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Due to some useful mechanical, dynamic, and dielectric properties along with the ease of processing and forming, liquid rubbers are ideal materials for fabricating dielectric elastomer actuators in various configurations and for many potential applications ranging from automation to automobile and medical industry. In this study, we present a cross-linkable liquid rubber composition where amine-catalyzed esterification reactions lead to the formation of a network structure based on anhydride functional isoprene rubber, carboxyl-terminated nitrile-butadiene rubber, and epoxy end-capped prepolymers. The success of this intricate network formation procedure was verified by HR-MAS NMR spectroscopy. The new isoprene-based elastomeric material exhibits actuation-relevant attributes including a low elastic modulus of 0.45 MPa, soft response to an applied load up to a large deformation of 300%, and a dielectric constant value (2.6) higher than the conventional Elastosil silicone (2.2). A dot actuator comprising of an isoprene dielectric elastomer film in unstretched state and carbon paste electrodes was fabricated that demonstrated an electrode deformation of 0.63%, which is nearly twice as high as for the commercial Elastosil 2030 film (â¼0.30%) at 5 kV. Compared to the Elastosil silicone film, the enhanced performance is attributed to the low modulus and high dielectric constant value of the new isoprene elastomer.
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The complex multiphase morphology of thermoplastic elastomers based on styrene-block copolymers (TPSs) affects their flow behavior significantly and in a way which may not be considered by commonly used characterization and evaluation procedures. To evaluate the relevance of non-Newtonian flow phenomena for the validity of rheometric data in processing, three commercially available TPSs with comparable hardness of about 60 Shore A but with different application fields were selected and characterized using parallel plate and high-pressure capillary rheometry. The validity of the rheometric data is assessed by modeling the flow in a high-pressure capillary rheometer by a computational fluid dynamics (CFD) simulation. The results were discussed in conjunction with close-up images of samples taken after the measurement. The materials show clearly different rheological behaviors but depend on the respective shear and geometrical conditions. In particular, for the material with the lowest viscosity, doubling the capillary diameter resulted in a disproportionate increase of the pressure loss by up to one third. Only the capillary flow of this material could not be reproduced by the CFD simulation. The results indicate that conventionally determined rheometric data of TPSs are of limited use in evaluating process flows for various material grades.
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Self-powered tactile module-based electronic skins incorporating triboelectric nanogenerator (TENG) appears to be a worthwhile alternative for smart monitoring devices in terms of sustainable energy harvesting. On top of it, ultra-stretchability and detection sensitivity are imperative to mimic human skin. We report, for the first time, a metal-free single electrode TENG-based self-powered tactile module comprising of microwells (diameters 2 µm and 200 nm, respectively) on fluoroelastomer (FKM) and laser induced graphene (LIG) electrodes by in situ simultaneous transfer printing method. Direct imprinting of both the active surface and LIG electrode on a tribonegative FKM has not been attempted before. The resulting triboelectric module exhibits impressive maximum power density of 715 mW m-2, open circuit voltage and maximum output current of 148 V and 9.6 µA respectively for a matching load of 10 MΩ. Moreover, the TENG unit is very robust and sustained high electrical output even at 200% elongation. A dielectric-to-dielectric TENG-based tactile sensor is also constructed using FKM (negative tribolayer) and TiO2 deposited micropatterned PDMS. Resulting tribo-sensor demonstrates remarkable motion and force sensitivity. It can also distinguish subtle human contact force that can simulate skin with high sensitivity and therefore, can be utilized for potential e-skin/bionic skin applications in health and human-machine interfaces.
Asunto(s)
Nanotecnología , Dispositivos Electrónicos Vestibles , Elasticidad , Electrodos , Humanos , Impresión TridimensionalRESUMEN
The preparation of intelligent structures for multiple smart applications such as soft-robotics, artificial limbs, etc., is a rapidly evolving research topic. In the present work, the preparation of a functional fabric, and its integration into a soft elastomeric matrix to develop an adaptive fiber-elastomer composite structure, is presented. Functional fabric, with the implementation of the shape memory effect, was combined with liquid polybutadiene rubber by means of a low-temperature vulcanization process. A detailed investigation on the crosslinking behavior of liquid polybutadiene rubber was performed to develop a rubber formulation that is capable of crosslinking liquid rubber at 75 °C, a temperature that is much lower than the phase transformation temperature of SMA wires (90-110 °C). By utilizing the unique low-temperature crosslinking protocol for liquid polybutadiene rubber, soft intelligent structures containing functional fabric were developed. The adaptive structures were successfully activated by Joule heating. The deformation behavior of the smart structures was experimentally demonstrated by reaching a 120 mm bending distance at an activation voltage of 8 V without an additional load, whereas 90 mm, 70 mm, 65 mm, 57 mm bending distances were achieved with attached weights of 5 g, 10 g, 20 g, 30 g, respectively.
