Transient effects in dynamic modulus measurement of silicone rubber,part 2: Effect of mean strains and strain history

The strain‐dependent dynamic storage modulus of a poly(dimethyl‐siloxane‐co‐methylvinyl‐siloxane‐co‐methylphenyl‐siloxane)‐based silicone elastomer (PVMQ), which is reinforced with fumed silica and crosslinked with peroxide, is investigated. The time dependence of the dynamic storage modulus on the magnitude of the mean strain at a particular test condition is investigated. The dynamic modulus results are shown to depend on the time of cycling as well as the relative magnitudes of the dynamic and mean strains. The relaxation of the force required to maintain the mean strain is observed to depend on the magnitude of the dynamic strains and the data are shown to be consistent with static stress relaxation experiments in the limit of zero dynamic strain. Recovery of the dynamic modulus from the exposure to higher strain cycling is seen to be facilitated by dynamic cycling with higher cycling strains yielding faster recovery rates. The observed phenomena are interpreted in terms of the role of entanglements in the polymer phase on the dynamic behavior of the elastomer material. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2197–2204, 2007     

Dynamic properties of crosslinked epoxy resin at large cyclic and static deformation

Measurement of dynamic properties of crosslinked epoxy resin have been performed under torsional cyclic deformation with different amplitudes and frequencies and with extensional creep under different loads. It is found in both cases that the dynamic modulus decreases above a certain critical value of deformation. Truncation of the glassy state region and shifting of the transition zone to lower temperatures and higher frequencies have been observed as effects of large amplitude deformation. The maximum reduction in the modulus value and the minimum in the critical amplitude both occur in the region of T_g Shear fatigue of the material has been observed in the glassy state with a frequency- and temperature-dependent fatigue life. It is found that the loss modulus under extensional creep depends upon the values of the deformation and stress whereas the storage modulus depends solely upon the deformation. The ratio of energy expended during static and cyclic deformations is shown to depend only upon the extensional deformation.     

Transient effects in dynamic modulus measurement of silicone elastomers 1. Zero mean strain measurements

The strain‐dependent dynamic storage modulus of a poly(dimethyl‐siloxane‐co‐methylvinyl‐siloxane‐co‐methylphenyl‐siloxane) based silicone elastomer, which is reinforced with fumed silica and crosslinked with peroxide, is investigated. The dependence of the resulting dynamic storage modulus on the duration of cycling at a particular test condition is investigated and compared to static stress relaxation measurements in the same strain range. The dynamic modulus results are shown to depend on the time of cycling at the current test conditions as well as the time of cycling at prior conditions of lower strains. The relaxation is shown to be related to the time of cycling rather than the number of cycles performed. The pattern of behavior of the relaxation of the dynamic modulus with respect to peak strain amplitude is different than that observed in a static stress relaxation test, both of which show significant nonlinear effects in strain. The observed phenomena are interpreted in terms of the role of the polymer phase on the dynamic behavior of the elastomer material. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1001–1009, 2005     

Silks cope with stress by tuning their mechanical properties under load

We compare the nonlinear mechanical properties of silks under load with the quasi-static and isothermal dynamic mechanical properties of nylon as well as human hair. For silk and nylon, the dynamic storage modulus increases with increasing static load, while the quasi-static modulus decreases considerably through yield. However, the modulus of hair decreases irreversibly for both loading conditions. For silk, the increase in storage modulus is only partially reversible after high-loading and is accompanied by a non-recoverable strain. For nylon, the dynamic modulus increase is largely reversible after increased static loading up to a second high stress yield point, where modulus then decreases. Taken together, our data suggest that the dynamic modulus increases with increasing order in the silk and nylon structures under static load, whereas the morphology of hair is gradually degraded under load.     

