Rheological properties of liquid crystalline solutions of ethyl celluloses with different molecular weight in m-cresol

Steady-state shear rheological properties of liquid crystalline solutions of four ethyl celluloses (ECs) were determined at a low shear rate (1 s^?1) and at relatively high shear rates by using two rheometers (cone-plate and capillary types), and were compared with those of liquid crystalline hydroxypropyl cellulose (HPC). The effect of molecular weight (MW) on the viscoelastic behavior was also determined. The viscoelastic behavior was also determined. The viscometric behavior of EC solutions was similar to that of HPC solutions: (1) with respect to temperature, the shear viscosity (η) at shear rate of 1 s^?1 exhibited a minimum (η_min) and a maximum (η_max), and the concentration–temperature superposition for η could be applied; (2) the behavior of η at relatively high shear rates as a function of shear rate or polymer concentration was typical of lyotropic liquid crystals. The MW dependence of η_min was greater than that of η_max for EC solutions. The behavior of the elastic parameters such as Bagley correction factor (v), entrance pressure drop (ΔP_ent), and die swell (B) at relatively high shear rates for EC solutions was essentially similar to that for HPC solutions: (1) the shear rate or stress dependence of the elastic parameters was greatly dependent on whether the polymer solution was in a single phase or biphase; (2) with respect to concentration the elastic parameters showed a maximum and a minimum and the maximum or minimum point for each parameter was not always identical to each other. η for the isotropic or fully anisotropic solutions at a given concentration (C) increased, whereas η for the solutions in the vicinity of the biphasic region showed a minimum, with respect to MW. The slope of η at a given shear rate vs. CM _w depended on shear rate, and this slope for the isotropic solutions appeared to be greater than that for fully anisotropic solutions. ΔP_ent and v at a given concentration showed either a monotonical increase or a maximum or minimum with MW, and this behavior was not fully consistent with that of η. B for the isotropic solutions increased and B's for both biphasic and fully anisotropic solutions were almost constant, with MW.     

VIscometric behaviour of Kevlar fibre filled liquid crystalline solutions of ethyl cellulose in m-cresol

Liquid crystalline solutions of ethyl cellulose in m-cresol were mixed with Kevlar® fibres, and the viscometric behaviour with respect to temperature of those filled systems was determined with a cone-plate type viscometer. The viscosity of the systems exhibited a maximum and a minimum at temperatures denoted by T_max and T_min' respectively. The effects of fibre on the critical temperatures (T_max and T_min) and critical concentrations (C_a and C_b) and on the viscosity enhancement are discussed. T_max and T_min decreased with fibre concentration for single-phase anisotropic solutions, whereas they increased for the biphasic solution. The critical concentrations increased with fibre concentration and C_b was more sensitive to the fibre than C_a. The viscosity enhancement due to the fibre depended on the phase of solution. In the single-phase (isotropic and anisotropic), the viscosity enhanced with fibre; however, in the biphasic solution, the effect was not simple. The viscosity enhancement for the single-phase anisotropic solutions with fibre was lower than that for the isotropic solutions.     

Effect of addition of cellulose powder on the viscometric behavior of liquid crystalline solutions of ethyl cellulose in m-cresol

Steady-state shear viscosity for the liquid crystalline ethyl cellulose solution filled with cellulose powders was determined using a cone-plate-type viscometer and the effects of cellulose powder content, powder aspect ratio and temperature on the viscometric behavior and phase transformation were discussed. The addition of powder increased the viscosity and decreased the activation energy (E_a) for flow, but did not affect the phase transformation. The viscosity and E_a depended on the aspect ratio; with greater aspect ratio, the viscosity enhancement was accelerated and E_a as well as the decrease in E_a with powder content increased. The phase transformation did not depend on the aspect ratio, the dependences of viscosity and of E_a on powder content depended on the solution phase; the dependences for the anisotropic phase were smaller than those for the isotropic one. The findings appeared to originate from the alignments of powders and rod-like molecules.     

Electro-rheological effect and dynamic rheological properties of a blend composed of two liquid crystalline materials with different molecular weight

Electro-rheological (ER) effect of a blend composed of two liquid crystalline materials with different molecular weights is described in this article. The results indicated that ER effect of the blend was observed at the temperature range where each neat sample did not show ER effect. Furthermore, both storage modulus (G′) and loss modulus (G″) decreased drastically at the temperature range for the blend in dynamic viscoelastic measurements. We show that steady ER effect could be obtained by using a blend made up of two liquid crystalline components, whereas remarkable increment in shear stress was not observed for each component under applied electric field.     

