Influence of orthogonal prestrain on the viscoelastic behaviour of highly-filled elastomers

Highly-filled elastomers exhibit a complex nonlinear mechanical behaviour that is difficult to characterize experimentally. This paper presents a Dynamic Mechanical Analysis (DMA) method coupled with orthogonal prestrains, applied in two distinct steps. A localization operator between measurements at the arms of a cross-shaped specimen and the stress and strain fields at its center was determined using elastic small strain finite element computations. The operator makes estimating the storage and loss moduli at the center of the specimen possible. A mathematical model is then fitted to the moduli values. These results are compared to DMA measurements of highly-filled elastomers under uniaxial prestrain. Although the storage and loss moduli increase with the prestrain under both loadings, the nonlinear behaviour is quantitatively modified by adding an orthogonal prestrain. In addition, the modification of the behaviour under a horizontal prestrain is cancelled out by an increase of the vertical prestrain, which may be explained by fillers aligning in the direction of the prestrain.     

Biaxial tensile behavior and strength of architectural fabric membranes

The utilization of composite fabric membrane materials for large-span membrane structures has attracted considerable attention in recent decades due to enhanced material properties. Biaxial mechanical properties with respect to real engineering applications are essential and indispensable in comparison with uniaxial ones. This study focuses on true biaxial characteristics of a typical polyvinylidene fluoride (PVDF)-coated polyester membrane material in terms of stress-strain characteristics and breaking criteria.The true stress-strain curves obtained from an experimental study, i.e. seven loading ratios on the basis of symmetry and typical conditions, are investigated with digital image correlation method. The interpolation of these curves in combination of least square method achieves a three-dimensional strain surface as a function of warp and weft strains, which is useful to assess reasonable structural behavior. A new breaking criteria intended for architectural fabric membrane is proposed in analogy to Tsai-Hill, Yeh-Stratton and Norris failure criteria. The basic constants in the criteria are determined using experimental results. A comparative analysis between available uniaxial and biaxial criteria shows that the new criteria can cover all criteria due to the fact that biaxial mechanical properties are larger than uniaxial ones. Furthermore, a similar but glued specimen is employed to compare welded specimens. It is obtained that observations, values and curve tendency are similar, demonstrating the suitability of using new specimens to identify true biaxial properties.     

A new biaxial compression fixture for polymeric foams

This article presents a new biaxial compression test fixture designed for polymeric foam materials. The main advantage of the new fixture is that it is designed for uniaxial testing machines, therefore the biaxial compression measurement does not require a multiaxial test system. The geometries of the fixture and the test specimen, respectively, ensure equibiaxial loading conditions. In order to demonstrate the performance of this new device, equibiaxial measurements of a polymeric foam material are presented. The particular material under consideration is a closed-cell polyethylene foam. In addition, the relation between uniaxial compression tests and equibiaxial compression tests are presented.     

Nonlinear stress relaxation of a styrene–butadiene random copolymer

The isothermal uniaxial stress relaxation response in the vicinity of the glass-to-rubber transition has been measured for a lightly crosslinked poly(styrene–butadiene) random copolymer, 85% styrene by weight. The volume change during stress relaxation was determined by measuring the time-dependent lateral contraction of the specimen with a Hall-effect proximity detector. The specimen exhibited an instantaneous dilation upon application of the strain and a subsequent time-dependent volume decrease. The stress relaxation behavior and the associated volume relaxation were determined for a variety of strains and temperatures in both the linear and nonlinear viscoelastic regime. As the applied strain was increased the isothermal tensile modulus decreased and the shape of the log(modulus) vs. log(time) curve was altered. At equal levels of strain the tensile modulus exhibited increasing deviations from the linear viscoelastic response as the temperature was decreased. The maximum difference between the nonlinear tensile modulus and the linear viscoelastic response was observed at short times. Subsequently, the nonlinear tensile modulus began to approach the linear viscoelastic modulus with increasing time. Both the instantaneous dilation and the magnitude of the time-dependent part of the volume change increased as the level of applied strain was increased and/or as the temperature was decreased. The observed nonlinearity in the tensile stress relaxation response has been quantitively related to the experimentally measured volume relaxation with a free-volume model.     

