Crosslinked hydroxypropyl cellulose films retaining cholesteric liquid crystalline order. I. Effects of cast conditions and heat treatment on the textures and order of films

To eliminate the shear-induced band texture and wrinkled texture observed on the free surface of cellulosic solid cast films retaining cholesteric liquid crystalline order, we proposed a storing process of the cast solutions: the solution is stored in the same solvent vapor atmosphere as the solution. The effect of cast conditions (the storing time) on those textures and the cholesteric liquid crystalline order was determined using the lyotropic liquid crystalline solution of hydroxypropyl cellulose in methanol with crosslinker. Furthermore, the effect of heat treatment on the liquid crystalline order in the cast films was determined. The resultant crosslinked films were observed with a polarized microscope and a scanning electron microscope, and were investigated with circular dichroism. Our findings showed that the proposed storing process is needed before starting the cast process. During the process the textures vanished, due to the relaxation of the residual stress in the solution, the cholesteric liquid crystalline order became stable, and the cholesteric pitch decreased with increasing storing time. The heat treatment also affected the liquid crystalline order of the films; the peak in the circular dichroism spectrum sharpened and shifted with heat treatment, and the shift in peak seemed to depend on the crosslinker concentration. Furthermore, the crosslinking proceeded with heat treatment. © 1995 John Wiley & Sons, Inc.     

Chemical crosslinking of hydroxypropyl cellulose and chitosan blends

Two liquid crystal forming polysaccharides, hydroxypropyl cellulose and chitosan, were blended in aqueous acetic acid solutions and were crosslinked with dialdehydes (glyoxal and glutaraldehyde) as crosslinker and hydrochloric acid as catalyzer. The crosslinkability, morphology, solubility, and tensile properties of the cross linked blend films are determined and the dependence of those properties on the blend composition and on crosslinker species are discussed. The crosslinked blend films cast from the aqueous acetic acid solutions were amorphous. The solubility, Young's modulus, and tensile strength of the crosslinked blend films greatly depended on blend composition; those properties appeared to exhibit a maximum and a minimum around given blend compositions. The solubility for the crosslinked blend film cast from glyoxal system was greater than that from glutaraldehyde one. © 1996 John Wiley & Sons, Inc.     

Permeability of oxygen and nitrogen gases in ethyl cellulose solid films retaining cholesteric liquid crystalline order

Ethyl cellulose (EC) films that retain lyotropic and thermotropic cholesteric liquid crystalline order, and an amorphous EC film were prepared. The liquid crystalline order was identified by optical measurements. The comparative permeability of oxygen and nitrogen gases for three kinds of EC film was determined, and the applicability of the EC films that retained cholesteric liquid crystalline order to oxygen enrichment are discussed. The permeability of oxygen or nitrogen gas for the liquid crystalline films was lower than that for the amorphous ones. The activation energy for the permeability coefficient of oxygen gas was ca. 3.5 kcal/mol. The ratio of permeability coefficient for oxygen gas to that for nitrogen gas was less than 4. Interestingly, the permselectivity of oxygen and nitrogen gases for the liquid crystalline films was greater than that for the amorphous ones. © 1996 John Wiley & Sons, Inc.     

Static tensile and dynamic mechanical properties of hydroxypropylcellulose films prepared under various conditions

The films of hydroxypropyl cellulose (HPC), which is a lyotropic and thermotropic liquid crystal, were cast under various conditions of temperature and concentration. The effects of the casting conditions on the static tensile and dynamic mechanical properties of the cast films were determined, and the results were compared with those of films prepared by means of hot compression. The tensile properties of the films prepared by both processes (cast and hot compression) were unsatisfactory in comparison with other liquid crystalline polymers, and this was partly due to water absorbed during the test. In dynamic properties, two distinct transitions were detected. The higher one, around 110°C, was associated with the rotation of an unhydroglucose ring and the lower one, around 25°C, was associated with the T_g. There were no marked differences in the properties between cast films and hot-compressed films, except the disappearance of the T_g for hot-compressed film prepared at a relatively higher temperature. The basis for defining the liquid crystalline structure in cast and hot-compressed films are not directly given in this preliminary paper. However, judging from the dynamic mechanical properties and refractive index data for films prepared by both processes, it appears that dimethylacetamide-cast films and films compressed at 180 and 200°C may have some structures related to liquid crystalline phase and that inter- and intramolecular hydrogen bonding play an important role in lyotropic and thermotropic liquid crystalline behavior for HPC.     

