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.     

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.     

Dissipative crystallization of aqueous solutions of hydroxypropyl cellulose

Drying dissipative structures of aqueous solutions of hydroxypropyl cellulose, their viscosities of 2 wt.% solutions ranging from 2 to 2,000 mPa.s were studied on a cover glass, a watch glass, and a Petri glass dish. The thickness profile of the dried film shows the coexistence of a low round hill and a high broad ring on a cover glass. The broad ring size increased as molecular weight and/or concentration of the polymers increased on a cover glass and a watch glass. Microscopic drying crystal patterns of HPC changed as a function of the distance from the film center, which is one of the typical results of the dissipative crystallization. Rod-like microscopic drying patterns originated in the cholesteric liquid crystalline structures were observed. The rods oriented mainly parallel and in some case perpendicularly to the radial direction of the dried film except the central area, where the rods distributed at random. These orientation effects were significant for low molecular weight samples and in a watch glass.     

Morphological studies of liquid-crystalline cellulose derivatives. I. Liquid-crystalline characteristics of hydroxypropyl cellulose in 2-hydroxyethyl methacrylate solutions and in polymer composites prepared by bulk polymerization

The formation of liquid-crystalline structure in hydroxypropyl cellulose (HPC) in the solvent 2-hydroxyethyl methacrylate (HEMA) is described. In addition, an attempt is made to preserve the ordered structure of HPC in a composite by polymerizing the solvent. Optical evidence, including refractive index, absorption spectra, polarized-light microscopy, and x-ray diffraction, indicates that HPC-HEMA solutions exhibit the cholesteric nature of the mesophase over limited concentration and temperature ranges. The polymer composite (HPC-PHEMA) prepared from the liquid-crystalline solution by polymerization of HEMA is endowed with anisotropic organization reflecting liquid-crystalline character. Detailed morphological observations of the composite by electron microscopy show many round particles composed of parallel-stacked, disklike lamellae, and aggregate bodies developed by coalescence of neighboring particles.     

Morphological studies of liquid-crystalline cellulose derivatives. II. Hydroxypropyl cellulose films prepared from liquid-crystalline aqueous solutions

A morphological study of hydroxypropyl cellulose (HPC) was performed on solid films prepared by casting from a liquid-crystalline aqueous solution at rest or under shear. Electron microscopic observations reveal that many round particles composed of stacked disks are densely packed in the interior of a quiescently cast HPC film, while on the film surface formation of fibrous textures is also noted. Shear-deformed HPC films exhibit some interesting morphological features according to the shearing conditions. It is found by electron microscopy that the originally round particles become more and more elongated as shear stress increases. The resulting rodlike fibrillar entities are considerably aligned in the shear direction (SD), but form a banded structure with periodic discontinuities of molecular orientation distribution along the SD. A new mechanism of structural transformation is proposed in order to interpret these results.     

Mechanism of interaction between hydroxypropyl cellulose and water in aqueous solutions: Importance of polymer chain length

The utilization of hydroxypropyl cellulose (HPC) can be regarded as unexpected with regard to certain applications, such as being employed as a solubility enhancer for poorly soluble drugs and as a solubilizing agent for nano-suspensions and amorphous solid dispersions. However, the best results were obtained for low-molecular weight (M_w) HPC grades with a short-chain structure. Therefore, in this study, seven grades of HPC with different polymer chain lengths (M_w) are analyzed in various aqueous solutions by a combination of ¹H quantitative NMR spectroscopy, diffusion NMR spectroscopy, and water ligand observed via gradient spectroscopy; these investigations provide insights into the remarkable solubilizing property of HPC at the molecular and supramolecular levels. Furthermore, the hydration and the water residence time are found to be strongly dependent on the polymer chain length of HPC. The quantitative results obtained herein indicate that HPCs with shorter chain lengths retain smaller amounts of water around their hydrated molecules, as compared to their counterparts with longer chain lengths.     

Phase transitions in liquid-crystalline cyanoethyl cellulose solutions in magnetic field

The cloud-point method and polarization microscopy have been used to investigate the phase transitions and the phase state of cyanoethyl cellulose-dimethylacetamide and cyanoethyl cellulose-dimethylformamide systems in the presence and absence of magnetic field with the help of polarization photoelectric and magnetic setups. The temperature-concentration region of the existence of the liquid-crystalline phase in solutions widens in the magnetic field; the higher the field strength and polymer concentration, the more pronounced this widening. Cyanoethyl cellulose solutions are found to possess “memory”: after the magnetic field is switched-off, the orientation of macromolecules and the increased phase transition temperature are preserved for many hours.     

