Phase transitions in solutions of hydroxypropoyl cellulose and cyanoethyl cellulose

LC phase transitions in mixtures of cyanoethyl cellulose and hydroxypropyl cellulose with different solvents have been studied by the cloud point and polarization microscopy methods and polarization photoelectric measurements. It has been found that, as the solvent polarity is decreased and the molecular mass of a polymer is increased, boundary curves delimiting the regions of isotropic and anisotropic solutions shift to the region of lower concentrations.     

Effect of magnetic field on phase transitions in solutions of cellulose derivatives

LC transitions occurring in mixtures of cyanoethyl cellulose with DMAA or DMF and hydroxypropyl cellulose with ethanol, DMAA, or water in the presence and absence of magnetic field have been studied. With an increase in the polarity of solvent molecules and a decrease in the molecular mass of the polymer, the LC phase develops at higher concentrations and lower temperatures. Under application of magnetic field, the domain structure is formed in solutions and the temperature-concentration region of the LC phase widens. Cyanoethyl cellulose and hydroxypropyl cellulose solutions are found to possess memory: after the magnetic field is switched off, the orientation of macromolecules and the increased temperature of phase transitions are preserved for many hours. As the molecular mass of the polymer is increased, the ability of macromolecules to orient themselves in the magnetic field declines. The threshold mechanism governing the effect of magnetic field on LC transitions in polymer solutions has been discovered. The critical value of magnetic intensity that brings about a shift in boundary curves is consistent with the value of H _cr necessary for the cholesteric liquid crystal-nematic liquid crystal phase transition.     

Effect of a magnetic field on the rheological properties of the systems hydroxypropyl cellulose–ethanol and hydroxypropyl cellulose–dimethyl sulfoxide

With the use of viscometry, the cloud-point method, polarization microscopy, the turbidity-spectrum method, and a polarization photoelectric apparatus, the relaxation pattern of the rheological behaviors, phase transitions, and structures of the systems hydroxypropyl cellulose–ethanol and hydroxypropyl cellulose–dimethyl sulfoxide are studied. The regions of existence of isotropic and anisotropic phases and the concentration dependence of the sizes of supramolecular particles are determined. It is found that a magnetic field increases the viscosities of solutions. The concentration dependences of viscosity and particle size are described by curves with maxima.     

Phase behavior and structure of liquid crystalline solutions of cellulose derivatives

Summary Structural and thermodynamic characteristics of liquid-crystalline solutions of four cellulose derivatives in a range of solvents were studied. Basic observations were made on these systems using polarized light microscopy, small angle light scattering, dilute solution and concentrated solution viscosities. The polymers studied include hydroxypropyl cellulose (HPC), cellulose acetate butyrate (CAB), ethyl cellulose (EC), and cellulose triacetate (CT). The formation of the liquid crystalline phase was shown to strongly depend on polymer concentration, solvent type and temperature. The critical volume fraction of polymer required to form the liquid crystal phase varied significantly as the solvent changed. The critical volume fraction decreased with increasing solvent acidity and polymer intrinsic viscosity in a given solvent. The breadth of the two phase region seems to decrease with increasing acidity. The liquid crystalline phase was in most cases determined to be cholesteric. In all cases positively birefringent cellulose derivatives form negative spherulitic domains. In one case, the negativity birefringent system (cellulose triacetate) formed positively birefringent spherulitic liquid crystalline domains. This is interpreted to mean the structure organizes itself by a tangential alignment of polymer chains within the domain. SALS measurements appear to detect domains and in some cases cholesteristic pitch.With 5 figures and 4 tables     

Rheology of liquid-crystalline solutions of hydroxylpropyl cellulose filled with layered silicate particles