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In this work, studies are carried out to understand the crosslinking reaction of epoxidized natural rubber (50 mol% epoxy, ENR-50) by metal ion namely ferric ion (Fe3+, FeCl3, ferric chloride). It is found that a small amount of FeCl3 can cure ENR to a considerable extent. A direct interaction of the ferric ion with the epoxy group as well as internal polymerization enable the ENR to be cured in an efficient manner. It was also found that with the increased concentration of FeCl3, the crosslinking density of the matrix increased and therefore, the ENR offers higher mechanical properties (i.e., modulus and tensile strength). In addition, the glass transition temperature (tg) of ENR vulcanizate is increased with increasing concentration of FeCl3. Moreover, the thermal degradation temperature (Td) of the ENR-FeCl3 compound was shifted toward higher temperature as increasing concentration FeCl3.
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Thermal conductivities of polybutadiene rubbers crosslinked by 2.4 and 2.8 phr of sulfur have been found to be functions of temperature via molecular dynamics (MD) simulations using the Green-Kubo method. From an analysis of the heat flux autocorrelation functions, it has been revealed that the dominant means of heat transport in rubbers is governed by deformations of polymeric chains. Thermal conductivities of rubber samples vulcanized by 2.4 and 2.8 phr of sulfur have been measured by the heat flow meter method between 0 ∘C and 60 ∘C at atmospheric pressure. The temperature dependencies of the thermal conductivities of rubbers and their glass transition temperatures derived from MD simulations are in good agreement with the literature and experimental data. Details are discussed in the paper.
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This work analyzes the thermal degradation and mechanical properties of iron (Fe)-containing MgAl layered double hydroxide (LDH)-based polypropylene (PP) nanocomposite. Ternary metal (MgFeAl) LDHs were prepared using the urea hydrolysis method, and Fe was used in two different concentrations (5 and 10 mol%). Nanocomposites containing MgFeAl-LDH and PP were prepared using the melt mixing method by a small-scale compounder. Three different loadings of LDHs were used in PP (2.5, 5, and 7.5 wt%). Rheological properties were determined by rheometer, and flammability was studied using the limiting oxygen index (LOI) and UL94 (V and HB). Color parameters (L*, a*, b*) and opacity of PP nanocomposites were measured with a spectrophotometer. Mechanical properties were analyzed with a universal testing machine (UTM) and Charpy impact test. The thermal behavior of MgFeAl-LDH/PP nanocomposites was studied using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). The morphology of LDH/PP nanocomposites was analyzed with a scanning electron microscope (SEM). A decrease in melt viscosity and increase in burning rate were observed in the case of iron (Fe)-based PP nanocomposites. A decrease in mechanical properties interpreted as increased catalytic degradation was also observed in iron (Fe)-containing PP nanocomposites. Such types of LDH/PP nanocomposites can be useful where faster degradation or faster recycling of polymer nanocomposites is required because of environmental issues.
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Computational fluid dynamics (CFD) simulation is an important tool as it enables engineers to study different design options without a time-consuming experimental workload. However, the prediction accuracy of any CFD simulation depends upon the set boundary conditions and upon the applied rheological constitutive equation. In the present study the viscoelastic nature of an unfilled gum acrylonitrile butadiene rubber (NBR) is considered by applying the integral and time-dependent Kaye-Bernstein-Kearsley-Zapas (K-BKZ) rheological model. First, exhaustive testing is carried out in the linear viscoelastic (LVE) and non-LVE deformation range including small amplitude oscillatory shear (SAOS) as well as high pressure capillary rheometer (HPCR) tests. Next, three abrupt capillary dies and one tapered orifice die are modeled in Ansys POLYFLOW. The pressure prediction accuracy of the K-BKZ/Wagner model was found to be excellent and insensitive to the applied normal force in SAOS testing as well as to the relation of first and second normal stress differences, provided that damping parameters are fitted to steady-state rheological data. Moreover, the crucial importance of viscoelastic modeling is proven for rubber materials, as two generalized Newtonian fluid (GNF) flow models severely underestimate measured pressure data, especially in contraction flow-dominated geometries.
