Permeation and separation of organic liquid mixtures through liquid-crystalline polymer networks

A side-chain liquid-crystalline polymer (LCP) was synthesized by the addition of the mesogenic monomer to poly(methyl siloxane) in presence of a Pt-catalyst. When an aqueous solution of 10wt% ethanol was permeated through a LCP membrane by pervaporation at various temperatures, the permeation rate increased with increasing temperature and drastically changed at glass-nematic (Tg) and nematic-isotropic (TNI) transition temperatures of the LCP membrane. The LCP membrane exhibited the waterpermselectivity in the glassy and liquid-crystalline states. The ethanol concentration in the permeate increased with increasing permeation temperature and the LCP membrane changed from the waterpermselectivity to the ethanol-permselectivity around TNI. These results suggested that the permselectivity was influenced by the change of the LCP membrane structure, that is, its state transformation. It was found that a balance of the orientation of mesogenic groups and flexibility of siloxane chains is very important for the permeability and selectivity.     

Effects of shear rate,viscosity ratio and liquid crystalline polymer content on morphological and mechanical properties of polycarbonate and LCP blends

Studies were conducted on the effects of shear rate, viscosity ratio and liquid crystalline polymer (LCP) content on the morphological and mechanical properties of polycarbonate (PC) and LCP blends. The LCP (LC5000) used was a thermotropic liquid crystalline polymer consisting of 80/20 of parahydroxybenzoic acid and poly(ethylene terephthalate) (PHB/PET). The viscosity ratio (viscosity of LCP: viscosity of matrix) was varied by using two processing temperatures. Due to the different sensitivity of materials to temperature, variation in the processing temperature will lead to varying viscosity of the components in the blends. Based on this principle, the processing temperature could be manipulated to provide a favourable viscosity ratio of below unity for fibre formation. To study the effect of shear rate, the flow rate of the blend and the mould thickness were varied. The shear rate has a significant effect on the fibrillation of the LCP phase. The effect was more prominent when the viscosity ratio was low and the matrix viscosity was high. At 5 wt% LCP, fibrillation did not occur even at low viscosity ratios and high shear rates. It was also observed that the LCP content must be sufficiently high to allow coalescence of the dispersed phase for subsequent fibrillation to occur. © 2002 Society of Chemical Industry     

Development of Micro-Debond Methods for Thermoplastics Including Applications to Liquid Crystalline Polymers

Micro-bead and related debond techniques were used to study adhesion of liquid crystalline copolyesters (LCPs) and other semi-crystalline thermoplastic polymers to glass fibers. For polymers with poor flow even at high temperatures, symmetric beads on fibers were difficult to prepare so an alternative sample preparation method was developed where glass fibers were inserted into thin sections of molten polymer. Glass fibers of widely-varying diameters were used in order to extend the dynamic range of the debond techniques in terms of debonding area, showing a significant improvement in precision over that demonstrated previously with micro debond techniques. The fibers were freshly prepared in our laboratory and silane coated when necessary, which allowed us to minimize fiber surface heterogeneity effects which are believed to influence strongly debond test results. It was found that chemical bonding of the LCPs was quite favorable as was indicated by fracture surface analysis and by comparison with the shear strength of the neat resins. The apparent poor interphase strength in fiber-reinforced LCP composites is proposed to be due to orientation of the LCP molecules near the fiber interface leading to a cohesively weak layer of LCP near the interface. Reactive silane coupling agents lead to no improvement in interface strength as compared with bare glass because chemical reaction occurs on both surfaces. This results in very strong interfaces leading to polymer cohesive failure near the interface of all thermoplastics studied here     

Rheology,morphology, and mechanical characteristics of poly(etherether ketone)-liquid crystal polymer blends

This paper is in continuation of our previous paper on Poly(etherether ketone)-liquid crystal polymer (PEEK-LCP) composites. Rheological, morphological, and mechanical properties of polyetherether ketone and a thermotropic liquid crystalline polymer based on hydroxybenzoic acid/hydroxynaphthoic acid have been reported. Addition of LCP resulted in a marked reduction of viscosity and improved processability. Tensile properties improved with increase in LCP concentration. Synergistic effects have been observed at certain LCP concentrations. The elongation at break was found to reduce drastically above 10% of LCP content. This is a characteristic typical of chopped-fiber-filled composites. Morphology of injection molded and capillary extruded samples of the blends showed that the in-situ formed fibrous LCP phase was preserved in a solidified form. The improvement in tensile properties is likely due to the reinforcement of the PEEK matrix by the fibrous LCP phase as observed by scanning electron microscopy. A distinct skin-core morphology was found to develop in the injection molded samples of these blends. Mechanical properties measured in the flow and transverse direction indicated an increase in the degree of anisotropy with an increase in LCP content.     