Room-temperature vulcanized silicone rubber/barium titanate–based high-performance nanocomposite for energy harvesting

Rubber composites were prepared for elastomer slab by mixing barium titanate (BaTiO₃), carbon nanotube (CNT), carbon black (CB), and room-temperature vulcanized (RTV) silicone rubber. An electrode was prepared from composite for energy harvesting with fillers such as CB and CNT, and RTV thinner was used to improve the processing of the specimen. At 50 phr of BaTiO₃, there is an increase in compressive modulus by 180%. There was a correlation between prestrain and biaxial strain in enhancing the energy generation. After poling of the rubber composite containing 50 phr of BaTiO₃ at 11 kV/mm, the energy harvesting was increased at all strains. In durability test at 70 phr of BaTiO₃ for 60% cyclic biaxial strain, the drop in voltage from the piezoelectric energy harvesting was almost zero for 3000 cycles.     

Artificial ageing of double base rocket propellant

The ageing of double base rocket propellants (DB rocket propellants), which is a consequence of chemical reactions and physical processes that take place over time, has significant effect on their relevant properties (e.g. chemical composition, mechanical properties, ballistic properties, etc.). The changes of relevant properties limit the safe and reliable service life of DB rocket propellants. This is the reason why numerous research efforts are devoted to finding out reliable methods to measure the changes caused by ageing, to assess the quality at a given moment of time, and to predict remaining life-time of DB rocket propellants. In this work we studied dynamic mechanical properties of DB rocket propellant artificially aged at elevated temperatures, in order to detect and quantify changes in dynamic mechanical properties caused by the ageing. Dynamic mechanical properties were studied using dynamic mechanical analyser (DMA). The results obtained have shown that the ageing causes significant changes of DMA curve’s shape and positions. These changes are quantified by following some characteristic points on DMA curves (e.g. glass transition temperatures; storage modulus, loss modulus and tanδ at characteristic temperatures, etc.). It has been found out that the most sensitive parameters to the ageing process are: storage modulus at viscoelastic and softening region, peak width and height on loss modulus curve, glass transition and softening temperature, and tanδ at viscoelastic region.     

The nonlinear viscoelastic behavior of a carbon-black-filled elastomer

The stress relaxation behavior of a carbon-black-filled elastomer is shown to be independent of the state of deformation, and the temperature dependence of its static modulus is in good accord with that predicted by the statistical theory of elasticity. The storage and loss moduli are found to be separable functions of frequency and overall strain effects in both simple tension and pure shear. A separability of static deformational and dynamic strain amplitude effects is found for the storage modulus, but could not be determined for the loss modulus. However, the loss tangent is found to be a function of the static state of deformation. From these experimental results, it is shown that an existing viscoelasticity theory for an unfilled system when specialized to uniaxial extensions has a form which can be made suitable for representing the dynamic behavior of filled systems by the introduction of two functions of the dynamic strain amplitude.     

A new high frequency dynamic mechanical analysis system: An approach to direct high frequency testing of tire tread rubber

Dynamic Mechanical Analysis (DMA) systems are measurement devices for obtaining master curves and complex modules of viscoelastic materials, such as rubbers. The conventional DMAs measurement systems in market have several limitations, which restrict their ability for operating at high frequencies. Thus, Williams, Landel and Ferry (WLF) relation is used to produce master curves and predict the material properties at high frequencies. In conventional DMAs, experiments are done in a range of temperatures, and then a master curve is made for a chosen reference temperature by shifting the measurements data to high frequencies. Therefore, the obtained results, which are not based on direct measurements, can be inaccurate. In order to overcome this problem a new simple shear high-frequency DMA (HFDMA) system is designed and built to directly measure the dynamic mechanical properties of viscoelastic material at high frequencies and the strain levels sufficient for tire manufacturers. The new HFDMA can be used to test any viscoelastic materials which have glass transmission temperature (Tg) lower than room temperature (about 23 °C) such as the Styrene-butadiene rubber (SBR). The SBR is the base material for tire tread. The designing process of this new HFDMA is presented in this paper. The rubber specimen shape is chosen by taking into account the shear elastic wave effect, bending, buckling effect and heat generation in the specimen. The repeatability test is accomplished to ensure that the results obtained from the new HFDMA are repeatable and the repeatability uncertainty is about 0.04%. The new HFDMA is validated by comparing to the direct test results of conventional DMA at 100 Hz. The direct high frequency (5 kHz) complex shear modulus and damping factor are compared with the master curve of the conventional DMA developed by the use of WLF relation for SBR. This comparison revealed that the complex shear modulus and damping factor of the SBR obtained from the HFDMA at 5 kHz and 0.05% strain amplitude are about 7% and 6.5% higher than those obtained from the conventional DMA, respectively.     

