhalten, sind numerische Modelle erforderlich, die wesentliche Eigenschaften der lokalen Materialstruktur abbilden. Dabei kommt der effizienten Modellierung von Diskontinuitäten, beispielsweise Materialgrenzen oder Rissen, eine deutlich größere Bedeutung zu als bei einer makroskopischen Betrachtung. In der vorliegenden Arbeit werden zwei unterschiedliche Modellierungsansätze für Unstetigkeiten diskutiert: (i) eine scharfe Abbildung, die üblicherweise konforme Berechnungsnetze erfordert. Da eine Evolution der Mikrostruktur bei einer derartigen Modellierung eine Topologieänderung bzw. eine aufwendige Neuvernetzung nach sich zieht, werden alternativ (ii) diffuse Modelle, die eine zusätzliche Feldvariable zur Regularisierung der Grenzfläche verwenden, betrachtet. Mit der Kombination von (i) Erweiterter Finite-Elemente-Methode (XFEM) + scharfem Grenzflächenmodell sowie (ii) Isogeometrischer Analyse (IGA) + diffuser Grenzflächenmodellierung werden in der vorliegenden Arbeit zwei fundamental verschiedene Zugänge zur Modellierung von Unstetigkeiten betrachtet. Bei der Diskretisierung mit XFEM wird die Kontinuität der Approximation durch eine Anreicherung der Ansatzfunktionen gemäß der abzubildenden Unstetigkeit reduziert. Demgegenüber erfolgt bei einer diffusen Grenzflächenmodellierung eine Regularisierung. Die dazu erforderliche zusätzliche Feldvariable führt oft zu Feldgleichungen mit partiellen Ableitungen höherer Ordnung und weist in ihrem Verlauf starke Gradienten auf. Die daraus resultierenden Anforderungen an den Ansatz werden durch eine Spline-basierte Approximation erfüllt. Um die Effizienz dieser isogeometrischen Diskretisierung weiter zu erhöhen, werden auf der Grundlage hierarchischer Splines adaptive Verfeinerungs- und Vergröberungstechniken entwickelt. Ausgewählte Diskretisierungsverfahren werden zur mehrskaligen Modellierung des gekoppelten magnetomechanischen Verhaltens von Magnetorheologischen Elastomeren (MRE) angewendet. In Kombination mit numerischen Homogenisierungsverfahren, ermöglichen die Mikrostrukturmodelle eine Vorhersage des effektiven magnetomechanischen Verhaltens von MRE. Außerderm wurden Verfahren zur Kopplung von FE-Modellen der MRE-Mikrostruktur mit einem Randelement-Modell der Umgebung vorgestellt. Mit Hilfe der entwickelten Verfahren kann das Verhalten von MRE in Form von Aktuatorspannungen, magnetostriktiven Deformationen und magnetischen Steifigkeitsänderungen vorhergesagt werden. Im Gegensatz zu zahlreichen anderen Modellierungsansätzen, stimmen die mit den hier vorgestellten Methoden für unterschiedliche Mikrostrukturen erzielten Vorhersagen sowohl mit analytischen als auch experimentellen Ergebnissen überein.

