Origin of shear-induced phase transitions in melts of liquid-crystal polymers

International audienceFlow induced mechanical properties are often coupled with instabilities, spurt effects, or induced phase transitions. Recent studies have revealed that side-chain liquid crystal polymers exhibit typically shear-induced phases inside the isotropic ͑nonmesomorphic͒ liquid state. We present an experimental approach which brings a new understanding for nonlinear flow behaviors. The strategy consists in comparing the critical times issued from the flow behavior of a liquid-crystal polymer to the equilibrium orientational-order relaxation time was characterized. We demonstrate that shear-induced phases do not originate from a flow coupling to conventional orientational order parameter fluctuations. It does not also correspond to a direct coupling with the viscoelastic terminal time, leading to the conclusion that an additional relaxation process takes place with time scales longer than the terminal time. The identification of a low-frequency elastic plateau by viscoelastic measurements corroborates this conclusion

Side-chain liquid-crystalline polyacrylates: Experimental evidence of a coexistence of a double main-chain confinement inside the smectic layer

International audienceDetailed profiles providing the main-chain/mesogen organisation within the smectic layers have been deduced from neutron diffraction measurements, by combination of the coherent scattering length profiles of the fully hydrogenated and the partially deuterated sidechain liquid-crystal polymers. Two different sites of the molecule (either on the main chain or on the mesogen extremity) have been labelled to prove that main chains can occupy the central zone of the mesogenic layers whereas most of them remains confined between the layers of mesogens. This surprising result can be explained considering symmetry arguments

Shear flow induced transition from liquid-crystalline to polymer behavior in side-chain liquid crystal polymers

International audienceWe determine the structure and conformation of side-chain liquid-crystalline polymers subjected to shear flow in the vicinity of the smectic phase by neutron scattering on the velocity gradient plane. Below the nematic-smectic transition we observe a typical liquid-crystal behavior; the smectic layers slide, leading to a main-chain elongation parallel to the velocity direction. In contrast, a shear applied above the transition induces a tilted main-chain conformation which is typical for polymer behavior

Identification of a low-frequency elastic behaviour in liquid water

International audienceThis article deals with the identification of solid-like properties measured at room temperature at a sub-millimetre length scale in liquid water. At a macroscopic scale, normal liquids (i.e. above melting temperature), and in particular water, are typically and empirically defined by the absence of shear elasticity, in contrast to solids or plastic fluids that require a stress threshold for flowing. A novel method optimizing the transmission of the shear stress to the sample enables a more complete probe of the mechanical response of liquids. It reveals that glass formers and viscous alkanes actually exhibit finite macroscopic shear elasticity away from any phase transition. This protocol is here applied for the first time to liquid water at room temperature, revealing, at the sub-millimetre scale, a low-frequency solid-like property

Identification of nonmonotonic behaviors and stick-slip transition in liquid crystal polymers