Rheological,mechanical, and adhesive properties of thermoplastic-LCP blends filled by glass fibers

Rheological, mechanical, and adhesive properties have been studied of two-phase polymer blends containing a liquid crystal copolyester of poly(ethylelene terephthalate) and p-hydroxybenzoic acid plus isotactic polypropylene (PP) with varying compositions and concentrations of glass fibers. Perfect fibrillation of the disperse LC-phase into the PP-matrix in capillary flow was observed at LCP concentrations >20 wt% and temperatures >488 K. This effect leads to a decrease of blend viscosity and a reinforcing of the extrudate's mechanical characteristics. At the same time, more essential reinforcement is achieved by the simultaneous addition of the reinforcing agents both of the LCP and glass fibers. Processing of PP is not impaired. It was found that the adhesive strength increases substantially when the amount of LCP in the blend exceeds a definite level, corresponding to a phase inversion. The results are explained by the formation near the interface of two adhesion layers: the first is composed of pure LCP having a higher surface tension, whereas the second layer represents the blend of various compositions. At small amounts of LCP, the adhesion failure proceeds in the interphase between the LCP and the blend. After the phase inversion, where adhesion strongly increases, the failure of adhesion joints proceeds near the interface between LCP and the glass.     

Blends of a thermotropic LCP and a thermoplastic elastomer. II: Formation and stability of LCP fibers

The formation of fibers during blending of a thermotropic liquid crystalline polymer (LCP) with a thermoplastic elastomer (TPE) using shear flow, and the stability of the fibers and the blend morphologies at elevated temperatures were studied. The polymers used were Vectra A900 (LCP) and Kraton G1650 (TPE). Fiber formation in (predominantly) shear flow was studied using a single screw extruder of which the die was removed. Fibers were obtained in blends with 5 vol% LCP at shear rates as low as 6.3 s^?1. Conventional extrusion through a die was used for preparing materials for the studies of the thermal stability of blends and isolated fibers–isolated LCP-fibers surrounded by a TPE-matrix disintegrate when held above the melting point of the LCP. Annealing of the blends at this melting temperature results in changes of the morphology and in a fairly rapid decrease of the modulus of elasticity.     

Polymer-dispersed liquid-crystal polymers (PDLCPs). Morphology of the LCP droplets

“Synthetic blends” of a flexible polymer forming the matrix and a liquid-crystalline polymer (LCP) forming the dispersed phase have been prepared by transesterification of PET with a mixture of sebacic acid (S), 4,4′-diacetoxybiphenyl (B) and 4-acetoxybenzoic acid (H) in the mole ratio 1:1:2. A change of the synthesis conditions causes marked variations of the chemical composition and the morphology of the phases. The SEM investigation of the inner morphology of the LCP droplets of blends consisting of two phases with fairly different aromatic content has shown that the LCP macromolecules are aligned tangentially at the matrix surface boundary, and that the nematic director configuration is toroidal. When the two phases have closer chemical composition, and are therefore supposed to possess improved mutual compatibility, a perpendicular anchoring of the LCP fibrils to the matrix cavity surface, and an axial configuration of the nematic director, are observed. The expected effect of the nematic configuration of the LCP droplets on their ability to deform into fibrils under appropriate flow conditions is preliminarily discussed.     

Hierarchical structure in LCP/PET blends

The structural hierarchy in injection molded blends of poly(ethylene terephthalate) (PET) and a commercial liquid crystal polymer (LCP), two immiscible polymers, was characterized at various blend compositions. The macroscopic core and skin have a gradient structure and are subdivided into ordered and disordered layers. The sublayers consist of rodlike domains at 25% LCP. The domains become thinner, longer, and more fibril-like with increasing LCP concentration. The interconnection between the LCP domains also becomes more significant at higher LCP concentrations. The highest degree of orientation in the injection direction is at the mold surface and the lowest at the sample center. The LCP orientation reflects the elongational and fountain flow in the mold and increases with increasing LCP concentration. Schematic structural models were used to illustrate the levels of structure in these blends. A minimum exists in the tensile strength, elongation at break, and impact strength with varying blend composition at approximately 50% LCP. The tensile strength of the LCP-rich blends is significantly lowered by the presence of a weldline or an angle between the stress and orientation directions. The unique mechanical properties of the LCP depend on the formation of a highly oriented and highly connected hierarchical structure that does not exist in blends with 75% or less LCP.     

