Free-energy density functions for nematic elastomers

The recently proposed neo-classical theory for nematic elastomers generalizes standard molecular-statistical Gaussian network theory to allow for anisotropic distributions of polymer chains. The resulting free-energy density models several of the novel properties of nematic elastomers. In particular, it predicts the ability of nematic elastomers to undergo large deformations with exactly zero force and energy cost—so called soft elasticity. Although some nematic elastomers have been shown to undergo deformations with unusually small applied forces, not all do so, and none deform with zero force. Further, as a zero force corresponds to infinitely many possible deformations in the neo-classical theory, this non-uniqueness leads to serious indeterminacies in numerical schemes. Here we suggest that the neo-classical free-energy density is incomplete and propose an alternative derivation that resolves these difficulties. In our approach, we use the molecular-statistical theory to identify appropriate variables. This yields the choice for the microstructural degrees of freedom as well as two independent strain tensors (the overall macroscopic strain plus a relative strain that indicates how the deformation of the elastomeric microstructure deviates from the macroscopic deformation). We then propose expressions for the free-energy density as a function of the three quantities and show how the material parameters can be measured by two simple tests. The neo-classical free-energy density can be viewed as a special case of our expressions in which the free-energy density is independent of the overall macroscopic strain, thus supporting our view that the neo-classical theory is incomplete.     

Energy analysis and improved regularity estimates for multiscale deconvolution models of incompressible flows

This paper presents new analytical results and the first numerical results for a recently proposed multiscale deconvolution model (MDM) recently proposed. The model involves a large‐eddy simulation closure that uses a novel deconvolution approach based on the introduction of two distinct filtering length scales. We establish connections between the MDM and two other models, and, on the basis of one of these connections, we establish an improved regularity estimate for MDM solutions. We also prove that the MDM preserves Taylor‐eddy solutions of the Navier–Stokes equations and therefore does not distort this particular vortex structure. Simulations of the MDM are performed to examine the accuracy of the MDM and the effect of the filtering length scales on energy spectra for three‐dimensional homogeneous and isotropic flows. Numerical evidence for all tests clearly indicates that the MDM gives very accurate coarse‐mesh solutions and that this multiscale approach to deconvolution is effective. Copyright © 2015 John Wiley & Sons, Ltd.     

First principles simulation of a superionic phase of hydrogen fluoride (HF) at high pressures and temperatures

We have conducted ab initio molecular dynamics simulations of hydrogen fluoride (HF) at pressures of 5-66 GPa along the 900 K isotherm. We predict a superionic phase at 33 GPa, where the fluorine atoms are fixed in a bcc lattice while the hydrogen atoms diffuse rapidly with a diffusion constant between 2 x 10(-5) and 5 x 10(-5)cm(2)s. We find that a transformation from asymmetric to symmetric hydrogen bonding occurs in HF at 66 GPa and 900 K. With superionic HF we have discovered a model system where symmetric hydrogen bonding occurs at experimentally achievable conditions. Given previous results on superionic H(2)O [Goldman et al., Phys. Rev. Lett. 94, 217801 (2005)] and NH(3) [Cavazzoni et al., Science 283, 44 (1999)], we conclude that high P, T superionic phases of electronegative element hydrides could be common.     

Incompatible strains associated with defects in nematic elastomers

In a nematic elastomer the deformation of the polymer network chains is coupled to the orientational order of the mesogenic groups. Statistical arguments have derived the so-called neoclassical free energy that models this coupling. Here we show that the neoclassical model supplemented by the usual Frank energy predicts incompatible network strains associated with the formation of standard nematic textures. The incompatibility is measured by the Riemann curvature tensor, which we find to be nonzero for both radial hedgehog defects and escaped disclinations of strength +1 in circular cylinders. Analogous problems for conventional nonlinearly elastic solids do not possess solutions with such incompatibilities. Compatibility in nematic elastomers would require either more complicated nematic textures in elastomers than in conventional (polymeric and low molecular weight) liquid crystals or a free-energy density more complicated than the neoclassical expression.     

Lyotropic mesophases of hydroxypropylcellulose in pure acetic acid,in water,and in mixed solvents

Photomicrographys of concentrated lyotropic hydroxypropylcellulose solutions confirm the cholesteric nature of the anisotropic phases in acetic acid and water. They reveal the existence of biphasic separation. Typical liquid-crystal solvent-dependent textures are observed. The behavior of liquid-crystalline phases in mixed solvents is also studied, and the cholesteric pitch of the twist structure is measured for various relative concentrations of solvents. Spherical droplets, or “spherulites,” in well-defined relative concentrations of solvents have been observed.     

Quantitative molecular thermochemistry based on path integrals

The calculation of thermochemical data requires accurate molecular energies and heat capacities. Traditional methods rely upon the standard harmonic normal-mode analysis to calculate the vibrational and rotational contributions. We utilize path-integral Monte Carlo for going beyond the harmonic analysis and to calculate the vibrational and rotational contributions to ab initio energies. This is an application and an extension of a method previously developed in our group [J. Chem. Phys. 118, 1596 (2003)].     

Generalized Swift–Hohenberg and phase-field-crystal equations based on a second-gradient phase-field theory

Meccanica - The principle of virtual power is used derive a microforce balance for a second-gradient phase-field theory. In conjunction with constitutive relations consistent with a free-energy...     

Continua described by a microstructural field

Using a balance law for microforces and an appropriate statement of the second law of thermodynamics, a framework is provided for continuum theories that involve a microstructural variable. Examples of specific physical theories that fall within that framework—spanning internal state-variable theories for plasticity and polymeric solutions, order-parameter based theories for phase transitions, and various theories for liquid crystals-are given.