Stress–Strain Dependence of Segmented Polyurethanes and Polyurethane Ureas

The stress–strain dependences of segmented elastomers based on polyetherurethanes, polyesterurethane ureas, and polybutadieneurethane ureas were investigated. These dependences were adequately described using the generalized approach proposed earlier by the authors for amorphous elastomers. The experimental data obtained for four series of samples with chemical cross-linking confirmed an applicability of this approach for segmented elastomers. Unlike amorphous elastomers, the effective network density value was affected not only by the density of the chemical network, but the contribution of the network formed by the hard domains also needs be taken into account.     

Damping of Magnetorheological Elastomers

利用改装后的力磁耦合动态测试系统实验研究了磁流变弹性体在磁场下的阻尼性能. 实验得出了外加磁场的磁感应强度、基体的本征阻尼、铁粉含量、动态应变以及激励频率对磁流变弹性体阻尼的影响规律. 发现了磁流变弹性体的阻尼在很大程度上是由基体和颗粒之间的界面滑移所决定的. 而且该界面滑移不同于一般复合材料,它会受到外加磁场的影响..     

Isotropic-nematic transition in liquid-crystalline elastomers

In liquid-crystalline elastomers, the nematic order parameter and the induced strain vary smoothly across the isotropic-nematic transition, without the expected first-order discontinuity. To investigate this smooth variation, we measure the strain as a function of temperature over a range of applied stress, for elastomers cross-linked in the nematic and isotropic phases, and analyze the results using a variation on Landau theory. This analysis shows that the smooth variation arises from quenched disorder in the elastomer, combined with the effects of applied stress and internal stress.     

Stress–Strain Dependence of Cross-Linked Single-Phase Polyether Urethane

Stress–strain dependencies of cross-linked elastomers under stretching are considered. The capabilities to describe stress–strain plots of different types for elastomers, including curves with an inflection, by high-elasticity theories are examined. Limitations in the use of common high-elasticity models in the theoretical calculations of stress–strain plots are revealed. The analysis shows that the stress–strain plots with an inflection can be obtained with appropriate adjustment of the concept of finite chain extensibility. We propose a combined two-parameter model based on this concept and on the theory of high elasticity, taking into account the spatial constraints at the initial stage of stretching of the polymer network. Abilities of the new approach to describe the stress–strain dependencies in an adequate manner are demonstrated for five samples of cross-linked polyurethane over the entire range of strain under stretching.     

A Gaussian distribution model of anisotropic magnetorheological elastomers

A Gaussian distribution model was developed to examine the field-induced performance of anisotropic magnetorheological elastomers. The developed model was based on the assumption that the iron particles in magnetorheological elastomers aggregate into a large number of parallel body-centered tetragonal structure columns whose length obeys the Gaussian distribution. By using multi-pole approximation with local field effect and taking into account the nonlinearity and saturation of particle magnetization, the field-induced shear modulus was calculated as a function of distribution and dimension of the particle structures, the external magnetic field and the dynamic shear strain. Compared with other modes as well as the published experimental results, this model shows a remarkable improvement in accurately predicting the behavior of the magnetorheological elastomers.     

Elastic energies for nematic elastomers

We discuss several elastic energies for nematic elastomers and their small strain expansions both in the regime of large director rotations, and in the case that director changes are small. We propose two fully non-linear model anisotropic energies and compare the behavior they predict with the currently available experimental evidence.     

Nonlinear photoresponse of disordered elastomers

We model the polarization-dependent photocontractions of polydomain nematic elastomers. Contraction initially arises by light-induced director rotation. At higher light intensity, strain recovers because the local order parameter diminishes. Thus we predict photostrains to be nonmonotonic with light intensity and predict the induction of a negative global order parameter for the system of polydomains. Nonmonotonic strains would give curvature reversal in thick samples. Our model also predicts an elongational strain response to nonpolarized light.     

Deformation of cholesteric elastomers by uniaxial stress along the helix axis

The deformation of cholesteric elastomers by mechanical stress applied parallel to the helix axis is studied by calculation of the free-energy density. The Frank-elasticity contribution is taken into account. A chiral solvent, present at cross-linking time, is in general considered to be replaced after cross-linking by a solvent with different chirality. Two special cases considered are zero and unchanged solvent chirality, the first known as that of imprinted cholesteric elastomers, the latter equivalent to intrinsic cholesteric elastomers with chemically attached chiral groups. Depending on material parameters and imposed strain, the director can show a tilt towards the helix axis up to the maximum tilt, corresponding to a nematic state. In case of intrinsic elastomers with low conformation anisotropy, direct transitions from untilted to nematic states can be induced by straining. The helix structure of the director field is coarsened with an average wave number different to that of the information inscribed in the network at cross-linking time, if this lowers the average free-energy density. Switching between different states can be achieved with electric fields of reasonable values applied parallel to the helix axis. Spectra of the reflection of polarized light are calculated.     

