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Register a new userCross-linked polymers in strain: Structure and anisotropic stress
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Added by
Kartik Venkatraman Prof.
Publication date
2011
fields
Physics
and research's language is
English
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Molecular dynamic simulation enables one to correlate the evolution of the micro-structure with anisotropic stress when a material is subject to strain. The anisotropic stress due to a constant strain-rate load in a cross-linked polymer is primarily dependent on the mean-square bond length and mean-square bond angle. Excluded volume interactions due to chain stacking and spatial distribution also has a bearing on the stress response. The bond length distribution along the chain is not uniform. Rather, the bond lengths at the end of the chains are larger and uniformly decrease towards the middle of the chain from both ends. The effect is due to the presence of cross-linkers. As with linear polymers, at high density values, changes in mean-square bond length dominates over changes in radius of gyration and end-to-end length. That is, bond deformations dominate over changes in size and shape. A large change in the mean-square bond length reflects in a jump in the stress response. Short-chain polymers more or less behave like rigid molecules. Temperature has a peculiar effect on the response in the sense that even though bond lengths increase with temperature, stress response decreases with increasing temperature. This is due to the dominance of excluded volume effects which result in lower stresses at higher temperatures. At low strain rates, some relaxation in the bond stretch is observed from $epsilon=0.2$ to $epsilon=0.5$. At high strain rates, internal deformation of the chains dominate over their uncoiling leading to a rise in the stress levels.
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The structural properties of a linear polymer and its evolution in time have a strong bearing on its anisotropic stress response. The mean-square bond length and mean bond angle are the critical parameters that influence the time-varying stress developed in the polymer. The bond length distribution along the chain is uniform without any abrupt changes at the ends. Among the externally set parameters such as density, temperature, strain rate, and chain length, the density as well as the chain length of the polymer have a significant effect on the stress. At high density values, changes in mean-square bond length dominates over changes in radius of gyration and end-to-end length. In other words, bond deformations dominate as opposed to changes in size and shape. Also, there is a large change in the mean-square bond length that is reflected as a jump in the stress. Beyond a particular value of the chain length, $n = 50$, called the entanglement length, stress-response is found to have distinctly different behavior which we attribute to the entanglement effects. Short chain polymers more or less behave like rigid molecules. There is no significant change in their internal structure when loaded. Further, temperature and rate of loading have a very mild effect on the stress. Besides these new results, we can now explain well known polymeric mechanical behavior under dynamic loading from the point of view of the evolution of the molecular dynamics and the derived structural properties. This could possibly lead to polymer synthesis with desired mechanical behavior.
Numerous models have been developed in the literature to simulate the thermomechanical behavior of amorphous polymer at large strain. These models generally show a good agreement with experimental results when the material is submitted to uniaxial loadings (tension or compression) or in case of shear loadings. However, this agreement is highly degraded when they are used in the case of combined load cases. A generalization of these models to more complex loads is scarce. In particular, models that are identified in tension or compression often overestimate the response in shear. One difficulty lies in the fact that 3D models must aggregate different physical modeling, described with different kinematics. This requires the use of transport operators complex to manipulate. In this paper, we propose a mechanical model for large strains, generalized in 3D, and precisely introducing the adequate transport operators in order to obtain an exact kinematic. The stress strain duality is validated in the writing of the power of internal forces. This generalized model is applied in the case of a polycarbonate amorphous polymers. The simulation results in tension/compression and shear are compared with the classical modeling and experimental results from the literature. The results highly improve the numerical predictions of the mechanical response of amorphous polymers submitted to any load case.
We explore the effect of an attractive interaction between parallel-aligned polymers, which are perpendicularly grafted on a substrate. Such an attractive interaction could be due to, e.g., reversible cross-links. The competition between permanent grafting favoring a homogeneous state of the polymer brush and the attraction, which tends to induce in-plane collapse of the aligned polymers, gives rise to an instability of the homogeneous phase to a bundled state. In this latter state the in-plane translational symmetry is spontaneously broken and the density is modulated with a finite wavelength, which is set by the length scale of transverse fluctuations of the grafted polymers. We analyze the instability for two models of aligned polymers: directed polymers with a line tension and weakly bending chains with a bending stiffness.
We investigate by means of molecular dynamics simulation a coarse-grained polymer glass model focusing on (quasi-static and dynamical) shear-stress fluctuations as a function of temperature T and sampling time $Delta t$. The linear response is characterized using (ensemble-averaged) expectation values of the contributions (time-averaged for each shear plane) to the stress-fluctuation relation $mu_{sf}$ for the shear modulus and the shear-stress relaxation modulus $G(t)$. Using 100 independent configurations we pay attention to the respective standard deviations. While the ensemble-averaged modulus $mu_{sf}(T)$ decreases continuously with increasing T for all $Delta t$ sampled, its standard deviation $delta mu_{sf}(T)$ is non-monotonous with a striking peak at the glass transition. The question of whether the shear modulus is continuous or has a jump-singularity at the glass transition is thus ill-posed. Confirming the effective time-translational invariance of our systems, the $Delta t$-dependence of $mu_{sf}$ and related quantities can be understood using a weighted integral over $G(t)$. This implies that the shear viscosity $eta(T)$ may be readily obtained from the $1/Delta t$-decay of $mu_{sf}$ above the glass transition.
Extensive Monte Carlo results are presented for a lattice model of a bottle-brush polymer under good solvent or Theta solvent conditions. Varying the side chain length, backbone length, and the grafting density for a rigid straight backbone, both radial density profiles of monomers and side chain ends are obtained, as well as structure factors describing the scattering from a single side chain and from the total bottle-brush polymer. To describe the structure in the interior of a very long bottle-brush, a periodic boundary condition in the direction along the backbone is used, and to describe effects due to the finiteness of the backbone length, a second set of simulations with free ends of the backbone is performed. In the latter case, the inhomogeneity of the structure in the direction along the backbone is carefully investigated. We use these results to test various phenomenological models that have been proposed to interpret experimental scattering data for bottle-brush macromolecules. These models aim to extract information on the radial density profile of a bottle-brush from the total scattering via suitable convolution approximations. Possibilities to improve such models, guided by our simulation results, are discussed.
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