X-ray diffraction by liquid-crystalline elastomers

A new series of mesomorphic side chain polysiloxane networks has been recently synthesized in which the chemical nature of the linkage and the mesogenic group have been varied and the gelation conditions during the chemical reaction have been studied. This paper presents an X-ray diffraction study of the mesogenic group orientation in stretched samples of these networks. The angular extension of the so-called wide angle diffuse ring is used to estimate the orientational order of the mesogenic group versus strain. To perform these experiments, a special stretching device was developed and a new two-dimensional X-ray detector was used which allowed us to collect the data in a few minutes. On stretching, it was observed that the mesogenic groups orient themselves perpendicular to the stress direction for all of the samples but for one for which the parallel orientation prevailed. This prevents the establishment of a simple general law. From another point of view, the polymer concentration during the chemical reaction, which controls the gelation, is shown to be an important parameter with which to understand the physical properties: the networks synthesized below the gel point do not display reproducible and reversible behaviour, rather they flow when they are stretched. Conversely, all of the networks synthesized above the gel point really show the same well-defined behaviour independent of the sample history. Their orientational order increases regularly with the strain, first quickly, then moderately until it eventually saturates. This saturation value of the mesogenic group orientational order does not reach the nematic order parameter of the same (uncross-linked) mesomorphic side chain polymers. This suggests that the cross-links may create local tensions which disturb the nematic field.     

Azophenol-based liquid-crystalline elastomers for light-driven actuators

Para-substituted azophenols exhibit a fast thermal cis-to-trans isomerization rate in ethanol, which can be transferred to the solid state by obtaining liquid-crystalline elastomeric systems. The absence of protic solvent is compensated by the establishment of hydrogen bonding between azophenol monomers that are close to each other. Opto-mechanical experiments reveal that azophenol-containing liquid single-crystal elastomers are valuable materials for light-controlled actuators exhibiting relaxation times of 1 s at room temperature.     

Ferroelectric liquid-crystalline elastomers with short switching times

The crosslinking of ferroelectric liquid-crystalline (LC) polysiloxanes — performed within the region of microphase separation — allows the preparation of LC-elastomers which combine macroscopic form stability (insolubility) with nearly unchanged switching time (compared to the uncrosslinked polymers).     

Mesomorphic properties of side-chain cholesteric liquid-crystalline elastomers

New monomer cholesteryl 4-(10-undecylen-1-yloxybenzoyloxy)-4′-ethoxybenzoate (M₁), crosslinking agent biphenyl 4,4′-bis(10-undecylen-1-yloxybenzoyloxy-p-ethoxybenzoate) (M₂) and a series of side-chain cholesteric elastomers were prepared. The chemical structures of the monomers and elastomers obtained were confirmed by element analyses, FT-IR, and ¹H NMR. The mesomorphic properties and thermal stability were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction measurements. The influence of the content of the crosslinking unit on the phase behavior of the elastomers was examined. M ₁ showed cholesteric phase, and M ₂ displayed nematic phase. The elastomers containing less than 12 mol% of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability.     

Photomechanics of liquid-crystalline elastomers and other polymers

Muscle is a transducer that can convert chemical energy into mechanical motion. To construct artificial muscles, it is desirable to use soft materials with high mechanical flexibility and durability rather than hard materials such as metals. For effective muscle-like actuation, materials with stratified structures and high molecular orders are necessary. Liquid-crystalline elastomers (LCEs) are superior soft materials that possess both the order of liquid crystals and the elasticity of elastomers (as they contain polymer networks). With the aid of LCEs, it is possible to convert small amounts of external energy into macroscopic amounts of mechanical energy. In this Review, we focus on light as an energy source and describe the recent progress in the area of soft materials that can convert light energy into mechanical energy directly (photomechanical effect), especially the photomechanical effects of LCEs with a view to applications for light-driven LCE actuators.     