The rheological properties of nanocomposites with an anisotropic matrix are systematically studied. As a matrix, a 60% solution of hydroxypropyl cellulose in PEG is used. In accordance with the phase diagram, it demonstrates the LC-isotropic-state transition along the temperature scale. The solution is filled with Na-montmorillonite particles (1.0–7.5%). The rheological characteristics of solutions under steady-state shear flow, periodic (harmonic) oscillations with different amplitudes, and uniaxial extension at the constant stretching rate are investigated. Experiments are performed at various temperatures, and the properties of the system are compared with the phase state of the matrix. The viscoelastic properties of the material are described by a model with a single relaxation time. The abnormal behavior of the storage modulus in the low-frequency range is observed. When the matrix is transformed into the LC state, the yield point becomes well-defined and the shear viscosity abruptly increases with an increase in the content of the LC phase. The above-described effects are discussed in terms of the ideas that two competing structures exist in the system, one of which is formed by the LC domains of solution, while the other structure is based on the nanofiller capable of forming ordered structures. Deformation, especially longitudinal flow, facilitates self-organization of the system.     

Structural evolution of liquid-crystalline solutions of hydroxypropyl cellulose and hydroxypropyl cellulose-based nanocomposites during flow

The phase state and orientation and dissipative characteristics of biphasic LC HPC-water solutions and filled systems formed on their basis during shear flow are studied by various methods. The concentration of solutions is selected on the basis of the corrected phase diagram constructed with the use of optical interferometry. Flow curves and concentration dependences of viscosity provide additional information about the phase state and structure of the samples and the role of fillers in the rheological properties of solutions. X-ray diffraction data are obtained with the use of a Couette cell consisting of two coaxial capillaries. In the case of a clay suspension in water, practically no orientation is attained. However, in the isotropic 30% solution, clay particles easily orient, a result that indicates an important role of the viscoelasticity of a medium in the orientation process. The development of orientation of HPC macromolecules and clay particles in relation to the shear rate is analyzed separately for systems with the biphasic matrix (LC + isotropic phase). In addition, the time decay of the orientation parameter during relaxation is investigated. It is shown that higher shear rates cause a more rapid relaxation of orientation, for which recovery of the cholesteric helix typical for LC solutions of cellulose derivatives in the equilibrium state plays an important role. Order parameters (separately for the two components) are calculated, and their evolution with the shear rate and total deformation is investigated for systems containing clay nanoparticles (also the structure-active component) in LC solutions. On the basis of these data, it is hypothesized that clay particles form the columnar mesophase, which, under certain conditions, may transform into the discotic mesophase. This transition is responsible for a certain decrease in the order parameter of HPC apparently due to the instability effect of the director. It is found that shearing substantially affects the structure of the system composed of two mesophase species; specifically, it either facilitates the reinforcement of one of them or provokes structural transitions.     

Phase transitions,structures, and rheological properties of hydroxypropyl cellulose–ethylene glycol and ethyl cellulose–dimethylformamide systems in the presence and in the absence of a magnetic field

Phase transitions, structures, and rheological properties of hydroxypropyl cellulose–ethylene glycol and ethyl cellulose–dimethylformamide systems in the presence and in the absence of a magnetic field have been studied. The application of the magnetic-field results in increases in viscosity and supramolecular particle size in solutions of cellulose ethers. Concentration dependences of viscosity and particle size are described by curves with maxima.     

Effect of Component Nature on Liquid-Crystalline Transitions in Solutions of Cellulose Ethers

The experimental data on phase liquid-crystalline transitions in solutions of cellulose ethers are summarized. The effect of polymer molecular mass, the rise of which leads to the shift of boundary curves to the regions of higher temperatures and lower polymer concentrations, is considered. The replacement of the hydroxypropyl radical in cellulose ether units by the ethyl or hydroxyethyl radical leads to a decrease in the concentration of the LC phase. It is shown that the higher the polarity of solvent molecules, the more negative the Gibbs energy of mixing and the higher the second virial coefficients, i.e., the better the solubility of cellulose ethers.     