Viscometric behavior of ternary concentrated solutions of hydroxypropyl cellulose and ethyl cellulose in m-cresol

The shear viscosity of blend solutions of hydroxypropyl cellulose (HPC) and ethyl cellulose (EC) in m-cresol (both HPC/m-cresol and EC/m-cresol systems form lyotropic liquid crystals) was determined by cone-plate-type and capillary-type viscometers. The textures for the same systems at rest and undergoing shear were also observed with a polarized microscope. At shear rate of 1 s^?1, viscosity exhibited a maximum and a minimum with respect to temperature, and this suggested that the phase of the matrix dominated the viscometric behavior of the ternary systems; the blend composition dependence of the viscosity was not additive, and this suggested that HPC and EC were immiscible. At relatively high shear stress, the blend composition dependence of the viscosity greatly depended on the total polymer concentration of the solutions and was quite different from that at low shear rate; the texture of the anisotropic solutions was also different from that at low shear rate. Our findings suggested that the dependence of viscosity on shear and concentration for pure HPC solution was different from that for pure EC solution.     

Phase behaviour and bistable effect of a mixture comprising a dye side chain liquid crystalline polymer and a low molecular weight liquid crystal

Phase behaviour and bistable effect of dye side chain liquid crystalline polymer (dye LCP)/low molecular weight liquid crystal (LC) mixtures have been investigated. The smectic dye LCP was observed to be miscible with the nematic LC over wide ranges of concentration and temperature. The electro-optical effects of the dye LCP/LC mixtures could be classified into the turbid and the transparent states upon a respective application of electric fields at low and high frequencies. Both transparent and turbid states of the mixture could be maintained stable, despite an electric field having been turned off.     

Synthesis and characterization of high molecular weight side chain liquid crystalline/photoactive polymers

Various liquid crystalline and photoactive azobenzene monomers were synthesized and attached to copoly(methyl methacrylate‐glycidyl methacrylate) [copoly (MMA‐GMA)] to get high molecular weight side chain liquid crystalline (LC)/photoactive copolymers. Further, spacers are generated in situ and reactive groups are obtained after the modification. All monomers and polymers were thoroughly characterized by FTIR, ¹H and ¹³C NMR, UV‐VIS spectrophotometry, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy. All side chain LC polymers showed higher thermal stability than that of copoly(MMA‐GMA). Three LC and one azo monomer exhibited characteristic nematic mesophase where as one LC monomer has shown nematic and sanded smectic‐A texture. The rate of trans‐cis isomerization of polymer was lower than that of the monomer and both monomers and polymers showed slow back isomerization. Present approach offers convenient way to synthesize high/desired molecular weight photoactive LC polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Bistable light scattering effects in a (side chain liquid crystalline polymer)/(low molecular weight liquid crystal) composite and in a ferroelectric liquid crystalline polymer

The electro-optical effects and aggregation states of liquid crystalline polymer (LCP)/ low molecular weight liquid crystal (LC) composite and ferroelectric liquid crystalline copolymer (FLCP) have been investigated. The nematic LCP was observed to be miscible with the nematic LC over wide ranges of concentration and temperature. The binary mixture showed an induced smectic phase in the range of 80/20-20/80 mol%. The electro-optical effects of the LCP/LC composite in an induced smectic phase could be classified into the turbid (light- scattering) and the transparent states upon application of AC and DC electric fields, respectively. The transient scattering mode was obtained by repeated voltage polarity reversal in the chiral smectic C phase of FLCP. The reversible transparent-opaque (light scattering) change was observed in the chiral smectic C state upon application of DC and AC electric fields, respectively. Both transparent and light-scattering states of the LCP/LC composite and the FLCP could be maintained, even after the electric field had been turned off (memory effect). The bistable effects of LCP/LC composite and FLCP are opposite under the same conditions. A novel type of electro-optical effect on light scattering was obtained for liquid crystalline polymer in the smectic states.     

Measurement of molecular orientation in thermotropic liquid crystalline polymers

Procedures for obtaining molecular orientational parameters from wide angle X-ray scattering patterns of samples of thermotropic liquid crystalline polymers are presented. The methods described are applied to an extrusion-aligned sample of a random copolyester of poly(ethylene terephthalate) (PET) and p-acetoxybenzoic acid. Values of the orientational parameters are obtained from both the interchain and intrachain maxima in the scattering pattern. The differences in the values so derived suggest some level of local rotational correlation     

Dielectric relaxation and mechanical properties of liquid crystalline epoxy thermosets

This article describes the dielectric relaxation behavior and mechanical properties of novel liquid crystalline (LC) epoxy thermosets. Thermal simulated current experiments show that there is an additional relaxation caused by the local orientation of mesogens. From the mechanical test, it is found that the LC thermoset exhibits higher tensile strength and even little more deformation. It shows that the cured networks can be strengthened by LC domain orientation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1568–1573, 2000     

Acetylation behaviour of cotton and bagasse celluloses. III. Upgrading pulps by extraction with sodium hydroxide-borax solutions

The presence of borax during alkali refining of pulps increased the solubility of the short-chain celluloses and hemicelluloses and thus improved their chemical characteristics. Small improvements in the chemical characteristics of cotton linters took place. A stronger effect was observed in case of the dissolving pulp and a more pronounced effect took place in case of the kraft pulp. Cold 20% NaOH refining was more effective than hot 5% NaOH refining. The physical and sub-microscopic characteristics of linters were mainly affected. Refining lowered the D.P., increased the affinities towards water and alkali, decreased the crystallinity, and improved the reactivity towards xanthation. The presence of borax resulted in a more open and accessible fine structure and better reactivity. Cold refining of the dissolving and kraft pulps resulted in lower reactivity than hot refining and the presence of borax improved the reactivity. It also increased the yield of cellulose acetate. The increase in the solubility of the short-chain celluloses and hemicelluloses resulting from the presence of borax resulted in better homogenisation of the pulp. This was reflected in better chemical and physical characteristics of the acetate.     