Study on the Optical and Mesomorphic Properties of Cholesteric Side-Chain Liquid Crystalline Elastomers Containing a Nematic Cross-Linking Agent

To study the effect of the content of the nematic cross-linking units on the mesophase behaviors, the optical and mesomorphic properties of liquid crystalline elastomers (LCEs), aseries of LCEs have been synthesized by hydrosilylation reaction with poly(methylhydrogeno)siloxane, a cholesteric liquid crystalline monomer, and a nematic cross-linking agent. The chemical structures and properties of the synthesized LCEs have been investigated by use of various techniques. Homopolymer P₀ bearing only cholesteric component displays a smectic A phase, but elastomers P₁-P₅ containing different content of nematic cross-linking units show a cholesteric mesophase. The reflection wavelengths of theLCEs show a weak temperature dependence at lower temperatures but a strong temperature dependence at higher temperatures. Furthermore, the maximum reflection wavelengths of the LCEs can be stabilized over a wide temperature range when the LCEs are heated, suggesting that the helical structure and pitch of the cholesteric phase can be stabilized with a polymer network.     

Rod-rod and rod-coil self-assembly and phase behavior of polypeptide diblock copolymers

Poly(γ-benzyl l-glutamate) (PBLG) forms a rigid helical rod in organic solvents. Cholesteric liquid crystalline ordering of these rods has been observed in PBLG solutions and cast films. In this research, peptidic block copolymers were created using PBLG in order to determine the effect of an added block on the classic cholesteric ordering. Peptide blocks with varied lengths and inherent secondary structures, random coil or rigid rod, were attached to PBLG molecules. The self assembly/liquid crystalline ordering of these molecules in films cast from various organic solvents was probed with transmission electron microscopy (TEM), atomic force microscopy (AFM), and X-ray diffraction (XRD). In pure PBLG and PBLG diblock copolymers with relatively small additional blocks, cholesteric liquid crystalline ordering was observed in bulk films. However, depending on the kinetics of film formation and the amount of non-PBLG block, significant changes in the nanostructure and microstructure were observed. These purely peptidic block molecules provide the opportunity to pattern materials with peptidic functionalities by taking advantage of block copolymer phase behavior and liquid crystal ordering.     

Evidence for cholesteric morphology in films of cellulose acetate butyrate by transmission electron microscopy

Summary Transmission electron microscopy provides direct evidence of helicoidal cholesteric morphology in films of cellulose acetate butyrate prepared by solvent casting from liquid crystalline solutions in dimethylacetamide. We believe this is the first observation reported of cholesteric structure in a mixed cellulosic ester. Cholesteric morphology was also observed in solvent cast blended films of cellulose acetate butyrate and lignin from liquid crystalline solutions. There are indications that lignin particles may be serving as nucleating surfaces or sites of direct termination for some of the observed cholesteric fingerprint pattern.     

Swelling behavior of crosslinked hydroxypropylcellulose films retaining cholesteric liquid crystalline order,II. Effects of temperature,solvent, and pH

Crosslinked hydroxypropylcellulose (HPC) films were cast from the cholesteric liquid crystalline HPC solution in methanol. The films retained the cholesteric liquid crystalline order. The dependences of swelling behavior of our films in water and propanol on temperature and on pH of the solvent were determined. The response of our films to the changes in water, temperature and in pH was discussed. In water, the equilibrium swelling ratio (B_e) decreased with temperature whereas B_e increased with temperature in propanol. For a given composition of water and propanol, B_e was independent of temperature. B_e in the acidic solvents was higher than in the alkaline solvents. The response data to the stepwise change in temperature revealed that the deswelling behavior was more rapid than the swelling behavior in water, and the swelling-deswelling behavior was reversible. The response to the stepwise change in pH was almost the same as that of the change in temperature, but the surface of the film was attacked by the acid and became fluffy with increasing soaking time.     