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Dielectric elastomers (DEs) represent a class of electroactive polymers that deform due to electrostatic attraction between oppositely charged electrodes under a varying electric field. Over the last couple of decades, DEs have garnered considerable attention due to their much-coveted actuation properties. As far as the precise measurement systems are concerned, however, there is no standard instrument or interface to quantify various related parameters, e.g., actuation stress, strain, voltage and creeping etc. In this communication, we present an in-depth study of dielectric actuation behavior of dielectric rubbers by the state-of-the-art "Dresden Smart Rubber Analyzer" (DSRA), designed and developed in-house. The instrument allowed us to elucidate various factors that could influence the output efficiency of the DEs. Herein, several non-conventional DEs such as hydrogenated nitrile rubber, nitrile rubber with different acrylonitrile contents, were employed as an electro-active matrix. The effect of viscoelastic creeping on the prestrain, molecular architecture of the matrices, e.g., nitrile content of nitrile-butadiene rubber (NBR) etc., are also discussed in detail.
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The major controlling factors that determine the various mechanical properties of an elastomer system are type of chemical crosslinking and crosslink density of the polymer network. In this study, a catalytic amount of acrylonitrile butadiene copolymer (NBR) was used as a co-accelerator for the curing of polybutadiene (BR) elastomer. After the addition of this copolymer along with other conventional sulphur ingredients in polybutadiene compounds, a clear and distinct effect on the curing and other physical characteristics was noticed. The crosslinking density of BR was increased, as evidenced by rheometric properties, solid-state NMR and swelling studies. The vulcanization kinetics study revealed a substantial lowering of the activation energy of the sulphur crosslinking process when acrylonitrile butadiene copolymer was used in the formulation. The compounds were also prepared in the presence of carbon black and silica, and it was found that in the carbon black filled system the catalytic effect of the NBR was eminent. The effect was not only reflected in the mechanical performance but also the low-temperature crystallization behavior of BR systems was altered.
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The article focuses on comparing the friction, abrasion, and crack growth behavior of two different kinds of silica-filled tire tread compounds loaded with (a) in-situ generated alkoxide silica and (b) commercial precipitated silica-filled compounds. The rubber matrix consists of solution styrene butadiene rubber polymers (SSBR). The in-situ generated particles are entirely different in filler morphology, i.e., in terms of size and physical structure, when compared to the precipitated silica. However, both types of the silicas were identified as amorphous in nature. Influence of filler morphology and surface modification of silica on the end performances of the rubbers like dynamic friction, abrasion index, and fatigue crack propagation were investigated. Compared to precipitated silica composites, in-situ derived silica composites offer better abrasion behavior and improved crack propagation with and without admixture of silane coupling agents. Silane modification, particle morphology, and crosslink density were identified as further vital parameters influencing the investigated rubber properties.
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Each year, hundreds of millions of tires are produced and ultimately disposed into nature. To address this serious environmental issue, devulcanization could be one of the sustainable solutions that still remains as one of the biggest challenges across the globe. In this work, sulfur-vulcanized natural rubber (NR) is mechanochemically devulcanized utilizing a silane-based tetrasulfide as a devulcanizing agent, and subsequently, silica (SiO2)-based rubber composites are prepared. This method not only breaks the sulfur-sulfur cross-links but also produces reactive poly(isoprene) chains to interact with silica. The silica natural rubber composites are prepared by replacing 30% fresh NR by devulcanized NR with varying contents of silica. The composites exhibit excellent mechanical properties, tear strength, abrasion resistance, and dynamic mechanical properties as compared with the fresh natural rubber silica composites. The tensile strength of devulcanized rubber-based silica composites is â¼20 MPa, and the maximum elongation strain is â¼921%. The devulcanized composites are studied in detail by chemical, mechanical, and morphological analyses. Thus, the value added by the devulcanized rubber could attract the attention of recycling community for its sustainable applications.
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In this work, natural rubber (NR) was masticated using an internal mixer to fit the requirements of reactive blending with polylactide and characterized by size exclusion chromatography (SEC), Fourier-transform infrared (FT-IR) spectroscopy and dynamic rheology measurements. Subsequently, the effect of elevated temperatures (25 °C, 80 °C, and 170 °C) on the electron beam (EB) induced crosslinking and degradation of masticated natural rubber (mNR) in a nitrogen atmosphere without adding crosslinking agents has been investigated. The sol gel investigation showed that the gel dose of mNR slightly increased with increasing irradiation temperature, which is also confirmed by the swelling test. The chain scission to crosslinking ratio (Gs/Gx) was found to be less than 1 for irradiated mNR at 25 °C and 80 °C, suggesting a dominating crosslinking behavior of mNR. However, a significant increase of Gs/Gx ratio (~1.12) was observed for mNR irradiated at 170 °C due to the enhanced thermal degradation behavior at high temperature. A remarkably improved elasticity (higher complex viscosity, higher storage modulus, and longer relaxation time) for EB modified mNR was demonstrated by dynamic rheological analysis. Particularly, the samples modified at higher temperatures represented more pronounced elasticity behavior which resulted from the higher number of branches and/or the longer branched chains.
