Alain Dequidt

Mechanical properties of thin confined polymer films close to the glass transition in the linear regime of deformation: theory and simulations.

Over the past twenty years experiments performed on thin polymer films deposited on substrates have shown that the glass transition temperature Tg can either decrease or increase depending on the strength of the interactions. Over the same period, experiments have also demonstrated that the dynamics in liquids close to the glass transition temperature is strongly heterogeneous, on the scale of a few nanometers. A model for the dynamics of non-polar polymers, based on percolation of slow subunits, has been proposed and developed over the past ten years. It proposes a unified mechanism regarding these two features. By extending this model, we have developed a 3D model, solved by numerical simulations, in order to describe and calculate the mechanical properties of polymers close to the glass transition in the linear regime of deformation, with a spatial resolution corresponding to the subunit size. We focus on the case of polymers confined between two substrates with non-negligible interactions between the polymer and the substrates, a situation which may be compared to filled elastomers. We calculate the evolution of the elastic modulus as a function of temperature, for different film thicknesses and polymer-substrate interactions. In particular, this allows to calculate the corresponding increase of glass transition temperature, up to 20 K in the considered situations. Moreover, between the bulk Tg and Tg + 50 K the modulus of the confined layers is found to decrease very slowly in some cases, with moduli more than ten times larger than that of the pure matrix at temperatures up to Tg + 50 K. This is consistent with what is observed in reinforced elastomers. This slow decrease of the modulus is accompanied by huge fluctuations of the stress at the scale of a few tens of nanometers that may even be negative as compared to the solicitation, in a way that may be analogous to mechanical heterogeneities observed recently in molecular dynamics simulations. As a consequence, confinement may result not only in an increase of the glass transition temperature, but in a huge broadening of the glass transition.

Direct measurement of the thermomechanical Lehmann coefficient in a compensated cholesteric liquid crystal

The thermomechanical Lehmann coefficient ν is directly measured as a function of temperature in a compensated cholesteric liquid crystal. The method consists of observing the continuous rotation of the director in samples treated for planar sliding anchoring when a temperature gradient is applied perpendicularly to the director. The main result is that there is no relationship between the Lehmann coefficient and the equilibrium twist q. In particular, we confirm that ν does not vanish at the compensation temperature at which q=0, in agreement with previous static measurements of Eber and Janossy (Mol. Cryst. Liq. Cryst., 72 (1982) 233) and of ourselves (Europhys. Lett., 80 (2007) 26001). In addition, the sign of the Lehmann coefficient is determined by observing between crossed polarizers the sense of rotation of the extinction branches of the disclination lines.

Lehmann effect in compensated cholesteric liquid crystals

In 1900, Otto Lehmann observed that the texture of a cholesteric droplet heated from below can rotate continuously (Ann. Phys. (Leipzig), 2 (1900) 649). This observation (which has never been reproduced, to our knowledge) was explained in 1968 by Leslie (Proc. R. Soc. London, Ser. A, 307 (1968) 359) from symmetry arguments accounting for the chirality of the material. In 1982, Eber and Janossy showed experimentally that a similar thermomechanical effect also exists in a compensated cholesteric (in which the helix is completely unwound). This result was immediately questioned by Pleiner and Brand who claimed that only the symmetry of the phase (and not that of the molecule) determines the structure of the macroscopic constitutive equations (Mol. Cryst. Liq. Cryst. Lett., 5 (1987) 61). According to them, the Lehmann effect should necessarily vanish at the compensation temperature. In order to understand the correct interpretation, we conducted very carefully the experiment in two complementary geometries. Our results agree with those of Eber and Janossy, confirming the predominance of microscopic symmetries over macroscopic ones.

Thermalized Drude Oscillators with the LAMMPS Molecular Dynamics Simulator

LAMMPS is a very customizable molecular dynamics simulation software, which can be used to simulate a large diversity of systems. We introduce a new package for simulation of polarizable systems with LAMMPS using thermalized Drude oscillators. The implemented functionalities are described and are illustrated by examples. The implementation was validated by comparing simulation results with published data and using a reference software. Computational performance is also analyzed.