Viscoelastic properties of a gum vulcanizate at large static deformations

The loss tangent corresponding to small sinusoidal oscillations superposed on a large static deformation is found to decrease with increasing static deformation ratio for a natural rubber gum vulcanizate. Further, the response functions of the stress–relaxation and the incremental stress–relaxation vs. time and the storage modulus vs. frequency are found not to be separable functions of time and strain effects. These findings are shown to indicate that the elastic contribution to the viscoelastic response of this elastomer increases more rapidly with the static deformation than does the relaxation contribution. The loss modulus, however, is found to be a separable function of time and strain effects. Hence, only one relaxation function is needed in the viscoelastic constitutive theory applied to this elastomer. The finite linear viscoelasticity theory as modified by Morman has a form which can account for these results. Predictions of the incremental stress–relaxation function from dynamic data are within 1% of experimental values.     

PEG／N100／NG弹性体胶片交联结构及其低温力学性能研究

通过DSC（差示扫描量热法）对PEG／N100／NG弹性体胶片的结构进行了研究,并分析了其静态和动态力学性能。研究表明,结晶的聚乙二醇（PEG）微粒在弹性体中作为应力集中物吸收了大量的拉伸能量,从而大大提高了PEG／N100／NG弹性体胶片的韧性,且PEG相对分子质量越大,PEG／N100／NG的交联结构越稳定,从而弹性体胶片的静态力学性能越好;随着PEG相对分子质量增大,动态模量曲线都发生了很大变化,储能模量E下降,力学损耗已。和tanα的β松弛峰温下降,相对强度先大幅提高,后略有下降;随着N100含量增加即R值增大,β松弛峰温即玻璃化转变温度Tg逐步下降,峰强度也随之下降。     

Mechanical and dismantlement adhesion properties of grafted EPDM-silica hybrid

This study was carried out to confirm the effects of functional groups that could derive secondary bonding and silica contents on mechanical properties and thermo-reversible characteristics of grafted EPDM-silica composites, which was produced by blending silica or introducing silica hybrid through ionic bonding after grafting methacrylic acid onto EPDM. The storage modulus of graft copolymer had appeared to be higher than cross-linked EPDM vulcanizate at room temperature, and decreased by a gentle slope as temperature increased, and then began to decrease more sharply as secondary bonding force became weaker at higher temperature. When silica hybrid was introduced through ionic interaction, storage modulus and mechanical properties were found to be higher due to not only hydrogen and ionic bonding, but also nanosized silica particles, which were bonded to the elastomer structure in uniformed distribution. When the graft copolymer had only hydrogen bonding, recycling of the elastomer caused mechanical properties to be reduced by 20–30%. However, the recycling characteristics of elastomers having both hydrogen and ionic bonding were excellent as more than 90% of their initial mechanical properties were maintained even after five times of reprocessing. Graft copolymer composite had better adhesion strength with other rubber due to increased polarity than EPDM, and dismantlement of bonded adherends was possible by applying heat treatment of microwave.     

促进剂种类对NR硫化胶动态性能的影响

探讨促进剂NS、CZ、DZ对天然橡胶(NR)硫化胶动态性能的影响。结果表明,由不同的促进剂得到的硫化胶的交联密度不同,硫化胶的动态性能对频率、温度和应变的依赖性也不完全相同。由NS和CZ得到的硫化胶的交联密度较高且相近,其储能模量(G′)随频率和温度的升高而增加的变化趋势几乎重合,但在较低的应变下硫化胶的G′随应变振幅的提高而降低;而由促进剂DZ得到的硫化胶,由于交联密度较低,其G′随温度的升高而略有增加。     

Mechanical properties of polymer‐ceramic nanocomposite coatings by depth‐sensing indentation