Rheological properties and phase behavior of a hydroxypropyl cellulose-poly(ethylene glycol) system

The relaxation and phase behavior of solutions of hydroxypropyl cellulose in poly(ethylene glycols) of various molecular masses has been studied by dynamic mechanical analysis. The dynamic mechanical data are compared with the results of microinterferometry and polarization-microscopy measurements. The combination of optical and mechanical characteristics makes it possible to construct generalized phase- relaxation diagrams for the binary systems under study. Solutions based on lowmolecular-mass poly(ethylene glycol) are characterized by LC equilibrium. With an increase in the molecular mass of poly(ethylene glycol) in a certain temperature-concentration region, amorphous phase separation takes place and the phase diagram is the superposition of LC and amorphous equilibria. The relaxation properties of the systems are sensitive to the phase state and its transformation.     

Phase transitions in liquid crystalline solutions of hydroxypropyl cellulose under deformation

Phase transitions and the physical state of the hydroxypropyl cellulose-dimethylacetamide system under static conditions and in a shear field were studied by the cloud-point and polarized optical microscopy techniques with a polarization-photoelectric setup and a modified plasticorder. The deformation of solutions leads to a change in their structure and elevation of liquid-crystalline phase formation temperatures, a result that is due to the additional orientation of macromolecules in the flow direction. The ability of macromolecules to be oriented in a shear field decreases with an increase in the molecular mass of the polymer. The influence of deformation on phase transitions in hydroxypropyl cellulose solutions is nonmonotonic in character.     

The solubility of cellulose in liquid ammonia/salt solutions

The dissolution of cellulose in solutions of liquid ammonia and ammonium thiocyanate is discussed. Viscosity measurements on dilute solutions of cellulose in this solvent over a range of shear rates and shear stresses are reported. A four-bulb Ubbelohde suspended level viscometer was used for the measurements. Plots of log [η] versus log M gave Mark-Houwink coefficients of a = 0.95 and K = 6.686 × 10^?5 at 25°C for [η] as dl/g. The Bloomfield equation was used to calculate effective bond lengths (b) from limiting viscosity numbers of cellulose in solutions of ammonia/ammonium thiocyanate and Cuene, respectively. Results indicate that cellulose may have similar configurations in both solvents and also that the ammonia solutions are true cellulose solutions. Miscibility of the cell- ulose/ammonia/ammonium thiocyanate solutions with organic solvents, such as glycerol, is also reported. Further, a few interesting characteristics of the liquid ammonia/ammonium salt solutions, discussed briefly, are the convenient boiling point, the rheological behavior, and the relatively high concentration of cellulose obtainable.     

Rheological properties of poly(1-trimethylsilyl-1-propyne) solutions

The phase state and rheological properties of poly(1-trimethylsilyl-1-propyne) solutions in toluene and cyclohexane are studied. Samples of poly(1-trimethylsilyl-1-propyne) have the same backbone structure (cis-trans configuration ratio) but different molecular masses. Phase diagrams of these systems are derived via optical interferometry. It is found that they have an upper critical mixing temperature (UCMT) whose value exceeds the boiling points of the individual solvents. The two solvents exhibit limited solubility with respect to the studied polymer, and this parameter decreases with an increase in the molecular mass of the polymer. In the transition from dilute to concentrated solutions, the pattern of the rheological behavior changes from Newtonian to pseudoplastic. The concentration dependences of the zero-shear-rate viscosity of the solutions are typical for flexible-chain polymers. The viscous behavior of the poly(1-trimethylsilyl-1-propyne)-solvent system can be described through a single generalized viscosity-concentration relationship if dimensionless reduced values that take into account the contribution of the molecular mass, the nature of the solvent, and the pattern of intermolecular interactions in the solutions are used as the argument and the function.     

