Main-chain liquid-crystal elastomers versus side-chain liquid-crystal elastomers: similarities and differences in their mechanical properties.

After a general introduction on the main aspects of the mechanical properties of main-chain liquid-crystal elastomers (MCLCEs) and side-chain liquid-crystal elastomers (SCLCEs), new results will be presented dealing with several MCLCEs with a cross-linker density C = 8%, 6% and 4% and with a SCLCE with C = 10%, all prepared by the two-step cross-linking process. A non-SCLCE with bulky side-groups similar in shape to the mesogens was also synthesized for comparison with the SCLCE. Most of the experiments were performed with a piezorheometer allowing the determination of the shear anisotropy of the samples by applying shear in a direction parallel or perpendicular to the director, and with a thermo-elastic device for the E measurements. The main results concern: (a) the influence of the supercritical nature of SCLCE and the subcritical nature of MCLCEs on the mechanical properties of these elastomers, as well as that of SmC domains present in MCLCEs; (b) the relationship between the degrees of elongation and of anisotropy deduced from the variations of and during the poly-domain to mono-domain transition of the 10% SCLCE and the 8% MCLCE; (c) the determination of the Poisson's ratio showing that it is isotropic for the non-SCLCE, with a crossover between 0.5 (classical value for rubbers) for small strains and 0.38 for high strains, and anisotropic for the 10% SCLCE and 8% MCLCE, with values <0.5. The particular behaviors of the Poisson's ratios can be explained by confinement effects occurring when stretching increases.

Mechanical properties of monodomain nematic side-chain liquid-crystalline elastomers with homeotropic and in-plane orientation of the director.

We present the first study of the shear mechanical properties of monodomain nematic side-chain liquid-crystal elastomers (SCLCEs) prepared by cross-linking with UV irradiation a nematic side-chain liquid-crystal polymer oriented with an electric or a magnetic field. Their elastic behavior was studied in the dry, swollen and stretched states, in order to check the various theoretical descriptions of these systems. The shear measurements taken on the dry samples show that the shear anisotropy is much smaller than that of the usual twice cross-linked samples oriented by a mechanical stretching of the network formed after the first cross-linking step, demonstrating that the elasticity of the networks strongly depends on the preparation procedure used. The shear experiments performed on the swollen state of these two different types of elastomers reveal that the elasticity of the network is Gaussian for the elastomers oriented with the electric or the magnetic field, and non-Gaussian for the elastomers oriented with the usual stretching procedure. The analysis of the stress-strain curves of both types of elastomers with the neoclassical model based on Gaussian rubber elasticity confirms the Gaussian and non-Gaussian nature of their elasticity. The shear experiments performed as a function of the elongation of the homeotropically oriented elastomer when the shear is applied in a direction parallel to the elongation, do not show the decrease of the associated shear modulus, which is theoretically expected when the strain approaches the threshold value marking the beginning of the elastic plateau. However, the observation of this effect could be prevented by possible small misalignments of the director, as suggested by a calculation presented in one of the theories describing this effect.

Gel-like elasticity in glass-forming side-chain liquid-crystal polymers.