The mechanical properties of antimony‐doped tin oxide (ATO) nanoparticle/poly (vinyl acetate‐co‐acrylic) (PVAc‐co‐acrylic) coatings with various ATO contents were investigated using depth‐sensing indentation. These coatings were prepared from aqueous dispersions of ATO and PVAc‐co‐acrylic latex. Three types of methods, including a prolonged load holding time, analysis of the pull‐off portion of the unloading curve, and dynamic indentation, were used to characterize the mechanical properties of these composite coatings. As compared to dynamic indentation, quasistatic conventional indentation even with a prolonged load holding time and analysis of the pull‐off portion of unloading curves generate more scattered coating modulus data. This is due to the effect of creep deformation and inconsistency of the pull‐off portion dimension, respectively. The results obtained using dynamic indentation are more reliable because the technique minimizes the effect of creep deformation using a combination load including static and dynamic components. The dynamic indentation results indicate that the addition of the ATO nanoparticles made the composite coatings stiffer and more elastic solid–like. For example, the storage indentation modulus of the PVAc‐co‐acrylic coating is ～1 GPa and tan δ is ～1.6; the addition of 0.50 volume fraction of ATO increased the modulus to ～5 GPa and reduced the tan δ to ～0.01. POLYM. ENG. Sci. 45:207–216, 2005. © 2005 Society of Plastics Engineers.     

Lead magnesium niobate-filled silicone dielectric elastomer with large actuated strain

A silicone dielectric elastomer filled with lead magnesium niobate with a maximum actuated strain of 7.4% at 45 kV/mm was fabricated by optimizing the amount of dielectric filler, amount of plasticizing agent, and crosslink density of the elastomer. The actuated strain of dielectric elastomers (DEs) is determined by both the dielectric constant and the elastic modulus. Although the dielectric constant of the silicone elastomer increased with increasing loading amount of lead magnesium niobate, actuated strain did not increase as expected because the elastic modulus increased at the same time. The elastic modulus of silicone dielectric elastomer was decreased by reducing the crosslink density or adding plasticizing agent, leading to a visible increase in actuated strain. It was also revealed that actuated strain of silicone dielectric elastomer always goes up with increasing ratio of dielectric constant to elastic modulus. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Viscoelastic properties and heat generation in urethane elastomers

Static and dynamic properties were studied in a series of polyurethane elastomers as a function of selected compositional variables such as curative system, curative level, catalyst level, and curing temperature. A number of physical properties including swelling ratio, density, glass transition temperature, stress–strain behavior, and thermal conductivity were also measured on these elastomers. The selected variables affect dynamic mechanical properties as well as heat buildup. A good correlation was noted between the loss modulus and the heat generation. The loss modulus and the heat generation decrease with decreasing curative level. The elastomers cured with a mixture of triol and diamine give lower loss modulus and heat buildup than those cured with diamine alone. These responses are believed due to the increase in covalent crosslinks. The observed low heat generation of the elastomer cured with 0.2 phr azelaic acid as a catalyst level was also attributed to the high crosslink density. The curing temperature, in the range investigated, appears to have very little effect on the properties. Thus, the choice of formulation variables, especially the use of diamine–triol blends, provides an effective means of minimizing heat generation in dynamic applications of polyurethane elastomers.     

Fatigue behaviour of multiblock thermoplastic elastomers. 1. Stepwise increasing load testing of poly(aliphatic/aromatic-ester) copolymers

Fatigue properties of poly(aliphatic/aromatic-ester) (PED) multiblock copolymers were evaluated based on the hysteresis measurement method. This method allows the digitalization of the hysteresis loop and beside the determination of stress and strain-related parameters, stored energy, lost energy, damping and dynamic creep behaviour can be determined. The correlation between hard/soft segment concentration of PED copolymers, and fundamental parameters, which derived during the cyclic loading (using stepwise increasing load testing, SILT), has indicated a good load-carrying performance of polymers containing a high amount of the hard phase. PED copolymers compare very well with commercially available poly(ester-ethers) and show a much better performance than poly(ester-urethanes) when samples are loaded at the same fatigue stress level relative to their ultimate tensile strength. Softer PEDs and poly(ether-urethane) copolymer show much higher values of dynamic modulus than chemically cross-linked silicone elastomer. Therefore, these multiblock copolymers can be considered as good candidates for applications where materials are subjected to oscillatory deformations (for example passive flexor tendon reconstruction).     