Rheology of a mixture of liquid-crystal polymers in solution

The rheological behavior of a mixture of two liquid-crystal polymers, hydroxypropyl cellulose and ethyl cellulose, in acetone solution is studied. The total polymer concentration in the solvent is held constant (40%) as the ratio of the two polymers is varied. The mixtures are anisotropic, isotropic, or biphasic (isotropic/anisotropic), depending on the concentration. Curves of viscosity vs shear rate for all the mixtures studied show three regions of viscosity, as described by Onogi and Asada for liquid-crystal polymers. The viscosity as a function of the weight ratio of the two polymers at constant shear rate exhibits deviations from additivity of viscosities of the two components at all concentrations. In mixtures of two polymers in the melt, deviations are also observed; the negative ones are attributed to phase separation and the positive ones to homogenous mixing (comparison with the phase diagram). All the mixtures studied (anisotropic, isotropic, or biphasic), show ranges of shear rates where the first normal-stress difference is negative, as is generally observed for anisotropic liquid-crystal polymers. It is concluded that the isotropic solutions become anisotropic under shear, as they are not far from the critical concentration. © 1994 John Wiley & Sons, Inc.     

Phase transitions of liquid crystalline cyanoethyl cellulose solutions under static conditions and in shear field

Phase transitions in the systems cyanoethyl cellulose-DMF, cyanoethyl cellulose-DMAA, and cyanoethyl cellulose-(trifluoroacetic acid + methylene chloride) were studied by means of the cloud-point and polarization microscopy techniques, as well as with a photoelectric polarization unit and a modified plasticorder. It was shown that the LC phase appears at higher concentrations and lower temperatures as the polarity of solvent molecules increases. The shear deformation of cyanoethyl cellulose solutions in DMF and DMAA results in the expansion of the temperature-concentration region of existence of the LC phase. The effect of shear field on phase transitions in cyanoethyl cellulose solutions is nonmonotonic in character.     

Mesomorphic solutions of cellulose triacetate in halogenated organic acids and mixtures of trifluoroacetic acid and dichloromethane

Cellulose triacetate (CTA) forms liquid-crystalline solutions in trifluoroacetic acid, dichloroacetic acid, and mixtures of trifluoroacetic acid and dichloromethane. Brilliant iridescent coloration, high optical rotations, and birefringent regions with swirl-like fingerprint patterns suggested the formation of cholesteric liquid crystals. Trifluoroacetic acid–dichloromethane is a particularly excellent solvent mixture to form liquid-crystal solutions of cellulose acetate. Crude bulk viscosity measurements confirm the formation of an anisotropic phase, and the temperature dependence of the critical concentration for formation of the anisotropic phase, obtained by bulk viscosity measurements at various temperatures, provides confirming evidence. Viscosity decreases with aging, suggesting that CTA is slowly degraded in the solvents studied. This is also confirmed by optical rotatory measurements and by polarizing microscope observations. The miscibility gap is observed as a function of molecular weight, and the differences between the experimental data and Flory's prediction are discussed.     

Rheological properties of mixed solutions of cellulose and layered aluminosilicates in N-methylmorpholine-N-oxide

The structure and rheological behavior of cellulose solutions in the high-polarity donor solvent N-methylmorpholine-N-oxide containing particles of layered aluminosilicates of various natures, namely, natural hydrophilic montmorillonite (Cloisite Na⁺) and hydrophobized montmorillonite (Cloisite 20A), are studied. The rheological properties of the mixed systems cellulose-N-methylmorpholine-N-oxide-Cloisite Na⁺ and cellulose-N-methylmorpholine-N-oxide-Cloisite 20A are similar, although their structures are different. This similarity may be explained by the fact that the highly developed structure of the cellulose matrix phase resulting from strong interactions between polar components of the system exerts the decisive effect on the character of flow of mixed solutions. Therefore, the filler assumes the minor role. The concentration dependences of solution viscosity turn out to be atypical when the content of moisture in Cloisite 20A is increased above the equilibrium value and when M₂Cloisite Na⁺ nanoparticles modified in a certain manner are introduced into cellulose solutions.     