Mechano-Optical Response of Novel Polymer Composites Based on Elastic Polyurethane Matrix Filled with Low-Molar-Mass Cholesteric Droplets

Among the various types of liquid crystalline (LC) structures, the cholesteric mesophase attracts special attention in view of helical supramolecular structure determining their specific optical properties. The helix pitch of cholesteric liquid crystals is very sensitive to mechanical stress, resulting in change of their optical properties and position of selective light reflection peak. Here, films of polymer-dispersed cholesteric liquid crystals based on polyurethane elastomer are prepared and studied. Liquid crystal mixtures based on chiral cholesterol derivatives are uniformly dispersed in the form of micrometer-sized droplets in an elastomeric matrix. A significant mechano-optical response of the composites under the action of deformation is demonstrated, and the change in the position of the selective light reflection band during mechanical stress is studied in detail. A shift in the selective light reflection peak by 100 nm or more is found. This process is accompanied by color transformations of brightly colored films. Such materials can be promising for creating stress and deformation sensors, ripple and bending sensors, and other technical devices.     

Improved zein films using polyethylenemaleic anhydride

The effect on the physical properties and solubility of corn protein (zein) films was studied after reaction of zein with polyethylenemaleic anhydride (PEMA). Reactions were carried out in dimethylformamide (DMF) solution where the concentration of PEMA was varied between 0 and 6%. After reaction at room temperature, cast films were prepared, and the physical and solubility properties were determined. Incorporating more than 2% PEMA provided films with increased tensile strength and elongation. Incorporating 6% PEMA provided films with higher tensile strength (32–42 MPa) and improved solvent resistance (100–21% solubility) relative to control. If the films were heated in an oven, the film's solubility decreased further. Solution rheology experiments demonstrated that the zein and PEMA formed a cross‐linked gel with time in DMF. Dynamic mechanical analysis experiments have shown that the PEMA‐modified zein films undergo a dramatic loss in modulus on reaching 116°C, whereas the control experiences this loss at 98°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40122.     

Synthesis and characterization of optically active liquid crystalline polyacrylates containing mesogenic phenylbenzoate groups

A series of novel side chain liquid crystalline polyacrylates with pendant chiral groups were synthesized. It was found that monomers with electron releasing -OC₄H₉ terminal groups seem beneficial for the formation of liquid crystalline phases. Copolymerization of the monomers was carried out and the physical properties of the copolymers were investigated. All synthesized polymers revealed liquid crystalline phases and appeared highly thermally stable with decomposition temperatures (T_d) at 10% weight loss greater than 384 °C and about 50% weight loss occurred beyond 442 °C under nitrogen atmosphere. Two miscible chiral compounds were also synthesized and used as chiral dopants to induce cholesteric liquid crystalline phases of polymers. Liquid crystalline phases of the polymers were investigated using DSC and XRD, and confirmed with POM technique. The optical properties of the induced cholesteric liquid crystalline polymers were investigated using UV-vis spectrometer. The appearance and the color variation of the polymer films before and after UV irradiation were also investigated. Typical helical morphology of the cholesteric liquid crystalline film was analyzed by SEM technique.     

含异山梨醇和胆甾醇的侧链胆甾型液晶聚合物的合成与表征

异山梨醇类单体和胆甾类液晶单体与聚甲基含氢硅氧烷（PMHS）接枝共聚合成系列新型胆甾型侧链液晶聚合物。运用红外光谱（FTIR）、核磁共振谱（1HNMR）、差示扫描量热分析（DSC）、热失重分析法（TG）和偏光显微分析法（POM）等进行表征。单体M1和M2在升、降温过程中均呈现胆甾相液晶织构,聚合物P1～P7为胆甾相液晶。实验结果髭示,较低的玻璃化转变温度使得聚合物具有广阔的应用前景,随着胆甾液晶组分的增加,聚合物的玻璃化转变温度降低,清亮点先降低后升高,液晶相范围起初变化缓慢后变化很快。     

Gas transport phenomena in hydroxypropyl cellulose solid film retaining cholesteric liquid crystalline order