Dynamic compressive creep behaviour of structural silicone-to-aluminum and silicone-based sealant-to-aluminum joints

This paper outlines an experimental study on the static and dynamic compressive creep behaviour of structural silicone adhesively bonded joints. The silicone adhesives are subjected to dynamic compressive loading, which is a common case for structural façade and hybrid glazing system. Typical crack propagation of adhesives, relations between compressive load (stress) and displacement (creep strain) are examined experimentally. It is shown that the test specimen with adhesives featured by lower hardness and higher elongation at break exhibit notable crack distribution concentrated in the middle of the crack surface. The compressive behaviour consists of three regions as initial elastic, nonlinear transition and post linear, in which the latter has notable strength increase with the increase of compressive deformation. The secant compressive modulus are measured based on compressive stress and creep strain relations. It is demonstrated that the joint has higher secant compressive modulus due to less crack propagation. All test joints exhibit significant degradation of strength and energy absorption, which can be well fitted in similar exponential forms with normalized cycle numbers for test joints with different adhesives.     

RPA分析硫黄用量对天然橡胶动态性能的影响

用橡胶加工分析仪(RPA)分析硫黄用量对NR动态性能的影响。结果表明:不同硫黄用量的混炼胶的动态模量随频率的升高和温度的降低而增加,损耗因子降低;应变超过28%,混炼胶的储能模量下降。不同硫黄用量的硫化胶随交联密度的提高,动态性能对频率的依赖性变小,对应变的依赖性变强;而温度越高,硫化胶的"橡胶弹性"越明显。     

Effects of prior aging at 288°C in air and in argon environments on creep response of PMR‐15 neat resin

The creep behavior of PMR‐15 neat resin, a polyimide thermoset polymer, aged in air and in argon environments at 288°C for up to 1000 h was evaluated. Creep tests were performed at 288°C at creep stress levels of 10 and 20 MPa. Creep periods of at least 25‐h in duration were followed by 50‐h periods of recovery at zero stress. Prior isothermal aging increased the elastic modulus and significantly decreased the polymer's capacity to accumulate creep strain. The aging environment had little influence on creep and recovery behaviors. However, aging in air dramatically degraded the tensile strength of the material. Dynamic mechanical analysis revealed an increase in the glass transition temperature from ∼330°C to ∼336°C after 1000 h in argon or in air at 288°C. The rise in the glass transition temperature with aging time is attributed to an increase in the crosslink density of the PMR‐15 polyimide. Increase in the crosslink density due to aging in both air and argon environments is likely behind the changes in the elastic modulus and the decreased capacity for inelastic straining. A visibly damaged surface layer of ∼0.16 mm thickness was observed in specimens aged in air for 1000 h. Results indicate that the unoxidized core material governs the overall mechanical response, whereas the oxidized surface layer causes a decrease in tensile strength by acting as a crack initiation site and promoting early failures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical properties of cerium oxide-modified vulcanised natural rubber at elevated temperature

Cerium oxide (CeO₂) was used as the reinforcement filler to improve the mechanical properties of rubbers. Rubber components are often used at high temperature, so the mechanical properties of CeO₂-modified vulcanised natural rubbers (NR/CeO₂) were investigated at elevated temperatures. The tensile properties, stress relaxation and creep recovery response were studied from 30°C to 150°C. NR/CeO₂ demonstrated higher crosslink density and elastic modulus. The degradation of elastic modulus could be alleviated in the NR/CeO₂ at elevated temperatures. Moreover, a remarkable enhancement in stress relaxation resistance and creep resistance was achieved in the NR/CeO₂ at elevated temperatures. The improved stress relaxation resistance and creep resistance were attributed to the enhanced interaction and bonding force of rubber chains caused by CeO₂ filler. CeO₂ was an effective reinforcement filler to improve the mechanical properties of NR at elevated temperatures.     