Thermal and dynamic mechanical properties of poly(propylene carbonate)

Summary Thermal and dynamic mechanical properties of carbon dioxide and propylene oxide alternative copolymer, poly(propylene carbonate) (PPC), and the end-capped PPC with maleic anhydride were investigated by means of TG and DMA. A master curve of the storage modulus vs. frequency can be deduced from the isochronal curves. Physical parameters of both plain and MA end-capped PPC were discussed. The results showed that for maleic anhydride (MA) end-capping PPC, an improvement of its thermal stability and mechanical properties accompanied with some modifications of the viscoelastic behavior were obtained.     

A five-parameter fractional derivative temperature spectrum model for polymeric damping materials

To capture viscoelastic behavior of polymeric damping materials based on limited dynamic mechanical analysis tests, a simple fractional temperature spectrum model representing the viscoelastic materials is proposed in this paper and experimental tests aims at stressing the validity of the model. The storage modulus, the loss modulus, and the loss factor, are established based on the five-parameter fractional derivative model and the time–temperature superposition principle. The dynamic mechanical tests of two polymeric materials are carried out to verify this temperature spectrum model. Results indicate a good agreement between the temperature spectrum model and experimental tests at various temperature conditions. Furthermore, thermodynamic coupling of the viscoelastic material is investigated by temperature rise calculation and vibration experiment test. Comparison analysis shows that the temperature rise model can simulate the temperature rise process for the shear vibration of the constrained damping, which provide references for the damping capability, thermal damage and failure of viscoelastic material.     

Measurement of viscoelastic properties for polymers by nanoindentation

A new method has been proposed and verified to measure the viscoelastic properties of polymers by nanoindentation tests. With the mechanical response of load–displacement curves at different loading rates, the parameters of creep compliance and relaxation modulus are calculated through the viscoelastic contact model. Dynamic thermomechanical analysis (DMA) tests are conducted to compare the results by the proposed technique. The results show that the correlation coefficients between DMA tests and the new method are above 0.9 in the entire range, which verified the feasibility of the method. The loading curves fitted by the model are identical to the experimental curves within the discrete points and so it shows that this technique is more suitable for general linear viscoelastic materials. Numerical creep tests are carried out to examine the effectiveness of the proposed method by input the Prony series calculated by the three-element Maxwell model and the viscoelastic contact model. The good agreement shows that the proposed technique can be applied in practice.     

Mechanical and structural properties of native and alkali-treated bacterial cellulose produced by Gluconacetobacter xylinus strain ATCC 53524

Mechanical properties of hydrated bacterial cellulose have been tested as a function of fermentation time and following the alkali treatment required for sterilisation prior to biomedical applications. Bacterial cellulose behaves as a viscoelastic material, with brittle failure reached at approximately 20% strain and 1.5 MPa stress under uniaxial tension. Treatment with 0.1 M NaOH resulted in minimal effects on the mechanical properties of bacterial cellulose. Fermentation time had a large effect on both bacterial numbers and cellulose yield but only minor effects on mechanical properties, showing that the fermentation system is a robust method for producing cellulose with predictable materials properties. The failure zone in uniaxial tension was shown to be associated with large-scale fibre alignment, consistent with this being the major determinant of mechanical properties. Under uniaxial tension, elastic moduli and failure stresses are an order of magnitude lower than those obtained under biaxial tension, consistent with the fibre alignment mechanism which is not available under biaxial tension.     