Thermal characterisation of thermotropic nematic liquid-crystalline elastomers

Nematic liquid-crystalline elastomers (LCEs) are weakly cross-linked polymeric networks that exhibit rubber elasticity and liquid-crystalline orientational order due to the presence of mesogenic groups. Three end-on side-chain nematic LCEs were investigated using real-time synchrotron wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), and thermogravimetry (TG) to correlate the thermal behaviour with structural and chemical differences among them. The elastomers differed in cross-linking density and mesogen composition. Thermally reversible glass transition temperature, T_g, and nematic-to-isotropic transition temperature, T_ni, were observed upon heating and cooling. By varying the heating rate, T_g⁰ and T_ni⁰ were determined at zero heating rate. The temperature dependence of the orientational order parameter was determined from the anisotropic azimuthal angular distribution of equatorial reflections seen during real-time WAXS. Results show that the choice of cross-linking unit, its shape, density, and structure of co-monomers, all influence the temperature range over which the thermal transitions take place. Including multi-ring aromatic groups as cross-linkers increased the effective stiffness of the cross-linking, resulting in a higher glass transition temperature. The nematic-to-isotropic transition temperature increased in the presence of multi-ring aromatic structures, as either cross-linkers or mesogens, particularly when the multi-ring structures were larger than the low-molar-mass mesogen common to all three samples.     

Synthesis and characterization of fluorinated liquid-crystalline elastomers containing chiral liquid-crystalline crosslinking units

Fluorinated chiral liquid-crystalline elastomers (LCEs) were graft copolymerized by a one-step hydrosilylation reaction with polymethylhydrogenosiloxane, a fluorinated LC monomer 4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyloxy)phenyl 4-(undec-10-enoyloxy)benzoate (PPUB) and a chiral crosslinking LC monomer (3R,3aR,6S,6aR)-6-(undec-10-enoyloxy)hexahydrofuro[3,2-b]furan-3-yl 4′-(4-(allyloxy)benzoyloxy)biphenyl-4-carboxylate (UHAB). The chemical structure, liquid-crystalline behavior and polarization property were characterized by use of various experimental techniques. The effective crosslink density of the LCEs was characterized by swelling experiments. The thermal analysis results showed that the temperatures at which 5% weight loss occurred were greater than 250 °C for all the LCEs, and the residue weight nearby 600 °C increase with increasing chiral crosslinking components in the polymer systems. All the samples showed chiral smectic C mesophase when they were heated. The glass transition temperature and mesophase-isotropic phase transition temperature of fluorinated elastomers increased slightly with increase of chiral crosslinking mesogens in the polymer systems, but the enthalpy changes of mesophase-isotropic phase transition decreased slightly. In XRD curves, all the samples exhibited strong sharp reflections at small angles suggesting smectic layered packing arrangement. These fluorinated chiral LCEs showed 0.1–0.2 μC/cm² of spontaneous polarization with increasing chiral crosslinking component.     

Isotropic to smectic-C phase transition in liquid-crystalline elastomers

A phenomenological model is developed to describe the isotropic-smectic-C phase transition in liquid-crystalline side-chain elastomers. We analyze the influence of external mechanical stress on the isotropic-smectic-C phase transition. While this phase transition is first order in low-molecular-weight materials, we show here that the order of this transition does not change in liquid-crystalline elastomers. The temperature dependence of the heat capacity and the nonlinear dielectric effect in the isotropic phase above the isotropic-smectic-C phase transition in liquid crystalline elastomers are calculated. The theoretical results are found to be in good agreement with experiment.     

Spontaneous deformation of main-chain liquid-crystalline elastomers composed of smectic polyesters

We observe the spontaneous shape change of a uniaxially deformed liquid-crystalline elastomer composed of smectic main-chain liquid-crystalline polyesters in a cyclic heating–cooling process. Although the elastomer contracts by about 115% on heating up to the isotropic phase, the sample length recovers by 55% on cooling to room temperature in the first heating–cooling process, and the elastomer exhibits an almost complete reversible deformation in the second heating–cooling process. By a comparison of the results of sample observation with those of X-ray analysis, we recognise that the strain λ was linearly coupled with the orientational order parameter S. In addition, the results of the X-ray analysis imply that a cybotactic nematic state, in which smectic clusters lie scattered in a nematic-like matrix, emerges after exposure to the isotropic phase.     