Molecular mechanisms involved in creep phenomena of paper

The phenomenon of mechanosorptive creep (i.e., the increasing creep occurring in some hygroscopic materials subjected to moisture cycling) was studied for paper from a molecular point of view. Paper was tested in creep at different loading levels in a constant high humidity of 90% relative humidity (RH) and in a cyclic climate between 30 and 90% RH. Throughout the creep tests, spectra from the mid‐ and near‐IR, as well as dynamic mechanical data, were recorded to determine molecular changes occurring with time. In tensile stress scans the instantaneous, dynamic elastic modulus was found to increase. It is suggested that this increase was due to orientation of the cellulose molecules, which was detected as changes in the mid‐IR spectra at 1160 cm⁻¹ assigned to the C₁ O C₄ stretching. During creep in constant and cyclic humidity, the modulus was found to increase with time, more so for the cyclic humidity. Changes in the mid‐IR spectra at 1184 and 1030 cm⁻¹, which is assigned to CH₂, CH, and C O, may indicate sliding between the cellulose chains. The near‐IR measurements mainly showed differences in the moisture content. In stress scans the moisture content increased with increasing tensile load. In creep at constant 90% RH, the moisture content was also found to increase in a manner similar to the stress scan. In the cyclic humidity with a conditioning time of 70 min at 90% RH the moisture content decreased successively with increasing numbers of cycles. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1590–1595, 2001     

Shear creep behaviour of elastomeric adhesives

The shear creep behaviour of elastomeric adhesives has been investigated at various temperatures, loading stresses and adhesive thicknesses. Three adhesive types were included in the study: two polysulphides, one silicone and one polyurethane elastomer. The creep compliance of the two polysulphide adhesives could be described by an Arrhenius-type relationship incorporating time, temperature and stress. The silicone and polyurethane adhesives, on the other hand, showed an initial creep response followed by a long period of zero creep over the ranges of temperature and load studied.     

Apparent Enhanced Fatigue Resistance under Cyclic Tensile Loading for a HIPed Silicon Nitride

Cyclic tensile loading tests of a commercial HIPed silicon nitride at elevated temperatures have indicated apparent "enhanced" fatigue resistance compared to static tensile loading tests under similar test conditions. At 1150°C, stress rupture results plotted as maximum stress versus time to failure did not show significant differences in failure behavior between static, dynamic, or cyclic loading conditions, with all failures originating from preexisting defects (slow crack growth failures). At 1260°C, the stress rupture results showed pronounced differences between static, dynamic, and cyclic loading conditions. Failures at low static stresses (<175 MPa) originated from environmentally assisted (oxidation) and generalized creep damage, while failures at similar times but much greater (up to 2 x) cyclic stresses originated from preexisting defects (slow crack growth failures). At 1370°C, stress rupture results did not show as pronounced differences between static, dynamic, and cyclic loading conditions, with most failures originating from environmentally assisted (oxidation) and generalized creep damage.     

Tensile Creep Behavior of a Vitreous-Bonded Aluminum Oxide under Static and Cyclic Loading

Creep deformation and rupture behavior of a vitreousbonded aluminum oxide was investigated under uniaxial static and cyclic tensile loadings at 1000°, 1100°, and 1175°C. The material was more creep resistant, i.e., having lower creep strain rates, under cyclic loading compared to that under static loading. For the same maximum applied stress, the ratio of steady-state creep rate under static loading to that under cyclic loading at 1100°C was approximately 100. However, the value of this ratio decreased to about 10 when the testing temperature was raised to 1175°C or lowered to 1000°C. Under static loading the material had more propensity to develop creep damage in the form of micro- and macrocracks, leading to early failure, whereas under cyclic loading the creep damage was more uniformly distributed in the form of cavities confined to the multigrain junctions. Viscous bridging by the grain boundary second phase may be the primary contributor to the lower creep deformation rate and improved lifetime under cyclic loading.