Electrical and mechanical behavior of filled elastomers. I. The effect of strain

Electrical and mechanical property tests have been used to examine the changes in the carbon black network structure that occur in a filled elastomer at large strains in tension and compression. These changes have been examined both in materials that have no previous loading history and in test pieces that have been subjected to a specific known prestrain. When a previously unstrained, filled elastomer specimen is stretched to moderate extensions, the electrical resistivity increases. This is ascribed to the breakdown of the carbon black network structure. At higher tensile extensions, the resistivity decreases. This reduction in the electrical resistivity is attributed to the alignment of the shaped carbon black aggregates under strain. During unloading, the resistivity behavior is different from that during loading, with the final unloaded electrical resistivity being significantly higher than that measured in the unstrained elastomer. This dramatic change in the electrical properties after unloading is in marked contrast to the relatively modest changes observed in the mechanical behavior. After the first cycle, the electrical behavior becomes much more reversible, and this indicates that the bulk of the damage experienced by the carbon black network is developed during the first cycle. After unloading from a large strain, the electrical anisotropy is small, whereas the mechanical anisotropy is more marked. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2079–2089, 2003     

Nonlinearity and slip behavior of n-hexadecane in large amplitude oscillatory shear flow via nonequilibrium molecular dynamic simulation

Molecular dynamic simulation is used to investigate the viscoelastic properties of n-hexadecane under oscillatory shear flow. Rheometric simulations of an ultra-thin molecular film are studied and compared with the results of a bulk simulation. Strain amplitude sweep tests at a fixed frequency show that strain thinning (the dynamic modulus monotonically decreases with increasing strain amplitude) exists at extreme strain for both bulk and thin film systems. Fourier analysis is performed to characterize the nonlinear behavior of the viscoelasticity. No even harmonic was found in our study even though wall slip occurs. Furthermore, we show that a Fourier series with odd harmonics can be used to perfectly describe the simulation results by plotting Lissajous loops. Shear wave propagation appears when the frequency is larger than a certain value. Moreover, the molecular orientation and molecular potential energies, including those for bonding potential, intra- and intermolecular van der Waals interactions are plotted against the strain amplitude to examine the changes in the microscopic structures with respect to the macroscopic thermodynamic states.     

Mechanical properties of fluorinated ethylene propylene (FEP) foils in use for neutrino detector project

The use of fluorinated ethylene propylene (FEP) foils as engineering materials for aerospace, solar thermal collector and neutrino detector applications has attracted considerable attention in recent decades. Mechanical properties are indispensable for analyzing corresponding structural behavior to meet the demands of safety and serviceability. In this paper, uniaxial tensile tests taking into account loading speeds, uniaxial tensile cyclic tests in terms of stress amplitude and loading cycles and creep tests considering loading stress and time were carried out to characterize mechanical properties. For uniaxial tensile properties, elastic modulus, yield stress, breaking strength and elongation were analyzed in detail. It is found that these mechanical properties except breaking elongation increased with loading speeds and that mechanical properties obtained in transverse direction were more sensitive than those obtained in machine direction. For cyclic properties, elastic modulus and ratcheting strain tended to be stable after certain cycles, demonstrating that cyclic elastic moduli were more suitable for analyzing structural behavior than those obtained in uniaxial tensile experiments. For creep properties, apparent strain at 6 MPa suggested that special attention was necessary for analyzing structural behavior if maximum stress was larger than 6 MPa. In general, this study could provide useful observations and values for understanding mechanical properties of FEP foils.     

Mechanical behavior of films of miscible polyamide 6/polyamide 6I‐6T blends

The deformation behavior of miscible PA6/aPA blends films under uniaxial and biaxial tensile drawing has been investigated in relation to blend composition. Whatever be the composition, the initial crystalline structure is ill‐ordered and no evidence of spherulitic morphology was shown. At temperatures beyond the activation of the viscoelastic α relaxation, a ductility improvement upon addition of aPA has been revealed in both uniaxial and biaxial stretching. The decrease in the yield stress with increasing aPA content mainly originates from the reduction in crystal fraction. Regarding the observed evolution in ultimate drawability and strain hardening upon addition of aPA, the latter component of the blend is considered to act as a diluent of the macromolecular network, and the experimental data are fairly well accounted for according to Graessley's theory. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1690–1701, 2006     