The morphology and rheology of polymer blends containing a liquid crystalline copolyester

The morphology of blends of polycarbonate and nylon 6,6 with a copolyester of 60 mole percent p-hydroxybenzoic acid/40 mole percent poly(ethylene terephthalate) was characterized under different processing conditions. In particular, single-screw extrusion, steady simple shear flow, and flow through a capillary were studied to determine what conditions were necessary for the development of a fibrillar morphology of the liquid crystalline polymer (LCP). Results indicate that some extensional flow is required for the coalescence and extension of the particulate LCP phase. The viscosity of the blends was determined both in a cone-and-plate geometry of a Rheometrics Mechanical Spectrometer at low shear rates and in the Instron Capillary Rheometer at higher rates. In general, only a small (10 or 30 percent) weight fraction of LCP was required to reduce the viscosity of the thermoplastics to that of the polymeric liquid crystal. An attempt was made to correlate the structure of the blends seen under the scanning electron microscope with the observed rheology. Not all aspects of the morphology were possible to explain in terms of the viscous properties of the blends.     

Self‐reinforced polypropylene/LCP extruded strands and their moldings

Polypropylenes (PP) of various molecular weights were mixed with a thermotropic liquid crystal polymer (LCP) and strands were prepared by extrusion and stretching. The strands were subsequently pelletized and then injection molded at temperatures below the melting point of LCP. The mechanical properties and the morphology of the strands and injection‐molded specimens were investigated as a function of draw ratio, LCP concentration, and PP molecular weight. The results for strands show that an increase in the draw ratio, LCP concentration and matrix molecular weight in general enhance the modulus and tensile strength. However, the tensile properties of injection‐molded specimens are found to be reduced compared with those of the original strands, in particular at high LCP concentration. The morphology of LCP changes from spherical or ellipsoidal droplets to elongated fibrils in the strands as the draw ratio increases, but this aligned LCP fibrillar morphology was not transferred to the injection‐molded specimens because of the disorientation of fibrils during injection molding. Compatibilization of PP/LCP blends was also studied by using various polymers. Maleic anhydride and acrylic acid modified PPs improved the tensile properties modestly, but maleic anhydride modified EPDM reduced the tensile properties.     

Self-reinforced thermoplastic-LCP prepregs and laminates

Self-reinforced sheets (prepregs) have been prepared by stretching extruded sheets made of thermoplastic (TP) and a thermotropic liquid crystalline polymer (LCP) blend. The sheets are formed by extrusion through a coathanger die, device. Processing at this stage is done at a temperature at which both components in the blend are melt processable. These prepregs are laid up in multi-layers in a direction parallel to the stretching direction or in the direction of 45° with respect to each previous layer. The lay-ups are compression molded into unidirectional or isotropic laminates at temperatures below the melt processing temperature of the LCP. Various pairs of TP and LCP have been studied. These include polypropylene and an LCP based on p-oxybenzoyl, terephthaloyl and hydroquinone moieties, polyphenylene oxide (PPO) and polystyrene/PPO alloy and a LCP based on 6-oxy-2-naphthoyl and p-oxybenzoyl moieties. Mechanical properties of the prepregs and laminates were measured and compared with those obtained from injection molded samples. Surprisingly, tensile strength and modulus of isotropic laminates are found to be higher than those of injection molded samples in the flow direction. Morphlogical studies of the prepregs and laminates indicate the presence of well-defined LCP fibers in various thermoplastic matrices.     

Mechanical,morphological, and thermal properties of poly(ethylene 2,6-naphthalate) and copolyester LCP blends

Binary blends of a liquid crystalline polymer (LCP) and poly(ethylene 2,6-naphthalate) (PEN) were melt blended and injection molded. The mechanical properties were studied as a function of LCP content. Both the ultimate tensile strength and Young's modulus are higher than the theoretical values predicted by the rule of mixtures and they display a synergistic behavior at 70 wt % LCP content. However, the tensile strength decreases with LCP content and Young's modulus remained unchanged at lower LCP contents (10 to 30 wt %). The poor mechanical property is attributed to the immiscibility between PEN and LCP and the fibrillation behavior of LCP as revealed by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) results. However, LCP and PEN are found to be partially miscible at higher LCP content, ascertained by DSC and dynamic mechanical analysis (DMA). This is attributed to the transesterification reaction between PEN and PET moiety in the LCP molecules. SEM micrographs reveal a skin/core morphology in the tensile bars, that is, the LCP is better oriented in the skin than in the core region. At lower LCP content, the dispersed LCP phase is spherical in the core and ellipsoidal in the skin, with long axes oriented in the flow direction. DSC studies show that the crystallization rate is significantly enhanced by the presence of LCP up to 50 wt %, where the LCP acts as a nucleating agent for PEN crystallization. The melting temperature decreases with LCP content, probably as a result of imperfect crystals formed in the presence of LCP heterogeneous nucleating centers and the increasing miscibility between LCP and PEN. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 477–488, 2001     