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A new biomimetic stimuli-responsive adaptive elastomeric material, whose mechanical properties are altered by a water treatment is reported in this paper. This material is a calcium sulphate (CaSO4) filled composite with an epoxidized natural rubber (ENR) matrix. By exploiting various phase transformation processes that arise when CaSO4 is hydrated, several different crystal structures of CaSO4· xH2O can be developed in the cross-linked ENR matrix. Significant improvements in the mechanical and thermal properties are then observed in the water-treated composites. When compared with the untreated sample, there is approximately 100% increase in the dynamic modulus. The thermal stability of the composites is also improved by increasing the maximum degradation rate temperature by about 20 °C. This change in behavior results from an in situ development of hydrated crystal structures of the nanosized CaSO4 particles in the ENR matrix, which has been verified using Raman spectroscopy, transmission electron microscopy, atomic force microscopy, and X-ray scattering. This work provides a promising and relatively simple pathway for the development of next generation of mechanically adaptive elastomeric materials by an eco-friendly route, which may eventually also be developed into an innovative biodegradable and biocompatible smart polymeric material.
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Specific physical and reactive compatibilization strategies are applied to enhance the interfacial adhesion and mechanical properties of heterogeneous polymer blends. Another pertinent challenge is the need of energy-intensive blending methods to blend high-tech polymers such as the blending of a pre-made hard polyurethane (-urea) with rubbers. We developed and investigated a reactive blending method to prepare the outstanding blends based on polyurethane-urea and rubbers at a low blending temperature and without any interfacial compatibilizing agent. In this study, the polyurethane-urea (PUU) was synthesized via the methylene diphenyl diisocyanate end-capped prepolymer and m-phenylene diamine based precursor route during blending at 100 °C with polar (carboxylated nitrile rubber (XNBR) and chloroprene rubber (CR)) and non-polar (natural rubber (NR), styrene butadiene rubber (sSBR), and ethylene propylene butadiene rubber (EPDM)) rubbers. We found that the in situ PUU reinforces the tensile response at low strain region and the dynamic-mechanical response up to 150 °C in the case of all used rubbers. Scanning electron microscopy reveals a stronger rubber/PUU interface, which promotes an effective stress transfer between the blend phases. Furthermore, energy filtered transmission electron microscopy (EFTEM) based elemental carbon map identifies an interphase region along the interface between the nitrile rubber and in situ PUU phases of this exemplary blend type.
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A mechanically adaptable elastomer composite is prepared with reversible soft-stiff properties that can be easily controlled. By the exploitation of different morphological structures of calcium sulfate, which acts as the active filler in a soft elastomer matrix, the magnitude of filler reinforcement can be reversibly altered, which will be reflected in changes of the final stiffness of the material. The higher stiffness, in other words, the higher modulus of the composites, is realized by the in situ development of fine nanostructured calcium sulfate dihydrate crystals, which are formed during exposure to water and, further, these highly reinforcing crystals can be transformed to a nonreinforcing hemihydrate mesocrystalline structure by simply heating the system in a controlled way. The Young's modulus of the developed material can be reversibly altered from â¼6 to â¼17 MPa, and the dynamic stiffness (storage modulus at room temperature and 10 Hz frequency) alters its value in the order of 1000%. As the transformation is related to the presence of water molecules in the crystallites, a hydrophilic elastomer matrix was selected, which is a blend of two hydrophilic polymers, namely, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer and a terpolymer of ethylene oxide-propylene oxide-allyl glycidyl ether. For the first time, this method also provides a route to regulate the morphology and structure of calcium sulfate nanocrystals in a confined ambient of cross-linked polymer chains.
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A sol-gel transformation of liquid silica precursor to solid silica particles was carried out in a one-pot synthesis way, where a solution of styrene butadiene elastomer was present. The composites, thus produced, offered remarkable improvements of mechanical and dynamic mechanical performances compared to precipitated silica. The morphological analysis reveals that the alkoxy-based silica particles resemble a raspberry structure when the synthesis of the silica was carried out in the presence of polymer molecules and represent a much more open silica-network structure. However, in the absence of the polymer, the morphology of the silica particles is found to be different. It is envisaged that the special morphology of the in situ synthesized silica particles contributes to the superior reinforcement effects, which are associated with a strong silica-rubber interaction by rubber chains trapped inside the raspberry-like silica aggregates. Therefore, the interfaces are characterized in detail by low-field solid-state 1H NMR spectroscopy, 29Si solid-state NMR spectroscopy, and energy-dispersive X-ray spectroscopy. Low-field 1H NMR-based double-quantum experiments provide a quantitative information about the cross-link density of the silica-filled rubber composites and about the influence of silane coupling agent on the chemical cross-link density of the network and correlates well with equilibrium swelling measurements. The special microstructure of the alkoxy-based silica was found to be associated with the interaction between alkoxy-based silica and rubber chains as a consequence of particle growth in the presence of rubber chains.