Two kinds of hydroxypropyl cellulose (HPC) films were prepared: one retained cholesteric liquid crystalline order (HPC-A), and another was amorphous (HPC-B). Gas transport phenomena in the HPC-A films were determined at 20°C, which is below the T_g of HPC, compared with those in the HPC-B films, by using mainly oxygen and nitrogen gases; herium and carbon dioxide gases were also used. The permeability coefficient P for the HPC-A films was smaller than that for the HPC-B films by approximately 10 times. The gas permselectivity, defined as the ratio of P for each gas, was affected by the liquid crystalline order, as follows: The permselectivity for the HPC-A films was greater than that of the HPC-B films. The trends of gas permeability and permselectivity for the liquid crystal-forming HPC films were the same as those reported for other liquid crystal-forming cellulosic films. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1465–1470, 1998     

Structures and tensile properties of a magnetically and mechanically oriented liquid crystalline copolyester,Xydar

A wholly aromatic thermotropic liquid crystalline copolyester consisting of p-hydroxybenzoic acid, terephthalic acid, and p,p′-biphenol, one from the Xydar series, was aligned by means of magnetic fields and mechanical methods. The tensile properties of these samples were different depending on the orientation degree and the means used for the orientation. Magnetically oriented films exhibited lower elastic modulus and ultimate tensile strength than mechanically oriented films of the same orientation degree, but the elastic modulus of magnetically oriented films was comparable to that of the mechanically stretched films of lower orientation degrees. This suggests that magnetic fields could be used as an additional means of controlling the orientation of thermotropic liquid crystalline copolyesters during molding or film fabrication. The difference in tensile properties was discussed in relation to the oriented structures examined by scanning electron microscopy, polarizing microscopy, and wide angle X-ray measurement.     

Liquid crystalline polymer laminates

On the basis of a poly(ethylene terephthalate) copolyester containing 60 mol % p-hydroxybenzoic acid, thin liquid crystalline films (160 μm thick) are obtained by melting the polymer at 300°C and chilling at 0°C. The undrawn films obtained have a high degree of orientation as evidenced by X-ray measurements. Due to molecular orientation, these films are characterized by their excellent mechanical properties. In order to avoid losses in the mechanical strength due to increase in their thickness, laminates are prepared using thin liquid crystalline films. Lamination is carried out by annealing under pressure at 170°C for 6 h, resulting in samples with excellent mechanical properties regardless of their thickness. A method is proposed that makes it possible to combine the unique mechanical properties of thin films of liquid crystalline polymers with a lamination process in order to obtain thick and very strong materials.     

Effect of processing on the crystalline orientation, morphology, and mechanical properties of polypropylene cast films and microporous membrane formation

Cast films of a high molecular weight linear polypropylene (L-PP) were prepared by extrusion followed by stretching using a chill roll. An air knife was employed to supply air to the film surface right at the exit of the die. The effects of air cooling conditions, chill roll temperature, and draw ratio on the crystalline orientation, morphology, mechanical and tear properties of the PP cast films were investigated. The crystallinity and crystal size distribution of the films were studied using differential scanning calorimetry (DSC). It was found that air blowing on the films contributed significantly to the uniformity of the lamellar structure. The orientation of crystalline and amorphous phases was measured using wide angle X-ray diffraction (WAXD) and Fourier transform infrared (FTIR). The amount of lamellae formation and long period spacing were obtained via small angle X-ray scattering (SAXS). The results showed that air cooling and the cast roll temperature have a crucial role on the orientation and amount of lamellae formation of the cast films, which was also confirmed from scanning electron microscopy (SEM) images of the films. Tensile properties and tear resistance of the cast films in machine and transverse directions (MD and TD, respectively) were evaluated. Significant increases of the Young modulus, yield stress, tensile strength, and tensile toughness along MD and drastic decreases of elongation at break along TD were observed for films subjected to air blowing. Morphological pictograms are proposed to represent the molecular structure of the films obtained without and upon applying air cooling for different chill roll temperatures. Finally, microporous membranes were prepared from annealed and stretched films to illustrate the effect of the PP cast film microstructure on the morphology and permeability of membranes. The observations of SEM surface images and water vapor transmission rate of the membranes showed higher pore density, uniform pore size, and superior permeability for the ones obtained from the precursor films prepared under controlled air cooling.     