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.     

Self-organization of macromolecules and liquid-crystalline phase transitions in solutions of cellulose esters

For hydroxypropyl cellulose-ethanol, hydroxyethyl cellulose-water, and cyanoethyl cellulose-DMAA systems, phase diagrams are constructed and the regions of existence of isotropic and anisotropic phases and the dimensions of macromolecules and supramacromolecular particles in a wide composition range are determined through the use of the cloud-point method, polarization microscopy, the turbidityspectrum method, dynamic light-scattering measurements, and a polarization optical apparatus. It is shown that the formation of LC phases with an increase in the polymer concentration is associated with a significant enlargement of supramolecular particles.     

Investigation of water mobility and diffusivity in hydrating micronized low-substituted hydroxypropyl cellulose,hydroxypropylmethyl cellulose,and hydroxypropyl cellulose matrix tablets by magnetic resonance imaging (MRI)

The water mobility and diffusivity in the gel-layer of hydrating low-substituted hydroxypropyl cellulose (LH41) tablets with or without a drug were investigated by magnetic resonance imaging (MRI) and compared with those properties in the gel-layer of hydroxypropylmethyl cellulose (HPMC) and hydroxypropyl cellulose (HPC) tablets. For this purpose, a localized image-analysis method was newly developed, and the spin-spin relaxation time (T(2)) and apparent self-diffusion coefficient (ADC) of water in the gel-layer were visualized in one-dimensional maps. Those maps showed that the extent of gel-layer growth in the tablets was in the order of HPC>HPMC>LH41, and there was a water mobility gradient across the gel-layers of all three tablet formulations. The T(2) and ADC in the outer parts of the gel-layers were close to those of free water. In contrast, these values in the inner parts of the gel-layer decreased progressively; suggesting that the water mobility and diffusivity around the core interface were highly restricted. Furthermore, the correlation between the T(2) of (1)H proton in the gel-layer of the tablets and the drug release rate from the tablets was observed.     

Velocity sedimentation transport properties in dilute and concentrated solutions of hydroxypropyl cellulose in water at different temperatures up to phase separation

Velocity sedimentation measurements have been performed for the system hydroxypropyl cellulose in water in both dilute and concentrated solutions (0–100 kg m^?3) and at temperatures remote from as well as close to θ-conditions (25–40°). In dilute solutions, the experimentally determined concentration dependence of the sedimentation coefficient was compared with that calculated from the theory of Yamakawa; fairly good agreement was obtained. The difference between the sedimentation behaviour under good and poor solvent conditions is also discussed. Furthermore, the frictional properties are discussed and compared with those deduced from diffusion measurements.     

Investigation of molecular order in liquid-crystalline solutions of cellulose triacetate using PMR spectroscopy

Liquid-crystalline solutions of cellulose triacetate (CTA) in trifluoroacetic acid (TFA)–CH₂Cl₂, TFA–1.2-dichloroethane (1,2-DCE) solvent mixtures were examined by means of PMR spectroscopy. CTA forms both cholesteric and nematic phases in these solvents depending on the CTA concentration. In cholesteric solutions the CH₂Cl₂ signal is initially a singlet and then splits into a doublet. The time dependence of the splitting and the effect of CTA concentration are reported. The results suggest that the cholesteric phase slowly changes into a nematic phase in the magnetic field. The splitting of the CH₂Cl₂ proton signal into a doublet and the 1,2-DCE signal into a quartet are due to direct magnetic dipole-dipole interactions. Rotation of the sample in the magnetic field results in the disappearance of the doublet or quartet and suggests that the solvent molecules are originally oriented in the direction of the magnetic field. In the biphasic region, immediate splitting of the CH₂Cl₂ proton signal suggests that the anisotropic phase is nematic.     

Synthesis and characterization of hydroxypropyl cellulose from bacterial cellulose

Bacterial cellulose produced by Acetobacter xylinum has been reacted with propyleneoxide to synthesize hydroxypropyl cellulose(HPC) under different reaction conditions while diluted by toluene. The effects of mass ratio of bacterial cellulose to propyleneoxide, dilutability of toluene, reaction temperature(T) and time(t) were investigated by series of experiments. The degree of substitution(DS), hydroxypropyl content(A) and yield(η) were compared. The optimized product exhibited cold-water solubility and hot-water gelatinization in aqueous medium. Further study was carried out with FTIR, TGA, XRD, SEM and 13C-NMR for characterization. The water/air contact angle measurement reveals that it is a good hydrophobic material with good mechanical properties.     