Influence of Liquid Isoprene Rubber on Strain Softening of Carbon Black Filled Isoprene Rubber Nanocomposites

The reinforcement of rubbers by nanoparticles is always accompanied with enhanced dissipation of mechanical energy upon large deformations. Methods for solving the contradiction between improving reinforcement and reducing energy dissipation for rubber nanocomposites have not been well developed. Herein carbon black(CB) filled isoprene rubber(IR)/liquid isoprene rubber(LR) blend nanocomposites with similar crosslink density(ν_e) are prepared and influence of LR on the strain softening behaviors including Payne effect under large amplitude shear deformation and Mullins effect under cyclic uniaxial deformation is investigated. The introduction of LR could improve the frequency sensitivity of loss modulus and reduce critical strain amplitude for Payne effect and loss modulus at the low amplitudes.Meanwhile, tuning ν_e and LR content allows reducing mechanical hysteresis in Mullins effect without significant impact on the mechanical performances. The investigation is illuminating for manufacturing nanocomposite vulcanizates with balanced mechanical hysteresis and reinforcement effect.     

PMVS/SiO2复合体系中粒子表面处理对动态粘弹特性的影响

粘弹性是高分子材料最本质的特征,其与高分子结构的关系一直是多组分高分子材料研究的热点。目前,对于填料增强聚硅氧烷体系的研究主要集中于填料在聚合物中的分散以及增强机理等方面,而有关不同填料表面特性体系的粘弹响应的研究报道尚不多见．在前文报道未经表面处理的超细SiO2填充聚甲基乙烯基硅氧烷(Polymethylvinylsiloxane,PMVS)的粘弹性研究的基础上,本文采用双(γ-三乙氧基硅基丙基)四硫化物IBis(3-triethoxysilyl)tetrasul{ane,TESPT]对SiO2进行表面处理,并采用溶液共混法制备样品,研究了经表面处理的SiO2填充PMVS体系的动态粘弹行为,并探讨了其结构变化与粘弹响应的关系。     

Viscoelastic properties of chitosan with different hydration degrees as studied by dynamic mechanical analysis

Dynamic mechanical analysis, DMA, is an adequate technique for characterizing the mechanical features of biomaterials, as one can use test conditions that can more closely simulate the physiological environments in which they are going to be applied. In this work it was possible to perform different tests on chitosan membranes using low/moderate hydration levels, as well in completely wet conditions. In the first case the data obtained at different relative humidity environments were rationalized under a time-humidity superposition principle, where a master curve for the storage modulus could be obtained along a wide range of frequencies. The temperature dependence of the shift factors exhibited a curvature opposite to that expected by the WLF equation, and is consistent with relaxation dynamics behavior below the glass transition. Temperature scans above room temperature in both dry and wet conditions did not reveal strong variations in the viscoelastic properties. It was possible to follow in real time the water uptake in an initially-dry membrane. During the initial strong and fast decrease of the storage modulus the loss factor exhibited a peak that should correspond to the occurrence of the glass transition resulting from the plasticization effect of water. Upon equilibration the loss factor reached similar values as for the dry material (tandelta approximately equal to 0.5). The viscoelastic characterization reported in this work for chitosan may be useful in the use of such material for a variety of biomedical applications.     

The evaluation and implementation of magnetic fields for large strain uniaxial and biaxial cyclic testing of Magnetorheological Elastomers

Magnetorheological Elastomers (MREs) are “smart” materials whose physical properties are altered by the application of magnetic fields. In previous studies the properties of MREs have been evaluated under a variety of conditions, however little attention has been paid to the recording and reporting of the magnetic fields used in these tests [1]. Currently there is no standard accepted method for specifying the magnetic field applied during MRE testing. This study presents a detailed map of a magnetic field applied during MRE tests as well as providing the first comparative results for uniaxial and biaxial testing under high strain fatigue test conditions. Both uniaxial tension tests and equi-biaxial bubble inflation tests were performed on isotropic natural rubber MREs using the same magnetic fields having magnetic flux densities up to 206 mT. The samples were cycled between pre-set strain limits. The magnetic field was switched on for a number of consecutive cycles and off for the same number of following cycles. The resultant change in stress due to the application and removal of the magnetic field was recorded and results are presented.