Cyclosiloxane-based liquid-crystalline elastomers containing fluorinated mesogens and chiral crosslinking groups

A series of chiral fluorinated liquid-crystalline elastomers (LCEs) IP-VIP are prepared by 4-cyano-3-fluorophenyl 4′-(undec-10-enoyloxy)biphenyl-4-carboxylate, isosorbide bis(4-allyloxybenzoate) and 2,4,6,8-tetramethylcyclotetrasiloxane via Pt-catalyzed hydrosilylation. The chiral crosslinking moieties increase from IP to IVP. The elastomers IP, IIP, and IIIP containing low content of chiral crosslinking moieties display S_C ^* liquid-crystalline phase, but IVP, VP, and VIP do not show S_C ^* phase except for N^* mesophase. The mesophase is testified according to typical diffractogram measured by X-ray diffraction (XRD) analysis. The layer spacings of the LCEs decrease from IP (d-spacing of 34.2 Å) to VIP (d-spacing of 31.6 Å) with increase of chiral crosslinking groups in the polymers systems. Moreover, the optical properties are performed by ultraviolet–visible–near-infrared spectrophotometry. VP and VIP containing the most chiral crosslinking moieties display maximum reflection in near infrared spectra in the measurement of optical properties, while IP, IIP, IIIP, and IVP do not show obvious maximum reflection. It is interesting that a specific reflection of circularly polarized light appears along with a changing mesophase due to high enough concentration of chiral crosslinking dopants for VP and VIP. All these results suggest that the chiral crosslinking moieties exert influence on the structures of these kinds of LCEs.     

Amphiphilic liquid-crystalline networks — phase behavior and alignment by mechanical fields

A cross-linked polysiloxane carrying non-ionic amphiphilic side-groups attached with their hydrophobic end to the polymer backbone is synthesized. The amphiphilic groups are selectively deuterated at the α-position of the hydrophobic alkyl chains. The phase behavior with water is studied by deuterium nuclear magnetic resonance spectroscopy. A lamellar phase (L_a) is observed on the low-water-concentration side of the liquid-crystalline regime. The domains of the L_a-phase can be aligned macroscopically by uniaxial compression of the sample.     

Amphiphilic macrocyclic nickel(II) complex in a liquid-crystalline matrix: Specific effects of conductivity and self-organization

A study was made of the influence of an amphiphilic macrocyclic nickel(II) complex on the electrical and electro-optic properties of liquid-crystalline systems based on ZhK-440I. It was shown that addition of this complex leads to a decrease in the electrohydrodynamic instability threshold and formation of unusual tetragonal ordered structures in the systems studied.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 29, No. 6, pp. 522–526, November–December, 1993.The authors wish to express their gratitude to the Fundamental Research Fund of the General Committee of Science and Technology of the Ukraine for financial support of this investigation (Projects 3/114 and 46/3-2).     

Amphiphilic thermoset elastomers from metal‐free,click crosslinking of PEG‐grafted silicone surfactants

The hydrophobicity of silicone elastomers can compromise their utility in some biomaterials applications. Few effective processes exist to introduce hydrophilic groups onto a polysiloxane backbone and subsequently crosslink the material into elastomers. This problem can be overcome through the utilization of metal‐free click reactions between azidoalkylsilicones and alkynyl‐modified silicones and/or PEGs to both functionalize and crosslink silicone elastomers. Alkynyl‐functional PEG was clicked onto a fraction of the available azido groups of a functional polysiloxane, yielding azido reactive PDMS‐g‐PEG rake surfactants. The reactive polymers were then used to crosslink alkynyl‐terminated PDMS of different molecular weights. Using simple starting materials, this generic yet versatile method permits the preparation and characterization of a library of amphiphilic thermoset elastomers that vary in their composition, crosslink density, elasticity, hydrogel formation, and wettability. An appropriate balance of PEG length and crosslink density leads to a permanently highly wettable silicone elastomer that demonstrated very low levels of protein adsorption. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1082–1093     

Adhesive liquid-crystalline polymers

The synthesis and characterization of liquid-crystalline polymers with possible good adhesive properties is reported. These polymers are prepared by alternating copolymerization of maleic anhydride and mesogenic alkenes. The spacer length m is varied (m = 2, 3, 4, 6, 8 and 9) and methoxybiphenyl is used as the mesogenic group. The glass transition temperature decreases and the isotropization temperature increases with spacer length. Depending on the spacer length and temperature, S_B and S_Ad mesophases can be observed. After annealing, spin-coated films of these polymers show very regular layered structures with a layer spacing similar to that in the bulk.     

Ferrocene-containing liquid-crystalline dendrimers

We describe the synthesis and liquid-crystalline properties of two ferrocene-containing liquid-crystalline dendrimers of second generation, which differentiate by the position of the ferrocene unit within the structure and by the nature of the mesomorphic promoters. Both dendrimers gave rise to smectic phases in agreement with their structures. The title compounds were prepared by applying a convergent synthesis. To cite this article: T. Chuard et al., C. R. Chimie 6 (2003).