Sugarcane Bagasse Ash as a Reinforcing Filler in Thermoplastic Elastomers: Structural and Mechanical Characterizations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

On Designing Compliant Actuators Based On Dielectric Elastomers

Dielectric Elastomers (DE) are incompressible dielectrics which can experience deviatoric (isochoric) finite deformations in response to applied large electric fields. Thanks to the strong electro-mechanical coupling, DE intrinsically offer great potentialities for conceiving novel solid-state mechatronic devices, in particular linear actuators, which are more integrated, lightweight, economic, silent, resilient and disposable than equivalent devices based on traditional technologies. Such systems may have a huge impact in applications where the traditional technology does not allow coping with the limits of weight or encumbrance, and with problems involving interaction with humans or unknown environments. Fields such as medicine, domotic, entertainment, aerospace and transportation may profit. For actuation usage, DE are typically shaped in thin films coated with compliant electrodes on both sides and piled one on the other to form a multilayered DE. DE-based Linear Actuators (DELA) are entirely constituted by polymeric materials and their overall performance is highly influenced by several interacting factors; firstly by the electromechanical properties of the film, secondly by the mechanical properties and geometry of the polymeric frame designed to support the film, and finally by the driving circuits and activation strategies. In the last decade, much effort has been focused in the devolvement of analytical and numerical models that could explain and predict the hyperelastic behavior of different types of DE materials. Nevertheless, at present, the use of DELA is limited. The main reasons are 1) the lack of quantitative and qualitative models of the actuator as a whole system 2) the lack of a simple and reliable design methodology. In this thesis, a new point of view in the study of DELA is presented which takes into account the interaction between the DE film and the film supporting frame. Hyperelastic models of the DE film are reported which are capable of modeling the DE and the compliant electrodes. The supporting frames are analyzed and designed as compliant mechanisms using pseudo-rigid body models and subsequent finite element analysis. A new design methodology is reported which optimize the actuator performances allowing to specifically choose its inherent stiffness. As a particular case, the methodology focuses on the design of constant force actuators. This class of actuators are an example of how the force control could be highly simplified. Three new DE actuator concepts are proposed which highlight the goodness of the proposed method.

Liquid crystalline elastomers as stimuli-responsive microactuators

Liquid crystalline elastomers (LCEs) are known to perform a reversible change of shape upon the phase transition from the semi-ordered liquid crystalline state to the chaotic isotropic state. This unique behavior of these “artificial muscles” arises from the self-organizing properties of liquid crystals (mesogens) in combination with the entropy-elasticity of the slightly crosslinked elastomer network. In this work, micrometer-sized LCE actuators are fabricated in a microfluidic setup. The microtubular shear flow provides for a uniform orientation of the mesogens during the crosslinking, a perquisite for obtaining actuating LCE samples. The scope of this work was to design different actuator geometries and to broaden the applicability of the microfluidic device for different types of liquid crystalline mesogens, ranging from side-chain to main-chain systems, as well as monomer and polymer precursors. For example, the thiol-ene “click” mechanism was used for the polymerization and crosslinking of main-chain LCE actuators. The main focus was, however, placed on acrylate monomers and polymers with LC side chains. A LC polymer precursor, comprising mesogenic and crosslinkable side-chains was synthesized. Used in combination with an LC monomer, the polymeric crosslinker promoted a stable LC phase, which allowed the mixture to be isothermally handled in the microfluidic reactor. If processed without the additional LC components, the polymer precursor yielded actuating fibers. A suitable co-flowing continuous phase facilitates the formation of a liquid jet and lowers the tendency for drop formation. By modification of the microfluidic device, it was further possible to prepare core-shell particles, comprised of an LCE shell and filled with an isotropic liquid. In analogy to the heart, a hollow muscle, the elastomer shell expels the inner liquid core upon its contraction. The feasibility of the core-shell particles as micropumps was demonstrated. In general, the synthesized LCE microactuators may be utilized as active components in micromechanical and lab-on-chip systems.

Designing biostable polyurethane elastomers for biomedical implants

The chemical structure, synthesis, morphology, and properties of polyurethane elastomers are briefly discussed. The current understanding of the effect of chemical structure and the associated morphology on the stability of polyurethanes in the biological environments is reviewed. The degradation of conventional polyurethanes appears as surface or deep cracking, stiffening, and deterioration of mechanical properties, such as flex-fatigue resistance. Polyester and poly( tetramethylene oxide) based polyurethanes degrade by hydrolytic and oxidative degradation of ester and ether functional groups, respectively. The recent approaches to develop polyurethanes with improved long-term biostability are based on developing novel polyether, hydrocarbon, polycarbonate, and siloxane macrodiols to replace degradation-prone polyester and polyether macrodiols in polyurethane formulations. The new approaches are discussed with respect to synthesis, properties and biostability based on reported in vivo studies. Among the newly developed materials, siloxane-based polyurethanes have exhibited excellent biostability and are expected to find many applications in biomedical implants.