Rheological behavior of cellulose/silk fibroin blend solutions with ionic liquid as solvent

The rheological behavior of cellulose and silk fibroin blend in 1-butyl-3-methylimidazolium chloride was studied. The data from the rheological results was analyzed to understand the microstructure of the blend solutions. The viscosity and dynamic modulus of the blend solution decreased with increasing ratio of silk fibroin. While comparing the experimental results with the calculated data from the log-additivity rule, it is revealed that zero-shear viscosity, dynamic modulus show positive–negative deviations and a typical continuous–discrete type of morphology could be imaged. At lower shear rate, the change of phase morphology took place at the ratio of about 0.5 volume fraction of cellulose. However, the blend solution showed positive deviations for all cellulose/silk fibroin blend ratios at high shear rate, which indicates that the dispersion of cellulose and silk fibroin was improved under shear stress. The properties of cellulose/silk fibroin blends observed by Fourier transform infrared spectroscopy and scanning electron microcopy agreed with the result from rheology.     

Viscometric behavior of liquid-crystalline solutions of hydroxypropyl cellulose in N,N-dimethylacetamide and in dimethylsulfoxide: Effects of temperature and concentration

Viscometric properties of two kinds of hydroxypropyl cellulose (HPC) solutions which exhibit liquid-crystalline behavior under certain conditions were determined by using a cone–plate viscometer. Measurements included the temperature and concentration dependences of viscosity. A phenomenological superposition for the viscosity was also tried. The viscosity for the solutions of HPC both in N,N-dimethylacetamide and in dimethylsulfoxide displayed a minimum and a maximum with respect to temperature and the specific viscosities at the minimum and the maximum decreased with increasing concentration. Concentration–temperature superposition for the viscosity of both systems could be applied over a limited concentration range. The physical interpretation is still obscure.     

Approach to generalization of concentration dependence of zero-shear viscosity in polymer solutions

The possibility of constructing zero-shear viscosity master curves valid for the entire range of concentration for a large number of polymer solutions in different solvents independent of molecular weight and the nature of the solvent is considered. The results obtained show that the parameters characterizing the individual macromolecular chain., viz., the dimensions of the polymer coil and the rheological effectiveness of segmental interactions, are significant in determining the viscosity of polymer solutions from very dilute to highly concentrated ones. The relation between the parameter of rheological interaction and characteristics of polymer solutions such as the flexibility of the polymer chain and the Flory-Huggins parameter is discussed. This permits one to separate the influence of the energy and entropy factors on the concentration dependence of zero-shear viscosity.     

Structural investigations of polymer liquid-crystalline solutions: Aromatic polyamides,hydroxy propyl cellulose,and poly(γ-benzyl-L-glutamate)

A comparative structural investigation of the characteristics of polymer liquid-crystalline solutions including Kevlar® (PPD-T)/sulfuric acid, poly(Cl-p-phenylene terephthalamide) (Cl-PPD-T)/sulfuric acid, poly(γ-benzyl-L-glutamate) (PγBLG)/dioxane, and hydroxypropyl cellulose (HPC)/water was undertaken. Experimental procedures included polarized light microscopy, light scattering, absorption spectra, and x-ray diffraction on solutions at various concentrations and temperatures. Both the two-phase region at the onset of liquid-crystal formation and the wholly anisotropic phase were investigated. Each solution exhibited distinctive characteristics. The PPD-T and Cl-PPD-T solutions were nematic, and the PγBLG and HPC solutions were cholesteric. In the two-phase region the PPD-T, Cl-PPD-T, and PγBLG (but apparently not the HPC) exhibited negatively birefringent spherulites and aggregates of spherulites. The HPC solutions only exhibited spherulitic structures in the single-phase anisotropic system. The structures and orientations in the anisotropic phase for the various polymer solutions is considered. The helicoidal structural characteristics of the PγBLG and HPC solutions are contrasted.