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.     

Thermodynamics of 1,10-phenanthrolium ion in ethanol—water

Dissociation constants of the 1,10-phenanthrolium ion in different aqueous ethanolic solutions have been determined spectrophotometrically and pH-metrically. Some aspects of the role of the solvent have been discussed.     

Hydrostatic pressure effects on polymer cholesteric liquid-crystalline structure. I. Equilibrium structure of hydroxypropyl cellulose aqueous solution

The effect of pressure on the polymer cholesteric liquid-crystalline structure of hydroxypropyl cellulose aqueous solutions was studied using reflection spectra measurements. Pressures applied to the polymer liquid crystals ranged from 1 to 2000 bar. The equilibrium reflection spectrum of the cholesteric structure shifted to longer wavelengths, showing that the cholesteric pitch of the liquid-crystalline structure increases as the applied pressure increases. At pressures higher than 200 bar the maximum wavelength of reflection shifted linearly with the increase in applied pressure. At lower pressures, the cholesteric structure was influenced by the surface plane of the quartz window.     

Hydrostatic pressure effects on polymer cholesteric liquid-crystalline structure. I. Equilibrium structure of hydroxypropyl cellulose aqueous solution

Abstract

The effect of pressure on the polymer cholesteric liquid-crystalline structure of hydroxypropyl cellulose aqueous solutions was studied using reflection spectra measurements. Pressures applied to the polymer liquid crystals ranged from 1 to 2000 bar. The equilibrium reflection spectrum of the cholesteric structure shifted to longer wavelengths, showing that the cholesteric pitch of the liquid-crystalline structure increases as the applied pressure increases. At pressures higher than 200 bar the maximum wavelength of reflection shifted linearly with the increase in applied pressure. At lower pressures, the cholesteric structure was influenced by the surface plane of the quartz window.     

Interpolymer complex between hydroxypropyl cellulose and maleic acid-styrene copolymer: phase behavior of semi-dilute solutions

The phase behavior of a water/hydroxypropyl cellulose/maleic acid-styrene copolymer (H2O/HPC/MAc-S) system was investigated in the semi-dilute range by turbidimetry, rheology, and optical microscopy. The two polymers under investigation form interpolymer complexes via hydrogen bonding. In the case of a total polymer concentration of cpol = 5 mg . mL(-1) a second phase segregates upon heating the homogeneous ternary system. By applying a constant shear rate (gamma = 50 s(-1)) the phase separation temperature of the system is 10-15 degrees C lower than for an unsheared one. For cpol = 10 mg . mL(-1) phase separation has already occurred at room temperature when the two binary polymer solutions are mixed. The distribution of the partners among the coexisting phases was examined by FT-IR spectroscopy. The stoichiometry of the interpolymeric complex (IPC) was estimated to be HPC/MAc-S = 40:60 (w/w) independent of cpol.     

Aqueous solutions of hydroxypropyl cellulose,Tween 80 and their binary mixtures: Colloid-chemical aspects

Tensiometry, dynamic light scattering, and rheology have been used to study the colloid-chemical properties of hydroxypropyl cellulose, Tween 80, and binary mixtures thereof in an aqueous medium and at water/decane and water/air interfaces. The efficiency of a reduction in the interfacial energy under dynamic and static conditions, the surface activity of the components, capability of self-organization in bulk and at interfaces, as well as emulsifying efficiency of the systems, have been analyzed. It has been found that, in a narrow concentration range and at a certain ratio of the components, they exhibit a synergetic effect with respect to a reduction in the interfacial energy, with this effect being due to the formation of a Tween 80–polymer bilayer via hydrogen bonding between hydroxyl groups of hydroxypropyl cellulose and ethoxy units of Tween 80.     

Revisiting (hydroxypropyl) cellulose (HPC)/water liquid crystalline system

ABSTRACT

The discovery of a cholesteric liquid crystalline phase in concentrated aqueous solutions of (hydroxypropyl)cellulose (HPC) dates back to the 1970s. Due to its biocompatibility, low cost and ease of conversion to fibres and films, HPC is still the target of numerous studies. In this article, some of the properties of the HPC/water lyotropic system are reviewed, and original results describing a humidity-generated instability on HPC fibres are presented. The use of HPC films which respond to external stimuli is highlighted. In particular, novel applications include the manufacture of soft motors driven by a difference of humidity, and the production of electro-optical cells when the solid films are used in conjunction with low molecular mass thermotropic mesogens.