Long-term in vivo biostability of poly(dimethylsiloxane) / poly(hexamethylene oxide) mixed macrodiol-based polyurethane elastomers

The long-term biostability of a novel thermoplastic polyurethane elastomer (Elast-Eon(TM) 2 80A) synthesized using poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS) macrodiols has been studied using an in vivo ovine model. The material's biostability was compared with that of three commercially available control materials, Pellethane(R) 2363-80A, Pellethane(R) 2363-55D and Bionate(R) 55D, after subcutaneous implantation of strained compression moulded flat sheet dumbbells in sheep for periods ranging from 3 to 24 months. Scanning electron microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy were used to assess changes in the surface chemical structure and morphology of the materials. Gel permeation chromatography, differential scanning calorimetry and tensile testing were used to examine changes in bulk characteristics of the materials. The results showed that the biostability of the soft flexible PDMS-based test polyurethane was significantly better than the control material of similar softness, Pellethane(R) 80A, and as good as or better than both of the harder commercially available negative control polyurethanes. Pellethane(R) 55D and Bionate(R) 55D. Changes observed in the surface of the Pellethane(R) materials were consistent with oxidation of the aliphatic polyether soft segment and hydrolysis of the urethane bonds joining hard to soft segment with degradation in Pellethane(R) 80A significantly more severe than that observed in Pellethane(R) 55D. Very minor changes were seen on the surfaces of the Elast-Eon(TM) 2 80A and Bionate(R) 55D materials. There was a general trend of molecular weight decreasing with time across all polymers and the molecular weights of all materials decreased at a similar relative rate. The polydispersity ratio, M-w/M-n, increased with time for all materials. Tensile tests indicated that UTS increased in Elast-Eon(TM) 2 80A and Bionate(R) 55D following implantation under strained conditions. However, ultimate strain decreased and elastic modulus increased in the explanted specimens of all three materials when compared with their unimplanted unstrained counterparts. The results indicate that a soft, flexible PDMS-based polyurethane synthesized using 20% PHMO and 80% PDMS macrodiols has excellent long-term biostability compared with commercially available polyurethanes. (C) 2004 Elsevier Ltd. All rights reserved.

Bound antioxidants in elastomers

DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY WITH PRIOR ARRANGEMENT

An investigation into the network structures of eThylene propylene terpolymer elastomers

A series of ethylene propylene terpolymer vulcanizates, prepared by varying termonomer type, cure system, cure time and cure temperature, are characterized by determining the number and type of cross-links present. The termonomers used represent the types currently available in commercial quantities. Characterization is carried out by measuring the C1 constant of the Mooney Rivlin Saunders equation before and after treatment with the chemical probes propane-2-thiol/piperidine and n-hexane thiol/piperidine, thus making it possible to calculate the relative proportions of mono-sulphidic, di-sulphidic and poly- sulphidic cross-links. The cure systems used included both sulphur and peroxide formulations. Specific physical properties are determined for each network and an attempt is made to correlate observed changes in these with variations in network structure. A survey of the economics of each formulation based on a calculated efficiency parameter for each cure system is included. Values of C1 are calculated from compression modulus data after the reliability of the technique when used with ethylene propylene terpolymers had been established. This is carried out by comparing values from both compression and extension stress strain measurements for natural rubber vulcanizates and by assessing the effects of sample dimensions and the degree of swelling. The technique of compression modulus is much more widely applicable than previously thought. The basic structure of an ethylene propylene terpolymer network appears to be independent of the type of cure system used ( sulphur based systems only), the proportions of constituent cross-links being nearly constant.

Tailoring Magnetic, Mechanical and Dielectric Properties of Magnetorheological Elastomers based on Natural Rubber and Iron by Magnetic Field Assisted Curing for Possible Applications