Magneto-sensitive elastomers (MSEs) establish a special class of smart materials, which are able to change their shape and mechanical behavior under external magnetic field. Nowadays, MSEs are one of the most perspective smart materials, since they can be used for design of functionally integrated lightweight structures in sensors, robotics, actuators and damper applications. MSEs typically consist of micron-sized magnetizable particles (e.g. carbonyl iron) dispersed within a non-magnetic elastomeric matrix. The spatial distribution of magnetic particles in MSEs can be either isotropic or anisotropic, depending on whether they have been aligned by an applied magnetic field before the cross-linking of the polymer. Depending on the magnetic properties of the particles, their shape, size and spatial distribution, the MSEs can exhibit different mechanical behavior. Most experimental studies show that MSEs with isotropic distribution of magnetic particles demonstrate a uniaxial expansion along the magnetic field. On the other side, it was shown experimentally that MSEs with anisotropic particle distributions demonstrate a uniaxial contraction along the magnetic field. Also, the experimental works show that the shear moduli of MSEs increase with increasing strength of the magnetic field and depend on the magnetic properties, volume fraction and spatial distribution of particles. Different analytical approaches were used in theoretical studies of the mechanical behavior of MSEs. They can be roughly classified as phenomenological, continuum-mechanics and microscopic approaches. In the phenomenological approaches, the expansion into a series of the shear modulus as a function of the strength of the magnetic field has been proposed, the coefficients of the expansion being considered as phenomenological fitting parameters. In the continuum-mechanics approach, an MSE is considered as continuous magnetic media. It allows us to determine the shape and the change in volume of a spherical MSE sample, placed in a uniform magnetic field. However, this approach is restricted to homogeneous particle distributions. The microscopic approach has a clear advantage, while a discrete particle distribution and pair-wise interactions between induced magnetic dipoles can be considered explicitly. The aim of the present work is to develop a microscopic theory, which properly describes the mechanical behavior of MSEs in the external magnetic field. The theory takes a microscopic structure, finite shape of the samples and magneto-mechanical coupling between particle positions and sample deformation explicitly into account.

A new theoretical formalism is developed for the study of the mechanical behaviour of magneto-sensitive elastomers (MSEs) under a uniform external magnetic field. This formalism allows us to combine macroscopic continuum-mechanics and microscopic approaches for complex analysis of MSEs with different shapes and with different particle distributions. It is shown that starting from a model based on an explicit discrete particle distribution one can separate the magnetic field inside the MSE into two contributions: one which depends on the shape of the sample with finite size and the other, which depends on the local spatial particle distribution. The magneto-induced deformation and the change of elastic modulus are found to be either positive or negative, their dependences on the magnetic field being determined by a non-trivial interplay between these two contributions. Mechanical properties are studied for two opposite types of coupling between the particle distribution and the magneto-induced deformation: absence of elastic coupling and presence of strong affine coupling. Predictions of a new formalism are in a qualitative agreement with existing experimental data.

Block copolymers are commercially significant and fundamentally interesting class of polymeric materials. The ability to undergo interfacial thermodynamics-controlled microphase separation from a completely disordered state in the melt to a specifically defined ordered structure through self-organization makes the block copolymers based materials unique. Block copolymer are strongly replacing many of the commercially available polymers due to their unique microstructure and properties. The most practical interests of block copolymers lie in the area of thermoplastic elastomers (TPEs). The objective of the present thesis work is to developing novel roots for enhancing the physical and mechanical properties in block copolymer and multigraft copolymers. Initially the properties are tailored by controlling chemical architecture at synthesis level and by selective blending at production level. This gives an easy access for improvement of the material properties and this is one of my major tasks in the present research modules. Further the block copolymer based TPEs are cross-linked in presence of electron beam (EB) radiation for developing materials with superior properties. The electron beam radiation has the ability to alter material parameters at molecular level for enhancing the macroscopic properties. The desirable physical and chemical properties can be easily attained by varying the radiation beam parameters. In addition to that, controlling the material at nanometer scale is one of the greatest challenges for current nanocomposite research. In elastomeric materials it is very prominent to fill the rubber matrix with nano particles from carbon or silica by melt mixing technique for enhancing the material properties. Other than conventional melt mixing technique, sol–gel processing is also a versatile technique, which making it possible to produce a wide variety of materials and to provide existing materials with novel properties. A combination of in situ sol-gel reaction with electron beam cross-linking in TPEs from triblock copolymer has been demonstrated for the first time as one of the novel nanocomposite system in this work. The main advantage of this system lies in controlling the material behaviour by finely tuning the size of silica nano particle generated inside TPE during in situ sol-gel reaction. Finally, the various roots employed for enhancing the material behaviour in block copolymers in the above research module were secussfully employed on super elastic multigraft copolymers for improving their strength withour sacrificing the super elastic nature.