Pyroelectric and dielectric properties of side-chain liquid crystal polymers

Liquid crystal side-chain polymers (LCP), where the polymer architecture consists of a polymer backbone, flexible spacers, and mesogenic groups, are of considerable interest as they promise desirable electro-active properties, including pyroelectricity and electro-optic display phenomena. Induced polarization in the LCP system remains stable at ordinary temperatures, and therefore these systems are suitable for sensor materials for pyroelectric applications where switching times are less important. The dielectric applications of the polarized LCP system are also of importance if they are to be used as thin film electro-active devices. This paper reports the results of the dielectric and pyroelectric characterizations of six different polymers over a wide range of frequencies and temperatures. To elucidate the effect of a variation of chemical structure on the macroscopic properties, the structure of the mesogenic moiety was kept constant, and the length of the spacer and the size of the polymer backbone were varied.     

Dynamic mechanical behavior of LCP fiber/glass fiber–reinforced LLDPE composites

Liquid crystalline polymer (LCP) fibers and glass fibers have been used to rein force linear low density polyethylene (LLDPE) by using an elastic melt extruder and the compression molding technique. The impact behavior of hybrid composites of different composition is compared and is explained on the basis of the volume frac tion of the fibers. Addition of glass fibers decreases the Izod impact strength LLDPE. The impact strength of the composites increases when glass fibers are placed by LCP fibers. Dynamic mechanical α and β relaxations are studied and effect of variation of fiber composition on these relaxations is reported in the tem perature range from −50 to 150°C at 1 Hz frequency, a relaxation shifts toward higher temperatures with addition of fibers in LLDPE. Addition of fibers increases the storage modulus of LLDPE.     

Barrier and mechanical properties of pulp fiber/polymer laminates and blends

Paperboard laminates coated with two grades of poly(ε‐caprolactone) (PCL), poly(hydroxy butyrate‐co‐valerate) (PHBV) or a liquid crystalline copolyester (LCP) were prepared by compression molding, and the influence of the processing conditions and polymer content of the laminate on the laminate properties was studied. Ligno‐cellulose fiber/polymer blends were prepared from wet pulps and PCL and PHBV. The morphology, water vapor transmission rates, creasability, curl and twist and mechanical properties of the laminates and blends were studied. LCP and slowly cooled high molar mass PCL laminated paperboards showed the best creasing properties and the paperboards that were penetrated by the polymer showed the smallest degree of curl and twist. Extensive penetration occurred during compression molding of the paperboard with the low molar mass PCL at all temperatures and with PHBV and LCP at the higher molding temperatures. The water vapor transmission rates ranged from 1 to 300 times that of polyethylene depending on the polymer used and on the thermal history. In the case of blends, competitive properties were obtained only in those with a high polymer content. The laminate stiffness decreased and the strength increased in two polymer concentration regions, at ～20 wt% due to fiber‐fiber separation and at ～60 wt% due to phase inversion.     

Factors influencing microstructure formation in polyblends containing liquid crystalline polymers

Four isotropic polymers, poly(butylene terephthalate) (PBT), polycarbonate (PC), polyethersulfone (PES) and polysulfone (PSU), were blended by extrusion with a thermotropic liquid crystalline polymer (LCP) at different temperatures. The morphology of extrudates was observed by means of scanning electron microscopy and the intrinsic aspect ratio of LCP fibrils and particles separated from matrix resin was measured with an image analysis. Special attention was paid to the LCP fibrillation in these four matrices in a wide temperature range from 270 to 360°C and the internal relations among the effects of processing parameters, such as viscosity ratio, extrusion temperature, and LCP concentration. The results show that the viscosity ratio of the dispersed LCP phase to the continuous phase is a decisive factor determining the formation of LCP fibrils, but its effect closely relates with the LCP content. In the range of viscosity ratios investigated, 0.004 to 6.9, and lower LCP content of 10%, significant fibrillation took place only at viscosity ratios below 0.01. It is predicted that the upper limit of the viscosity ratio for LCP fibrillation will increase with increasing LCP content. A comparison of the morphologies of LCP/PES blends with different LCP concentrations reveals that the LCP phase becomes continuous at a concentration of less than 50%, and high LCP content does not always favor the formation of long and uniform LCP fibrils. The extrusion temperature has a marked effect on the size of the minor LCP domains. For fibril forming systems, the percentage of LCP fibrils with larger aspect ratios increases with increasing extrusion temperatures. All these results are explained by the combined role of deformation and coalescence of the LCP disperesed phase in the blend.     