International audienceThe recent identification of shear-induced phases in the isotropic melts of liquid crystal polymers shows that these materials are expected to display original nonlinear behaviors. We have investigated the flow behavior of a nematic sidechain polymer above its isotropic-nematic transition temperature. Nonlinear rheology and bire-fringence measurements indicate the appearance, above a critical shear rate, of the shear-induced isotropic-nematic phase transition. The rheological behavior of this induced phase is characterized by undamped time-periodic shear stress oscillations. These sustained oscillations are interpreted in terms of a stick-slip mechanism alternating high-friction static state and low-friction kinetic state. PACS number͑s͒: 83.80.Xz, 47.20.Hw, 83.50.Ax, 64.70.Md Polymers are non-Newtonian fluids ͓1͔ whereas liquid crystals do not behave as simple fluids close to phase transitions ͓2͔. When these two complex fluids are coupled to form a melt of sidechain liquid crystal polymers ͑SCLCPs͒, the resulting rheological behavior is expected to be peculiar. The very first flow studies ͓3͔ have indeed indicated that SCLCP melts display strong nonlinear behaviors above the isotropic-nematic transition temperature (T NI). This behavior looks similar to the well-studied shear-induced behavior of giant micelle solutions which display a shear-induced IN transition above T NI ͓4,5͔. The SCLCP shear-induced transition was revealed by flow birefringence and via the existence of a stress plateau in the stress versus shear rate curve. The stress plateau can be explained by entering an unstable flow region; above a critical shear rate, the region is characterized by a decreasing stress with increasing shear rate. The system is then supposed to phase separate into homogeneous bands ͑shear banding͒ to maintain the imposed shear rate ͓5͔. The existence of such nonequilibrium states opens the question of identification of the coupling parameters associated with the critical shear rate. Clearly, the shear induced SCLCP critical times are not associated with the lifetime of the pretransi-tional fluctuations, suggesting a coupling with slower time scales which could be rather consistent with the existence of macroscopic heterogeneities as proposed by Collin et al. ͓6͔. The shear-induced phase conformation of the polymer main chain was also determined using small angle neutron scattering. For a LC polymer characterized in the equilibrium nem-atic phase by a perpendicular main chain/mesogen coupling ͑oblate conformation͒, we observed that the initially perpendicular coupling is inverted in the shear-induced nematic phase to a parallel coupling with the main-chain conforma-tion becoming prolate ͓3͔. This structural rearrangement can be proposed as a working hypothesis to explain the appearance of shear-induced transitions in SCLCP isotropic melts. The purpose of the present paper is to analyze the flow behavior produced above T NI by a SCLCP whose main-chain conformation is already prolate in the equilibrium nematic phase ͓7͔. The experimental techniques used are nonlinear rheology and flow birefringence. A nonequilibrium phase compatible with shear-banding is identified together with the observation of a second nonlinear behavior corresponding to an oscillating regime. The SCLCP chosen, PA 4-CN, is characterized as a prolate nematic polymer ͓7͔. The monomers have been synthesized at the Laboratoire Lé on Brillouin and polymerized by Poly-merExpert via controlled radical polymerization. The polymer described here corresponds to a molecular weight of M W ϭ85 800 and a polydispersity index of Iϭ1.1. This molecular weight corresponds to a nonentangled polymer and no rubbery plateau was found in viscoelastic measurements. This PA 4-CN presents the following succession of me-sophases: Tg-30 °C-N-116 °C-I and corresponds to the formul

Unexpected giant elasticity in side-chain liquid-crystal polymer melts: A new approach for the understanding of shear-induced phase transitions

International audienceRecent studies have revealed that high molecular weight liquid crystals typically exhibit shear induced phases within the isotropic melt. From rheo-birefringence measurements, we demonstrate that those shear induced phases are not coupled with conventional orientational-order fluctuations. From rheo-SANS experiments, we show that the polymer chain is deformed at time scales longer than the viscoelastic relaxation time. Finally, careful visco-elastic measurements reveal a strong elastic behaviour; the melt is not a viscoelastic liquid but solid-like at equilibrium one hundred degrees over the glass transition temperature and up to 15°C over the Isotropic-Nematic phase transition. This supra molecular cohesion and its extra long relaxation times may explain the emergence of non-linear phenomena

Pressure-induced reduction of the Landau-Peierls instabilities in a side-chain polymer liquid crystal with reentrant polymorphism

International audienceCyanobiphenyl mesogens are known to exhibit partially bilayered smectic A (S Ad) and also reentrant nem-atic (N re) phases. Nematic and smectic orders are coupled parameters which depend both on temperature and pressure. We report the first structural study of the influence of a hydrostatic pressure on the smectic phase. This study was carried out on a side-chain liquid crystalline polymer, by neutron diffraction using two specifically designed pressure cells. These results concluded first that the pressure acts on the phase elastic constants via a reduction of the layer fluctuations giving rise to a hardening of the phase together with an extension of the smectic domain towards higher temperatures. Second, the S Ad-N re phase transition temperature remains unchanged in the studied pressure range revealing that the polymer component plays an important role which allows us to subtract the associated packing interactions from the pressure-induced volume reduction

Bringing to light hidden elasticity in the liquid state using in-situ pretransitional liquid crystal swarms