Lehmann effect in a compensated cholesteric liquid crystal: Experimental evidence with fixed and gliding boundary conditions

Abstract.In a recent letter (Europhys. Lett. 80, 26001 (2007)), we have shown that a compensated cholesteric liquid crystal (in which the macroscopic helix completely unwinds) may be subjected to a thermomechanical torque (the so-called Lehmann effect), in agreement with previous findings of Éber and Jánossy (Mol. Cryst. Liq. Cryst. Lett. 72, 233 (1982)). These results prove that one must take into account the chirality of the molecules and the absence of inversion symmetry at the macroscopic scale when deriving the constitutive equations of the phase at the compensation temperature. In this paper, we present the details of our experimental work and a new experiment performed in a sample treated for planar gliding anchoring. The latter experiment, coupled with a numerical simulation, supports the existence of a thermomechanical coupling in a compensated cholesteric.

Alloy hardening of a smectic A liquid crystal doped with gold nanoparticles

We measure the mobility of edge dislocations in a smectic A liquid crystal doped with gold nanoparticles. The mobility is found to decrease when the concentration of nanoparticles increases, which leads to a hardening of the smectic phase. It is found that the closer the temperature to the nematic phase, the weaker the hardening. The critical behavior of the mobility near the smectic A-to-nematic transition temperature is also investigated and compared to theoretical predictions.

Bayesian parametrization of coarse-grain dissipative dynamics models.

We introduce a new bottom-up method for the optimization of dissipative coarse-grain models. The method is based on Bayesian optimization of the likelihood to reproduce a coarse-grained reference trajectory obtained from analysis of a higher resolution molecular dynamics trajectory. This new method is related to force matching techniques, but using the total force on each grain averaged on a coarse time step instead of instantaneous forces. It has the advantage of not being limited to pairwise short-range interactions in the coarse-grain model and also yields an estimation of the friction parameter controlling the dynamics. The theory supporting the method is exposed in a practical perspective, with an analytical solution for the optimal set of parameters. The method was first validated by using it on a system with a known optimum. The new method was then tested on a simple system: n-pentane. The local molecular structure of the optimized model is in excellent agreement with the reference system. An extension of the method allows to get also an excellent agreement for the equilibrium density. As for the dynamic properties, they are also very satisfactory, but more sensitive to the choice of the coarse-grain representation. The quality of the final force field depends on the definition of the coarse grain degrees of freedom and interactions. We consider this method as a serious alternative to other methods like iterative Boltzmann inversion, force matching, and Green-Kubo formulae.

Lehmann effect in chiral liquid crystals and Langmuir monolayers: an experimental survey

In 1900 Otto Lehmann observed that the internal texture of cholesteric droplets, when submitted to a thermal gradient, was constantly rotating. This phenomenon was explained phenomenologically in 1968 from symmetry arguments by F.M. Leslie in the framework of the nematodynamics. Six years later, Pierre-Gilles de Gennes noted in a premonitory way, in his seminal book The Physics of Liquid Crystals, that the heat current responsible for the Lehmann effect could also be an electric or a diffusion current, suggesting the existence of an electric or chemical Lehmann effect. This led to numerous experiments, sometimes wrongly interpreted, and to the recent discovery of the chemical Lehmann effect in Langmuir monolayer and ferroelectric smectic films. These experiments are reviewed and discussed in this paper.

Lehmann rotation of twisted bipolar cholesteric droplets: role of Leslie, Akopyan and Zel’dovich thermomechanical coupling terms of nematodynamics

ABSTRACT We show that the Leslie and texture-dependent Akopyan and Zel’dovich thermomechanical coupling terms of nematodynamics cannot explain the thermal Lehmann rotation of the twisted bipolar droplets observed in the coexistence region between a cholesteric phase and the isotropic liquid. On the other hand, these terms are pertinent below the transition temperature and can be determined by measuring the director rotation velocity in two different molecular configurations. In addition, a complete characterisation of the liquid crystal used (CCN-37) is also given. Graphical Abstract

Development of DPD coarse-grained models: From bulk to interfacial properties

A new Bayesian method was recently introduced for developing coarse-grain (CG) force fields for molecular dynamics. The CG models designed for dissipative particle dynamics (DPD) are optimized based on trajectory matching. Here we extend this method to improve transferability across thermodynamic conditions. We demonstrate the capability of the method by developing a CG model of n-pentane from constant-NPT atomistic simulations of bulk liquid phases and we apply the CG-DPD model to the calculation of the surface tension of the liquid-vapor interface over a large range of temperatures. The coexisting densities, vapor pressures, and surface tensions calculated with different CG and atomistic models are compared to experiments. Depending on the database used for the development of the potentials, it is possible to build a CG model which performs very well in the reproduction of the surface tension on the orthobaric curve.