Structural transitions in liquid crystalline solutions of some cellulose derivatives

It was found that the domains of the mesophase of the investigated systems have cylindrical symmetry and a different direction of the maximum polarizability: for ethylcellulose and cellulose diacetate, the polarizability is directed along the axis of the cylinder, while it is at an angle of 45‡ for hydroxypropylcellulose. Formation of liquid-crystalline spherulites in the thermotropic transition of isotropic solutions of ethylcellulose in formic acid to the mesophase was demonstrated. In the liquid crystal—isotropic liquid phase transition, a characteristic extreme of the intensity of light scattering is observed near the region of melting of the liquid crystalline matrix, so that this method can be used for identifying the region of the existence of a two-phase “corridor”. Translated from Khimicheskie Volokna, No. 5, pp. 25–27, September–October, 1997.     

Conformational relaxation time in polymer solutions by elongational flow experiments: 1. Determination of extensional relaxation time and its molecular weight dependence

The nature of chain extension of high-molecular weight atactic polystyrene in an elongational flow field was investigated. In particular, we studied the sudden onset of high extension which, according to theory, is governed by the expression $\text{?}\text{?}{}_{\mathrm{c}}\text{τ = 1.}$ The molecular weight dependence of $\text{?}\text{?}{}_{\mathrm{c}}$ (the critical strain rate at which high extension occurs) was examined, and the corresponding relaxation time, τ, which would be relevant to the above expression was considered. The experimental measurements of absolute values and the functional dependence on molecular weight of the relaxation times demonstrates that it is the relaxation time associated with the Zimm non-free-draining model which is appropriate to this coil-stretch transition.     

Gel formation and liquid crystalline order in cellulose triacetate solutions

The formation of a liquid crystalline state of cellulose triacetate solution in trifluoroacetic acid was studied using optical microscopy, polarimetry and circular dichroism measurements. Below a critical concentration of $\text{34}\text{g}\text{100}\text{ml}$ a clear isotropic solution was formed. Solutions more concentrated than this were in the cholesteric liquid crystalline state. If water was added to the solution, a gel phase was formed if the polymer concentration was above a critical value. We interpret our observations in terms of the Pincus-de Gennes theory and show that the formation of liquid crystalline order involves both inter-and intramolecular forces.     

The synthesis and thermotropic liquid crystalline behavior of mesogenic moiety-linked ethyl cellulose

Summary In this paper, a new mesogenic moiety was synthesized and characterized by IR, NMR, and MS. The mesogenic moiety-linked ethyl cellulose derivative was prepared by reaction of 4-methyloxyphenyl-4-oxyaceticacid benzoate with ethyl cellulose [EC, degree of substitution (DS) 2.1] through esterification. The polymer was characterized by IR, NMR, DSC, and hot-stage coupled polarizing microscopy. The DS of mesogenic unit is 0.49. The mesogenic moiety-linked ethyl cellulose derivative showed a thermotropic liquid crystalline behavior. Received: 12 November 2001 /Revised version: 7 January 2002/ Accepted: 16 January 2002     

Properties of a thermotropic liquid crystalline polymer blended with different thermoplastics

Thermal, rheological, morphological, and mechanical properties of a thermotropic liquid crystalline polymer, TLCP (copolyester Vectra A-950 from Hoechst), blended with a polycarbonate (PC), a polyethylene glycol terephthalate (PETG), and a blend of PC and PETG (20/80) are presented and discussed. Important supercooling effects are observed for the TLCP. For the blends the glass transition temperature of the matrix is shown to decrease slightly, suggesting partial miscibility of the components. A finer dispersion is observed for the TLCP/PC blends, at least for TLCP concentrations lower than 20%, for which the mechanical properties are quite good. For higher TLCP concentrations, as well as for the other two matrices, the mechanical properties follow more or less the mixing rule, and the morphology of the blends suggests poor adhesion. We were unable to obtain fibrillar structures by extruding the blends through a capillary rheometer; in the TLCP/PC blends, the TLCP domains were too small, and for the other blends the extrudates had not enough melt strength.     

Infrared-spectroscopic investigations of molecular order in liquid crystalline side chain polymers

Summary Infrared dichroism was used to determine the order parameters of liquid crystalline side chain polymers. By this the order parameters of the main chain, of the spacer and of the mesogenic group can be obtained separately. Therefore spectra of two liquid crystalline polyacrylates were recorded with polarized light at different temperatures. In a poly(acrylate) with 6 CH₂ groups in the spacer a high order parameter was found not only for the mesogenic group, but also for the spacer and the main chain. The orientation of the poly(acrylate) with a spacer of only 2 CH₂ groups is lower due to the stronger interaction of main chain and mesogenic group.