International audienceThe present work reveals that at the sub-millimeter length-scale, molecules in the liquid state are not dynamically free but elastically correlated. It is possible to " visualize " these hidden elastic correlations by using the birefringent properties of pretransitional swarms persistent in liquids presenting a weak first order transition. The strategy consists in observing the optical response of the isotropic phase of mesogenic fluids to a weak (low energy) mechanical excitation. We show that a synchronized optical response is observable at frequencies as low as 0.01Hz and at temperatures far away from any phase transition (up to at least 15°C above the transition). The observation of a synchronized optical signal at very low frequencies points out a collective response and supports the existence of long-range elastic (solid-like) correlations existing at the sub-millimeter length-scale in agreement to weak solid-like responses already identified in various liquids including liquid water. This concept of elastically linked molecules differs deeply with the academic view of molecules moving freely in the liquid state and has profound consequences on the mechanisms governing collective effects as glass formation, gelation and transport, or synchronized processes in physiological media

Harmonic strain-optical response revealed in the isotropic (liquid) phase of liquid crystals

International audienceA strong optical birefringence is observed when applying a small amplitude oscillatory strain to theliquid phase of a liquid crystal. This unpredicted birefringence is found to oscillate at the samefrequency as the driving frequency, with frequencies down to 0.01 Hz. This birefringence is visibleup to 15 C above the liquid crystal transition. This opto-dynamic property is interpreted as a resultof a coupling of the orientational pretransitional fluctuations existing in the isotropic phase andlong range elastic interactions recently identified in liquids. The conversion of the mechanicalwave in an optical response is shapeable. Two examples of synchronized periodic signals areshown: the sine and the square waves. The optimization of the signal is analyzed using aHeaviside-step shear test. This optical property is immediately exploitable to design low energyon/off switching material

Hidden solidlike properties in the isotropic phase of the 8CB liquid crystal

International audienceNovel dynamic experiments have enabled the identification of a macroscopic solidlike response in the isotropic phase of a low molecular weight liquid crystal, 4,4'-n-octylcyanobiphenyl (8CB). This unknown property indicates that the low frequency shear elasticity identified in the isotropic phase of liquid crystal polymers is not reminiscent from the glass transition but reveals likely a generic property of the liquid state. The comparison to high molecular weight liquid crystals indicates, however, that the shear modulus is much enhanced when the liquid crystal moieties are attached to a polymer chain. The macroscopic length scales probed (0.050–0.100 mm) exclude wall-induced effects. DOI: 10.1103/PhysRevE.88.050501 PACS number(s): 61.30.Hn, 68.08.−p, 87.15.hg, 83.85.Vb The knowledge of the timescales involved in liquid crystalline systems is of outmost importance to understand, control, and improve their characteristics. The submillimeter scales properties attract a tremendous research interest [1–4]. However, few studies concern the isotropic phase away from pretransitional effects. Assimilated to ordinary viscous liquids, the isotropic phase is not supposed to exhibit solidlike properties, or at very high frequency only (mega-or gigahertz) as ordinary liquids. For this reason, the low frequency behavior of the isotropic phase remains mistakenly unexplored. Experimentally, the viscous or solidlike nature of a material is deduced from its response to a low frequency mechanical solicitation. A couple of years ago, careful dynamic experiments carried out in the isotropic phase of high molecular weight liquid crystals [side-chain liquid crystalline polymers (SCLCPs)] have revealed an as-yet unknown property: the isotropic melt does not flow but exhibits a finite shear elasticity of about several thousand Pascals at low frequency (0.1–10 Hz) [5–9]. The identification of low frequency shear elasticity in the isotropic phase of SCLCPs away from the isotropic-nematic transition opens numerous questions on the origin of this new property. It neither seems to result from the contribution of the liquid crystal moieties nor from surface anchoring effects, but likely from a generic property of the liquid state. Measurable in SCLCPs at macroscopic length scales as far as 100 • away from the glass transition temperature [5,7,9], the shear elasticity of SCLCPs still raises the debated question of reminiscent glass transition effects. In this Rapid Communication, we probe the dynamic properties of the low molecular counterpart: the 4,4'-n-octylcyanobiphenyl (8CB). The widely studied molecule can be considered as a representative liquid crystal molecule. 8CB exhibits a crystalline phase at low temperatures that enables one to rule on the question of pretransitional glass transition effects. We reveal a low frequency, solidlike response at several tens of micrometers sample thickness in the isotropic phase of 8CB, meaning that long range correlations are preserved when the orientational order is lost. This shear elasticity is detectable if special attention is paid to boundary conditions between the substrate and the sample. Under these conditions, the shear stress is optimally transmitted between the sampl