If magnetism is universal in nature, magnetic materials are ubiquitous. A life without magnetism is unthinkable and a day without the influence of a magnetic material is unimaginable. They find innumerable applications in the form of many passive and active devices namely, compass, electric motor, generator, microphone, loud speaker, maglev train, magnetic resonance imaging, data recording and reading, hadron collider etc. The list is endless. Such is the influence of magnetism and magnetic materials in ones day to day life. With the advent of nanoscience and nanotechnology, along with the emergence of new areas/fields such as spintronics, multiferroics and magnetic refrigeration, the importance of magnetism is ever increasing and attracting the attention of researchers worldwide. The search for a fluid which exhibits magnetism has been on for quite some time. However nature has not bestowed us with a magnetic fluid and hence it has been the dream of many researchers to synthesize a magnetic fluid which is thought to revolutionize many applications based on magnetism. The discovery of a magnetic fluid by Jacob Rabinow in the year 1952 paved the way for a new branch of Physics/Engineering which later became magnetic fluids. This gave birth to a new class of material called magnetorheological materials. Magnetorheological materials are considered superior to electrorheological materials in that magnetorheology is a contactless operation and often inexpensive.Most of the studies in the past on magnetorheological materials were based on magnetic fluids. Recently the focus has been on the solid state analogue of magnetic fluids which are called Magnetorheological Elastomers (MREs). The very word magnetorheological elastomer implies that the rheological properties of these materials can be altered by the influence of an external applied magnetic field and this process is reversible. If the application of an external magnetic field modifies the viscosity of a magnetic fluid, the effect of external magnetic stimuli on a magnetorheological elastomer is in the modification of its stiffness. They are reversible too. Magnetorheological materials exhibit variable stiffness and find applications in adaptive structures of aerospace, automotive civil and electrical engineering applications. The major advantage of MRE is that the particles are not able to settle with time and hence there is no need of a vessel to hold it. The possibility of hazardous waste leakage is no more with a solid MRE. Moreover, the particles in a solid MRE will not affect the performance and durability of the equipment. Usually MR solids work only in the pre yield region while MR fluids, typically work in the post yield state. The application of an external magnetic field modifies the stiffness constant, shear modulus and loss modulus which are complex quantities. In viscoelastic materials a part of the input energy is stored and released during each cycle and a part is dissipated as heat. The storage modulus G′ represents the capacity of the material to store energy of deformation, which contribute to material stiffness. The loss modulusG′′ represents the ability of the material to dissipate the energy of deformation. Such materials can find applications in the form of adaptive vibration absorbers (ATVAs), stiffness tunable mounts and variable impedance surfaces. MREs are an important material for automobile giants and became the focus of this research for eventual automatic vibration control, sound isolation, brakes, clutches and suspension systems

Synthesis and characterization of biodegradable thermoplastic elastomers for medical applications: Novel copolyesters as an alternative to polylactide and poly (e-caprolactone)

421 p.

Influence of curvature on the device physics of thin film transistors on flexible substrates

Thin film transistors (TFTs) on elastomers promise flexible electronics with stretching and bending. Recently, there have been several experimental studies reporting the behavior of TFTs under bending and buckling. In the presence of stress, the insulator capacitance is influenced due to two reasons. The first is the variation in insulator thickness depending on the Poisson ratio and strain. The second is the geometric influence of the curvature of the insulator-semiconductor interface during bending or buckling. This paper models the role of curvature on TFT performance and brings to light an elegant result wherein the TFT characteristics is dependent on the area under the capacitance-distance curve. The paper compares models with simulations and explains several experimental findings reported in literature. (C) 2014 AIP Publishing LLC.

A constitutive model for cavitation and cavity growth in rubber-like materials under arbitrary tri-axial loading

In this paper, we attempted to construct a constitutive model to deal with the phenomenon of cavitation and cavity growth in a rubber-like material subjected to an arbitrary tri-axial loading. To this end, we considered a spherical elementary representative volume in a general Rivlin's incompressible material containing a central spherical cavity. The kinematics proposed by [Hou, H.S., Abeyaratne, R., 1992. Cavitation in elastic and elastic-plastic solids. J. Mech. Phys. Solids 40, 571-722] was adopted in order to construct an approximate but optimal field. In order to establish a suitable constitutive law for this class of materials, we utilized the homogenisation technique that permits us to calculate the average strain energy density of the volume. The cavity growth was considered through a physically realistic failure criterion. Combination of the constitutive law and the failure criterion enables us to describe correctly the global behaviour and the damage evolution of the material under tri-axial loading. It was shown that the present models can efficiently reproduce different stress states, varying from uniaxial to tri-axial tensions, observed in experimentations. Comparison between predicted results and experimental data proves that the proposed model is accurate and physically reasonable. Another advantage is that the proposed model does not need special identification work, the initial Rivlin's law for the corresponding incompressible material is sufficient to form the new law for the compressible material resulted from cavitation procedure. (C) 2007 Elsevier Ltd. All rights reserved.