Thermally induced phase separation in liquid crystalline polymer/polycarbonate blends

Thermally induced phase separation in liquid crystalline polymer (LCP)/polycarbonate (PC) blends was investigated in this study. The LCP used is a main‐chain type copolyester comprised of p‐hydroxybenoic acid and 6‐hydroxy‐2‐naphthoic acid. Specimens for microscopic observation were prepared by melt blending. The specimens were heated to a preselected temperature, at which they were held for isothermal phase separation. The preselected temperatures used in this study were 265, 290, and 300°C. The LCP contents used were 10, 20, and 50 wt %. These parameters corresponded to different positions on the phase diagram of the blends. The development of the phase‐separated morphology in the blends was monitored in real time and space. It was observed that an initial rapid phase separation was followed by the coarsening of the dispersed domains. The blends developed into various types of phase‐separated morphology, depending on the concentration and temperature at which phase separation occurred. The following coarsening mechanisms of the phase‐separated domains were observed in the late stages of the phase separation in these blends: (i) diffusion and coalescence of the LCP‐rich droplets; (ii) vanishing of the PC‐rich domains following the evaporation‐condensation mechanism; and (iii) breakage and shrinkage of the LCP‐rich domains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Prepregs and laminates of polyetherimide-reinforced by a thermotropic LCP

Unidirectional sheets (prepregs) of blends of polyetherimide (PEI) with a liquid crystalline polymer (LCP) are prepared. The mechanical properties of prepregs at directions of 0°, 45°, and 90° to the machine direction are investigated as a function of draw ratio and LCP concentration. The results show that drawing significantly increases the tensile strength and modulus of prepregs in the machine direction and only slightly decreases these properties in the transverse direction. An increase in the LCP content greatly enhances the tensile strength and modulus in the machine direction but decreases these properties in the 45° and 90° directions. The strain at break of prepregs decreases with LCP content in all directions tested. An abrupt drop in the tensile strength, modulus, and strain at break of prepregs occurs in the 45° and 90° directions when LCP content reaches 40%. Prepregs are used to manufacture unidirectional and quasi-isotropic laminates. Unidirectional laminates show mechanical properties close to those of the corresponding prepregs. The tensile modulus of quasi-isotropic laminates exhibits a continuous increase with increasing LCP content while the tensile strength increases with an LCP content up to 30%, then it decreases rapidly. The morphology of LCP in prepregs is observed to change from disperse to continuous at LCP contents of 40 and 50%. This effect is found to be responsible for the large decrease in tensile strength of prepregs in the 45° and 90° directions and quasi-isotropic laminates at higher LCP concentration. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:329–340, 1997     

Self-Reinforcing Composite Based on Ethylene Acrylic Elastomer (AEM)/Liquid Crystalline Polymer (LCP) Blend

Abstract

Blends of ethylene acrylic elastomer (AEM) and thermotropic liquid crystalline polymer (TLCP) have been prepared by melt mixing technique. Processing studies indicated a decrease in the viscosity of the blends with the addition of liquid crystalline polymer (LCP). At lower level of LCP the tensile strength and tear strength increased. However, at higher level of LCP tensile strength values decreased due to insufficient adhesion between two phases. The modulus of the samples increased with the LCP content. The degree of crystallinity increased with increasing LCP content. This improvement in crystallinity is associated with the increase in crystallite size. For the blends, thermal studies indicated, the endothermic signals which were more prominent at all the peak temperatures. The heat of degradation values increased with the LCP content. Scanning electron microscope (SEM) study suggested the fibril formation, which affected the failure mechanism under DMA studies. Storage modulus and loss modulus of the blends increased with increasing LCP content. At above glass transition temperature (Tg) improvement in storage modulus is nearly five times higher than that of the pure AEM.     

Compatibilization of PPO/LCP blends by semi‐interpenetrating liquid crystalline polymer networks LCP/PS

A new approach for enhancing the compatibility of liquid crystalline polymers (LCPs) with engineering thermoplastics is developed in this paper. By adding a new type of compatibilizer to poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO)/LCP blends (semi‐interpenetrating LCP network (ILCPN) comprising the liquid crystalline polymer poly‐(ethylene terephthalate)/p‐hydroxybenzoic acid (PET/60PHB) and crosslinked polystyrene), a well‐compatibilized PPO/LCP composite with considerably improved mechanical properties was obtained. Compared with the uncompatibilized PPO/LCP blend, the bending strength and the Izod impact strength of the compatibilized sample with 5% semi‐ILCPN increase more than 2 and 4 times, respectively.