We study the complex shear modulus G of two side-chain liquid-crystal polymers (SCLCPs), a methoxy-phenylbenzoate substituted polyacrylate (thereafter called PAOCH3 ), and a cyanobiphenyl substituted polyacrylate supplied by Merck (thereafter called LCP105) using a piezoelectric rheometer. Two methods of filling the cell are used: (a) a capillary method, which can be used only at high temperature because of the low value of the viscosity, and (b) the classical one, thereafter called compression method, which consists in placing the sample between the two slides of the cell and to bring them closer. By filling the cell at high temperature either with the compression or the capillary method, we show that the response of both compounds is liquidlike ( G' approximately f2 and G'' approximately f , where f is the frequency) for temperatures higher than a certain temperature T0 and gel-like (G' approximately const, G'' approximately f) below T0. This change in behavior from the conventional flow response to a gel-like response, when approaching the glass transition, is observed for nonsliding conditions and for very weak-imposed shear strains. It can be explained by a percolation-type mechanism of preglassy elastic clusters, which correspond to long-range and long-lived density fluctuations that are frozen at the time scale of the experiment. The sample response is therefore the sum of two contributions: one is due to the flow response of the polymer melt and the other to the elastic response of the network formed by the preglassy elastic clusters. By filling the cell below T0 with the compression method, both compounds exhibit a gel-type behavior by gently bringing closer the slides of the cell and an anomalous low-frequency behavior characterized by G'=const and G''=const by increasing the pressure used to bring closer the slides of the cell. A compression-assisted aggregation of the preglassy elastic clusters can explain both the increase in the low-frequency elastic plateau when the sample thickness is decreased and the anomalous low-frequency behavior. Further evidence for the existence of these elastic clusters is provided by the following results: (a) the nonlinear response of the samples as a function of the strain amplitude, which can be explained by the Payne effect, and (b) the aggregation effects, which can be mimicked by a polydimethylsiloxane melt filled with silica particles, the silica particles playing the role of the preglassy elastic clusters. All these observations show that PAOCH3 is not a macroscopically solidlike material with an unconventional type of elasticity, as claimed by Mendil [Phys. Rev. Lett. 96, 077801 (2006)]. The gel-type behavior observed here on two SCLCPs ( PAOCH3 and LCP105) and previously on some conventional flexible polymers (atactic polystyrene, poly-n-butylacrylate) seems to be a generic effect of the glass transition. The presence of the preglassy elastic clusters questions the widely accepted hypothesis of ergodicity in the supercooled state.

Shear mechanical anisotropy of side chain liquid-crystal elastomers: influence of sample preparation.

We study the mechanical anisotropy of a series of uniaxial side chain nematic elastomers prepared with the same chemical composition but with different preparation protocols. For all the compounds, the experiments performed as a function of temperature show no discontinuity in both G' (//) and G' ( perpendicular) (the labels // and perpendicular stand for the director parallel, respectively perpendicular to the shear displacement) around the nematic-isotropic (N-I) phase transition temperature determined by DSC. They also all show a small decrease in G' (//) starting at temperatures well above this temperature (from approximately 4( degrees ) C to approximately 20( degrees ) C depending on the compound studied) and leading to a small hydrodynamic value of the G' ( perpendicular)/G' (//) ratio. The measurements taken as a function of frequency show that the second plateau in G' (//) and the associated dip in G (//)" expected from dynamic semi-soft elasticity are not observed. These results can be described by the de Gennes model, which predicts small elastic anisotropy in the hydrodynamic and linear regimes. They correspond to the behavior expected for compounds beyond the mechanical critical point, which is consistent with the NMR and specific heat measurements taken on similar compounds. We also show that a reduction in the cross-linking density does not change the non-soft character of the mechanical response. From the measurements taken as a function of frequency at several temperatures we deduce that the time-temperature superposition method does not apply. From these measurements, we also determine the temperature dependence of the longest relaxation time tau(E) of the network for the situations where the director is either parallel or perpendicular to the shear velocity. Finally, we discuss the influence on the measurements of the mechanical constraint associated with the fact that the samples cannot change their shape around the pseudo phase transition, because of their strong adherence on the sample-bearing glass slides.

Commentary on "Solid-like rheological response of non-entangled polymers in the molten state" by H. Mendil et al.

We discuss the rheology experiments on classical and liquid crystal polymer melts by Mendil et al., in the light of the old and new piezorheometry experiments we have carried out on both types of melt. The mechanical behavior we have observed in the linear and non-linear regimes are independent of the melt studied (classical or liquid crystal), and of their nature (siloxane-type, acrylate-type and styrene-type). In the linear regime, the mechanical behavior of the melts presents two components: the first one is the conventional contribution. It is due to polymer chains, and is independent of sample thickness. The second one, which can be observed only when a strong interaction between the compound and the substrate exists, is associated with the glass transition. This component displays an elastic response depending on the sample thickness, and disappears at high temperature. It can be explained by assuming the presence of long-range density fluctuations, which are associated with the glass transition, and frozen at the frequencies used in the experiments. The experiments as a function of the applied strain show that the value of the elastic component decreases when the applied strain increases. This slipping transition occurs progressively, which highlights the heterogeneous nature of the anchoring. The results on the classical polymer by Mendil et al. can be considered to be consistent with ours. In contrast, their results on the liquid crystal polymer differ markedly from ours, showing that the elastic response of this sample has not the same origin.