Nanocompósitos de elastômero termoplástico à base de PP/EPDM/argila organofílica

Neste trabalho foram preparados nanocompósitos de elastômeros termoplásticos à base de PP/EPDM/argila organofílica. Foram utilizados como agentes interfaciais polipropileno e terpolímero de etileno-propileno-dieno ambos modificados com grupos anidrido maleico, PP-MA e EPDM-MA, respectivamente. Dois tipos de argila organofílica, que se diferenciam pela estrutura química do surfactante e conseqüentemente pela estabilidade térmica, foram empregados como carga inorgânica. Os nanocompósitos foram preparados pela técnica de intercalação por fusão em câmara interna de mistura e a incorporação da argila foi feita pela adição de masterbatches previamente preparados. Foram investigadas as propriedades de tração, reométricas e ainda a morfologia (cristalinidade e estrutura obtida) dos nanocompósitos a fim de estabelecer a influência do tipo e quantidade de argila organofílica e agente interfacial. Os resultados mostraram que a adição de agente interfacial melhorou a dispersão da argila organofílica na matriz de PP/EPDM, particularmente o PP-MA. Foram obtidos nanocompósitos com estruturas mistas intercaladas e esfoliadas, que resultaram em maiores valores de módulo de elasticidade e manutenção dos valores de deformação. As propriedades reométricas confirmaram o maior grau de dispersão da argila organofílica em nanocompósitos contendo PP-MA. Teores crescentes de argila reduziram a cristalinidade dos nanocompósitos, os quais quando reprocessados, mantiveram as características inerentes ao TPE de origem. Por fim, a estrutura do surfactante presente

Avaliação da degradação de elásticos ortodônticos intraorais de látex

Avaliou-se a taxa de degradação de elásticos ortodônticos de látex de diferentes fabricantes e diâmetros em diversos intervalos de tempo. Grupos de 15 elásticos de força média dos fabricantes AmericanOrthodontics (Sheboygan, Wis, EUA), Tp (La Porte, IN, EUA), Morelli (Sorocaba, SP, Brasil) e Uniden (Sorocaba, SP, Brasil); de diâmetros 3/16, 1/4 e 5/16 foram analisados nos intervalos de 0,1,3,6,12 e 24 horas, totalizando-se 1080 espécimes. Os elásticos foram estirados individualmente à distância de 30mm, respeitando-se o intervalo de um minuto entre cada estiramento. Os materiais foram acondicionados imersos em água deionizada à 37C. Realizou-se leitura das forças na máquina de ensaios Emic DL 500 (Emic Co, Sao Paulo, Brasil) à velocidade de 30 mm/min, com uma célula de 2Kg (Emic Co, Sao Paulo, Brasil). A leitura de cada elástico consumiu aproximadamente um minuto. Teste Kruskal-wallis com correções por Dunns aferiu significância estatística dos resultados. Foram observadas diferenças entre os grupos analisados, exceto às marcas Morelli e Tp. Foram significativas as inferências das variáveis tempo e marca comercial. Em 0 hora, a relação entre as forças geradas foi Morelli>AO>Uniden>Tp para elásticos 3/16 (p=0,0016) e 1/4 (p=0,0016) e, de Morelli>AO>Tp>Uniden para elásticos 5/16 (p=0,0087). Após 24 horas, as porcentagens de degradação dos elásticos foram AO>Morelli>Uniden>Tp no diâmetro 3/16; AO>Tp>Morelli>Uniden no diâmetro 1/4 e Tp>AO>Uniden>Morelli para elásticos de diâmetro 5/16. O comportamento no intervalo de 0-24 horas demonstrou uma queda acentuada no período de 0-3 horas, um ligeiro aumento em 3-6 horas, seguido de uma queda progressiva no intervalo de 6-24 horas.

Tenacificação em Nanocompósitos de Poliamida 6 e Argila

Nanocompósitos de poliamida 6 (PA6) e montmorilonita modificada com sal de amônio quaternário têm sido estudados, visando melhorar as propriedades térmicas e mecânicas. De fato os efeitos da nano-escala e da interação carga-matriz resultam em maior módulo de elasticidade e resistência à tração, porém a deformação é reduzida. Assim, nesse trabalho, optou-se por adicionar elastômeros, terpolímero de etileno-propileno-dieno (EPDM) e terpolímero de etileno-propileno-dieno modificado com anidrido maleico (EPDM-MA), ao sistema PA 6/argila organofílica para recuperar os valores de deformação. Foi utilizada montmorilonita modificada com cloreto de dimetildioctadecil amônio. A intercalação por fusão foi realizada em câmara interna de mistura. Além das propriedades mecânicas, térmicas e reológicas, foram investigadas as modificações na cristalinidade da fase PA-6 em função da adição da argila modificada, EPDM e EPDM-MA, detectando-se as variações no grau de cristalinidade e nas temperaturas de fusão e cristalização. Os difratogramas de raios-x revelaram ocorrência de intercalação/esfoliação e também modificação da forma cristalina da PA 6, indicando a formação do cristal gama