Effect of swelling on the cholesteric structure of ethyl‐cyanoethyl cellulose/crosslinked poly(acrylic acid) composite films

The swelling behavior of ethyl‐cyanoethyl cellulose [(E‐CE)C]/crosslinked poly(acrylic acid) [PAA] cholesteric liquid crystalline composite films and the structural variation of the cholesteric phase during the swelling and the drying process were studied. It was found that the wavelength of the selective reflection of the composite films was shifted to the long wavelength direction during swelling. Both the pitch of the cholesteric phase and the distance between neighboring molecular layers were increased, and the helix axis was inclined after swelling. Moreover, the swelling behavior of the composite films in water was reversible, which means that the optical properties and structural characters of the films could be changed back to their original states after the films were dried from the equilibrium swelling state. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3574–3578, 2004     

Blends of a chlorinated poly(vinyl chloride) compound and a thermotropic liquid crystalline copolyester: Mechanical properties of squeezed flow films

The mechanical properties of squeezed flow films were measured on blends of a chlorinated poly(vinyl chloride) (CPVC) compound and a thermotropic liquid crystalline copolyester of p-hydroxybenzoic acid/poly(ethylene terephthalate) (60/40), hereafter referred to as LCC. CPVC is immiscible with LCC. The most serious and unique problem of liquid crystalline polymers is their tendency to fibrillate when fabricated into films and injection molded parts, primarily because of a high degree of mechanical anisotropy. It has been found that the mechanical anisotropy of LCC and blends could be lessened using nonisothermal squeezing equibiaxial extension flow. The maximum tensile properties of LCC are achieved when processed in the vicinity of 260°C. For blends of CPVC containing LCC, the mechanical properties are dependent on the processing temperature and compositions. Blends with no more than 20 wt% of LCC exhibit significant increases in tensile properties. This is due to the possibility of frozen-in macroscopic biaxial orientation of LCC in the blends during the nonisothermal squeezing flow. Within the range of processable temperatures, the reinforcement of CPVC due to the incorporation of LCC can be achieved at a temperature below the optimum processing temperature of LCC, although the thermal history of blends never reaches that temperature.     

Potential tissue implants from the networks based on 1,5-dioxepan-2-one and ε-caprolactone

The synthesis and characterization of degradable polymeric networks for biomedical applications was performed. Cross-linked films of poly(ε-caprolactone) (PCL) and poly(1,5-dioxepan-2-one) (PDXO) having various mole fractions of monomers and different cross-link densities were successfully prepared using 2,2′-bis-(ε-caprolactone-4-yl) propane (BCP) as cross-linking agent. Reaction parameters were carefully examined to optimise the film-forming conditions. Networks obtained were elastomeric materials, easy to cast and remove from the mould. Effect of CL content and cross-link density on the final properties of the polymer network was evaluated. High CL content or degree of cross-linking led to increase in Young's modulus and decrease in elongation at break. An increase in crystalline domains in films having a higher CL content was observed by optical microscopy. A greater thermal stability was observed in films having a high CL content. The hydrophilicity of the materials could be tailored by changing the CL content. The surface of the films became rougher with higher CL content.     

Crosslinked poly(vinyl alcohol) and starch composite films: Study of their physicomechanical,thermal, and swelling properties

Crosslinked poly(vinyl alcohol) was blended with 10, 20, 40, and 50 wt % starch by a solution‐casting process. The solution‐cast films were dried, and then their physicomechanical properties including tensile strength, tensile elongation, tensile modulus, tear strength and density, and burst strength and density were tested. Thermal analysis was performed by differential scanning calorimetry. A moisture analysis of the PVA/starch films was performed and their moisture content determined. Also investigated were the films'resistance to solubility in water, 5% acetic acid, 50% ethanol, and sunflower oil and their swelling characteristics in 50% ethanol and sunflower oil. The prepared PVA/starch blends showed significant improvement in tensile modulus and in resistance to solubility in water, 5% acetic acid, and 50% ethanol. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1127–1132, 2007