Autohesion Mechanisms at Interfaces Between Random Copolymer Melts: Mesoscopic Simulations with Realistic Coarse-Grained Models.

The increasing of welding time during the interdiffusion of a pair of non reacting random copolymer melts favors the strength rate of healing at the interface. Furthermore, the diffusion kinetic during the interpenetration of copolymer chains across the interface is strongly dependant on molecular weight. In this paper we perform mesoscopic simulations with realistic coarse grain models to study the autohesion mechanism across the interface between slightly entangled styrene-butadiene random copolymer melts.

Consistent and Transferable Force Fields for Statistical Copolymer Systems at the Mesoscale.

The statistical trajectory matching (STM) method was applied successfully to derive coarse grain (CG) models for bulk properties of homopolymers. The extension of the methodology for building CG models for statistical copolymer systems is much more challenging. We present here the strategy for developing CG models for styrene-butadiene-rubber, and we compare the quality of the resulting CG force fields on the structure and thermodynamics at different chemical compositions. The CG models are used through the use of a genuine mesoscopic method called the dissipative particle dynamics method and compared to high-resolution molecular dynamics simulations. We conclude that the STM method is able to produce coarse-grained potentials that are transferable in composition by using only a few reference systems. Additionally, this methodology can be applied on any copolymer system.

Lehmann rotation of cholesteric droplets driven by Marangoni convection.

We show experimentally and theoretically that the Lehmann effect recently observed by Yoshioka and Araoka (Nat. Commun., 2018, 9, 432) in emulsified cholesteric liquid crystal droplets under temperature gradients is due to Marangoni flows rather than to the thermomechanical or chemomechanical couplings often invoked to explain the phenomenon. Using colloidal tracers we visualize convection rolls surrounding stationary cholesteric droplets in vertical temperature gradients, while a shift in the position of internal point defects reveals the corresponding inner convection in nematic droplets thermomigrating in a horizontal temperature gradient. We attribute these phenomena to the temperature dependence of the surface tension at the interface between these partially-miscible liquids, and justify their absence in the usual case of purely lyophobic emulsions. We perform a theoretical analysis to help validate this hypothesis, demonstrating the strong dependence of the precession velocity on the configuration of the cholesteric director field.

How Does the Addition of a Third Ion Affect the Molecular Interactions and the Thermodynamic Properties of Acetate-Based Ionic Liquids?

The effect of the addition of a third ion to the ionic liquid 1-butyl-3-methylimidazolium acetate [C4C1Im][OAc] was studied through the measurement of the enthalpy of mixing and of the excess molar volume of its mixtures with 1-butyl-3-methylimidazolium trifluoroacetate [C4C1Im][CF3CO2], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4C1Im][NTf2], and tetrabutylphosphonium acetate [P4444][OAc]. Negative enthalpies of mixing (ΔmixH < 0) and positive excess molar volumes (VE > 0) were observed in all cases. The infrared and NMR studies of the pure ionic liquids and their mixtures show that the presence of a third ion with a weaker affinity with the common counterion contributes to prevailing the more favorable hydrogen-bond, herein always between the imidazolium cation and the acetate anion. Both radial and spatial distribution functions calculated by molecular simulation confirm this behavior. The remarkable enhancement of the viscosities of the [C4C1Im][OAc] + [P4444][OAc] mixtures could be discussed in light of the calculated friction coefficients.

Role of Dynamical Heterogeneities on the Mechanical Response of Confined Polymer.

Confinement induces various modifications in the dynamics of polymers as compared to bulk. We focus here on the role of dynamical heterogeneities on the mechanics of confined polymers. Using a simple model that allows computation of the mechanical response over 10 decades in frequency, we show that the local mechanical coupling controlling the macroscopic response in the bulk disappears in a confined geometry. The slowest domains significantly contribute to the mechanical response for increasing confinement. As a consequence, the apparent glass transition is broadened and shifted towards lower frequencies as confinement increases. We compare our numerical predictions with experiments performed on poly(ethylacrylate) chains in model filled elastomers. We suggest that the change of elastic coupling between domains induced by confinement should contribute significantly to the polymer mobility shift observed on filled systems.

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 T(g) 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 T(g) and T(g) + 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 T(g) + 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.

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

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 Eber 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.

Does the electric Lehmann effect exist in cholesteric liquid crystals?

Experiments have shown that cholesteric droplets or cholesteric fingers may be put into motion by the action of an electric field. The former rotate whereas the latter drift perpendicularly to their axes. In all cases, the texture moves without visible material transport. The electric Lehmann effect was initially used to interpret these observations but, recently, alternative explanations were found, based on electrohydrodynamics. Another experiment in this area was that of Padmini and Madhusudana (Liq. Cryst. 14, 497 (1993)). Performed in 1993 with a compensated cholesteric liquid crystal under fixed planar boundary conditions, it was also explained in terms of electric Lehmann effect. We conducted the same experiment and extended it to a pi -twisted planar geometry. Although our experimental results agree with those of Padmini and Madhusudana, we demonstrate that they are incompatible with an electric Lehmann effect. By contrast, an explanation based on flexoelectricity allows us to interpret the whole data set obtained in both geometries. The consequence is that there is at the moment no clear experimental evidence of the electric Lehmann effect.

Zigzag instability of a chi disclination line in a cholesteric liquid crystal.

We studied the formation of chi disclination lines in planar cholesteric samples placed in a temperature gradient near the cholesteric to smectic A phase transition. We observed that the first simple line which forms close to the smectic-cholesteric front zigzags when it is perpendicular to the direction of planar anchoring and is straight for other orientations. This instability is similar to Herring instability for crystalline surfaces. We show numerically that it originates from a strong increase of the elastic anisotropy close to the transition. In addition, we propose a new method to measure the pitch divergence at the smectic to cholesteric phase transition.