Nonequilibrium tensile deformation of amorphous polymers in the rubbery state: Temperature,strain rate,and strain effects. I

We analyze nonequilibrium tensile deformational behavior of an amorphous uncrosslinked random copolymer of styrene and acrylonitrile stretched above its Tg at various temperatures and constant strain rates. The variable investigated is the force required to pull the specimen to a certain strain level. Our results suggest the deformational behavior in the rubbery state can be incorporated in a universal scheme where strain, strain rate, and temperature effects are all superposed, e.g., the effect of strain is identical to the effect of temperature and strain rate. This unexpected result is true within two contiguous but distinct regimes of strain, on both sides of ca. 40% strain, suggesting that non-equilibrium extension at constant pulling speed in the rubbery state occurs by at least two successive mechanisms. Our results also reveal that the physical parameter which should be used to achieve a true superposition of strain rate and temperature data is not as simple as has long been commonly proposed. For instance, we cannot use force alone nor the true stress, nor even the stress divided by strain. The best results are obtained when the function used is a complex function of force and strain. We introduce and explore in depth in this paper and future ones a new method to analyze the data. This method does not impose the choice of the functions which yield superposition and it provides an empirical mean for finding these functions. We have applied our method to other classical elastomers (PIB and SBR) stretched under similar conditions: we find the same conclusions, in particular the same small strain-middle strain transition separating two regimes of deformational behavior in the rubbery state.     

Segmental anisotropy in strained elastomers detected with a portable NMR scanner

Single-side NMR is particularly suitable for measurements of segmental anisotropy induced in elastomers by uniaxial forces or local strain. Proton transverse nuclear magnetic relaxation was investigated with the NMR-MOUSE by recording the Hahn-echo decay in cross-linked natural rubber bands. This provided information on the dependence of the Hahn-echo decay on the angle between the direction of the uniaxial stretching force and the axis Z defined direction perpendicular to the magnet pole faces of the NMR-scanner. The anisotropy effect on the Hahn-echo decay is correlated with the extension ratio, and it is more evident in the liquid-like regime of the decay. A weaker segmental anisotropy is detected by 1H solid- and Hahn-echo decays recorded by multi-pulse sequences. A qualitative understanding of the angular dependence is obtained by an analytical theory of the Hahn-echo decay adapted to the case of stretched elastomers and to strongly inhomogeneous magnetic fields. Using angular-dependent 1H residual second van Vleck moments and correlation times reported previously [P.T. Callaghan and E.T. Samulski, Macromolecules 30, 113 (1997)] from stretched natural rubber bands the segmental anisotropy measured in inhomogeneous magnetic fields by the Hahn-echo decay was numerically simulated. As an example of a macroscopic distribution of local segmental anisotropy, 1H Hahn-echo decays were measured by the NMR-MOUSE sensor in a stretched cross-linked natural rubber plate with a circular cut in the center.     

Calorimetric study of the Paranematic-to-Nematic transition of polydomain side-chain liquid-crystalline elastomers with different mesogen composition

The phase transition behaviour of various nematic side-chain liquid-crystalline elastomers with different mesogen composition has been explored by means of high-resolution ac calorimetry. Polydomain samples of the same crosslinking density and different type of mesogens have been investigated. The results show a strong dependence of the phase transition features upon the composition of the mesogen. The distance from the critical point, reflected in the sharpness of the heat capacity anomalies, increases when adding a shorter-length mesogen. The results provide new insight for the impact of mesogens on the thermodynamic behaviour and, thus, on the thermomechanical response of nematic liquid-crystalline elastomers.     

Surface energy as a barrier to creasing of elastomer films: an elastic analogy to classical nucleation

In a soft elastic film compressed on a stiff substrate, creases nucleate at preexisting defects and grow across the surface of the film like channels. Both nucleation and growth are resisted by the surface energy, which we demonstrate by studying creases for elastomers immersed in several environments-air, water, and an aqueous surfactant solution. Measurement of the position where crease channeling is arrested on a gradient thickness film provides a uniquely characterized strain that quantitatively reveals the influence of surface energy, unlike the strain for nucleation, which is highly variable due to the sensitivity to defects. We find that these experimental data agree well with the prediction of a scaling analysis.     