Behavior of the layer compression elastic modulus near, above, and below a smectic C-hexatic I critical point in binary mixtures.

We present the first study of the layer compression modulus B carried out near, above and below the Smectic C-Hexatic I critical point in racemic mixtures of methylbutyl phenyl octylbiphenyl-carboxylate (8SI) and the octyloxy biphenyl analog (8OSI), at frequencies ranging from 0.2 Hz to 2 x 10(3) Hz. The behavior of B as a function of temperature shows a progressive evolution from a first order transition in 8SI to a continuous supercritical behavior in 8OSI. The latter is characterized by an increase in B, which appears above the transition, and which is followed by a leveling off when the temperature is decreased towards the transition. It is proposed that this behavior stems from the relaxation of the hexatic domains which are frozen in the frequency range studied. For the supercritical and near-critical compounds, B exhibits a small dip near the transition temperature, which is visible in the low frequency range only, indicating that the dynamics associated with the critical point is very slow. We also report measurements in the Crystal-J phase of the pure compounds, and show that 8SI behaves mechanically as a hexatic phase and 8OSI as a soft crystal phase.

Mechanical properties of mono-domain side chain nematic elastomers.

We investigate the behavior of the shear rigidity modulus G = G' + iG" of three mono-domain side chain liquid-crystalline elastomers composed of side chain polysiloxanes cross-linked by either flexible or rigid cross-linkers. The measurements were taken in a frequency domain ranging from approximately 0.02 Hz to approximately 10(4) Hz applying the shear in a plane perpendicular to or containing the director. The measurements as a function of temperature show an anisotropy of G' which appears around T(NI), when decreasing the temperature, and which is due to the expected lowering of G'(//) coming from the coupling between the shear and the director. The measurements as a function of frequency show that G has two components for both geometries, in both the isotropic phase and in the nematic phase around the phase transition. One reflects the network behavior in its hydrodynamic regime ( G' is constant and G'' is approximately f, where f is the frequency), the other which appears at higher frequencies is characterized by a scaling law behavior (G' is approximately G" is approximately f(0.5)) of the Rouse type. We discuss the results in the framework of available theories and show that the three elastomers present a non-soft behavior, even for the elastomer for which the contrary was claimed, and that there is no separation of time scales between the director and the network. We also present data on a poly-domain sample and a non-mesomorphic one which complement these results.

Behavior of the layer compression modulus as a function of frequency near the nematic-smectic-A and re-entrant nematic-smectic-A phase transitions.

A progressive cross-over of the layer compression modulus B from a simple power law behavior to a saturation behavior when the frequency is increased from 1 Hz to 2 x 10(3) Hz is observed for the first time near the nematic-smectic-A and the re-entrant nematic-smectic-A phase transitions of a mixture of 4-cyano-4'-( n-hexyloxy)biphenyl and 4-cyano-4'-( n-octyloxy)biphenyl (6OCB-8OCB). This result shows that the saturation of B determined by second sound near the nematic-smectic-A phase transition of a similar mixture is dynamic in nature, and cannot be associated with the static saturation effect predicted by the dislocation loop model, as proposed previously.

Critical behavior of the de gennes elastic constants near the nematic-smectic- A transition of TBBA

We have studied the behavior of elastic constants A, B, and C deduced from ultrasound velocity anisotropies in the vicinity of the nematic-smectic- A transition of terephthal-bis- p- p(')-butylaniline. A is associated with compressibility, B with layer compression, and C with the coupling between compressibility and layer compression. We show that the exponent of A is of the preasymptotic 3D- XY type, whereas those of B and C are in between the 3D- XY values and those associated with the anisotropic fixed point. This behavior is consistent with the extended crossover regime predicted by Patton and Andereck [Phys. Rev. Lett. 69, 1556 (1992)].

Dynamic scaling of ultrasonic damping near the nematic-smectic- A transition of TBBA

We report a detailed study of the ultrasonic damping near the nematic-smectic- A phase transition of terephtal-bis- p-p(')-butylaniline (TBBA). Two mechanisms contribute to the damping. One is isotropic; it is associated with the critical fluctuations, and leads to a scaling behavior of the 3D- XY type which is observed up to 15 degrees C from the transition, even though the transition is first order. The other is anisotropic; it appears only in the smectic- A phase, and is associated with the relaxation of the order-parameter modulus.