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A detail study concerning the strain (tensile) dependent electrical conductivity of elastomeric composites is reported in this present paper. Multiwall carbon nanotubes (CNT), conducting carbon black (CB), and their combinations were considered as conducting filler in cross-linked natural rubber matrix. The loadings of the fillers were considered from 3 to 11 phr (filler concentration close to their percolation threshold). Without hindering the elastic nature of the composite (reversible stretchability up to several 100%), the change of relative resistance, ΔR/R0 (ΔR is the change in the resistance with respect to strain and R0 is the initial resistance of the sample) of the CB filled composites was found to be as much as â¼1300 at around 120% elongation. This value is much higher than any other reported values obtained from conducting polymeric composites. It was found that CNT offered a strong strain dependent character in the regime 100% to 150% elongation, whereas, the carbon black filled natural rubber showed strong strain dependencies at 50% to 100% elongation strain. The combination of two different fillers could be exploited to tailor and manipulate the sensing operating regime from 50% to 150% strain depending on the ratios of the two filler system. Additionally, after several loading-unloading cycles, the conductivity of the sample was very stable for CB filled system but for CNT filled system the conductivity of the sample was altered. This type of elastic materials could be used in structural health monitoring, sensors in different dynamic elastomeric parts like tires, valves, gaskets, engine mounts, etc.
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This is the first study on the impact of ice crystals on glass transition and mechanical behavior of soft cross-linked elastomers. A hydrophilic elastomer such as epichlorohydrin-ethylene oxide-allyl glycidyl ether can absorb about â¼40 wt % of water. The water-swollen cross-linked network exhibits elastic properties with more than 1500% stretchability at room temperature. Coincidently, the phase transition of water into solid ice crystals inside of the composites allows the reinforcement of the soft elastomer mechanically at lower temperatures. Young's modulus of the composites measured at -20 °C remarkably increased from 1.45 to 3.14 MPa, whereas at +20 °C, the effect was opposite and the Young's modulus decreased from 0.6 to 0.03 MPa after 20 days of water treatment. It was found that a part of the absorbed water, â¼74% of the total absorbed water, is freezable and occupies nearly 26 vol % of the composites. Simultaneously, these solid ice crystals are found to be acting as a reinforcing filler at lower temperatures. The size of these ice crystals is distributed in a relatively narrow range of 400-600 nm. The storage modulus (E') of the ice crystal-filled composites increased from 3 to 13 MPa at -20 °C. The glass transition temperature (-37 °C) of the soft cross-linked elastomer was not altered by the absorption of water. However, a special transition (melting of ice) occurred at temperatures close to 0 °C as observed in the dynamic mechanical analysis of the water-swollen elastomers. The direct polymer/filler (ice crystals) interaction was demonstrated by strain sweep experiments and investigated using Fourier transform infrared spectroscopy. This type of cross-linked rubber could be integrated into a smart rubber application such as in adaptable mechanics, where the stiffness of the rubber can be altered as a function of temperature without affecting the mechanical stretchability either below or above 0 °C (above the glass temperature region) of the rubber.
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Invented by Charles Goodyear, chemical cross-linking of rubbers by sulfur vulcanization is the only method by which modern automobile tires are manufactured. The formation of these cross-linked network structures leads to highly elastic properties, which substantially reduces the viscous properties of these materials. Here, we describe a simple approach to converting commercially available and widely used bromobutyl rubber (BIIR) into a highly elastic material with extraordinary self-healing properties without using conventional cross-linking or vulcanising agents. Transformation of the bromine functionalities of BIIR into ionic imidazolium bromide groups results in the formation of reversible ionic associates that exhibit physical cross-linking ability. The reversibility of the ionic association facilitates the healing processes by temperature- or stress-induced rearrangements, thereby enabling a fully cut sample to retain its original properties after application of the self-healing process. Other mechanical properties, such as the elastic modulus, tensile strength, ductility, and hysteresis loss, were found to be superior to those of conventionally sulfur-cured BIIR. This simple and easy approach to preparing a commercial rubber with self-healing properties offers unique development opportunities in the field of highly engineered materials, such as tires, for which safety, performance, and longer fatigue life are crucial factors.