Thermal diffusion and bending kinetics in nematic elastomer cantilever

Vertically aligned monodomain nematic liquid-crystal elastomers contract when heated. If a temperature gradient is applied across the width of such a cantilever, inhomogeneous strain distribution leads to bending motion. We modelled the kinetics of thermally induced bending in the limit of a long thin strip and the predicted time variation of curvature agreed quantitatively with experimental data from samples with a range of critical indices and nematic-isotropic transition temperatures. We also deduced a value for the thermal diffusion coefficient of the elastomer.     

The role of Frank elasticity in cholesteric elastomers

The effect of Frank elasticity on deformations of cholesteric elastomers by mechanical stress applied perpendicular to the helix axis is studied by numerical minimization of the free energy. Above a critical strain, a solution with an only oscillating director is found to be stable in comparison to a distorted helix. At the critical strain, the contractions perpendicular to stress change discontinuously. The critical strain is found to increase with increasing Frank elasticity contribution to the free energy density, and to diverge when the conformation anisotropy of the polymer backbone vanishes. The results are compared with recent experiments which indicated that, in case of weak conformation anisotropies, the Frank elasticity contribution to the free energy cannot be neglected.     

Semisoft nematic elastomers and nematics in crossed electric and magnetic fields

Nematic elastomers with a locked-in anisotropy direction exhibit semisoft elastic response characterized by a plateau in the stress-strain curve in which stress does not change with strain. We calculate the global phase diagram for a minimal model, which is equivalent to one describing a nematic in crossed electric and magnetic fields, and show that semisoft behavior is associated with a broken symmetry biaxial phase and that it persists well into the supercritical regime. We also consider generalizations beyond the minimal model and find similar results.     

Phase transition in liquid crystal elastomers—A Monte Carlo study employing non-Boltzmann sampling

We investigate nematic-isotropic transition in liquid crystal elastomers employing a variant of Wang-Landau sampling. This technique facilitates calculation of the density of states from which other thermodynamic properties can be obtained. We consider a lattice model of a liquid crystal elastomer and a Hamiltonian which accounts for interactions among liquid crystalline units and interaction of local nematics with global strain. We investigate the effect of varying the strength of coupling between nematic and orientational degrees of freedom. When the local director is coupled strongly to the global strain, the transition is strongly first order. When the strength of the coupling decreases the transition becomes weakly first order. The transition temperature decreases when the coupling becomes weaker. We also report for the first time results on variation of free energy as a function of average energy at different temperatures and coupling constants.     

H NMR Imaging of Residual Dipolar Couplings in Cross-Linked Elastomers: Dipolar-Encoded Longitudinal Magnetization, Double-Quantum, and Triple-Quantum Filters

Contrastfilters for NMR imaging of residual ¹H dipolar couplings of elastomers are introduced based on dipolar-encoded longitudinal magnetization, as well as double- and triple-quantum coherences. The spin response is discussed in the initial excitation time regime for methylene, methyl, and methine protons applicable to poly(isoprene) and other elastomers, taking into account the hierarchy of dipolar couplings and the associated editing features of multiple-quantum experiments. The efficiency of these filters is investigated for a series of cross-linked poly(isoprene) samples. Spatially resolved dipolar-encoded longitudinal magnetization decays and double-quantum and triple-quantum buildup curves are presented for a phantom made of poly(isoprene) with different cross-link densities. Two-dimensional images representing residual dipolar couplings are presented using dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum contrast filters. Images from dipolar-encoded longitudinal magnetization and triple-quantum coherences show the highest resolution and contrast, respectively.     

1H NMR imaging of residual dipolar couplings in cross-linked elastomers: dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum filters.

Contrastfilters for NMR imaging of residual 1H dipolar couplings of elastomers are introduced based on dipolar-encoded longitudinal magnetization, as well as double- and triple-quantum coherences. The spin response is discussed in the initial excitation time regime for methylene, methyl, and methine protons applicable to poly(isoprene) and other elastomers, taking into account the hierarchy of dipolar couplings and the associated editing features of multiple-quantum experiments. The efficiency of these filters is investigated for a series of cross-linked poly(isoprene) samples. Spatially resolved dipolar-encoded longitudinal magnetization decays and double-quantum and triple-quantum buildup curves are presented for a phantom made of poly(isoprene) with different cross-link densities. Two-dimensional images representing residual dipolar couplings are presented using dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum contrast filters. Images from dipolar-encoded longitudinal magnetization and triple-quantum coherences show the highest resolution and contrast, respectively.