Experimental results for the rheological and rheo‐optical behavior of poly(ethylene terephthalate)/liquid‐crystalline polymer blends

The use of thermoplastic/liquid‐crystalline polymer (LCP) blends is recognized as a good strategy for reducing viscosity and improving mechanical properties relative to pure thermoplastics. This improvement, however, is only noticeable if the LCP fibrillates, in situ, during processing and the fibrils are kept in the solid state. In this article, we report a morphological, rheological, and rheo‐optics study performed with two blends of poly(ethylene terephthalate) with a LCP, Rodrun LC3000 (10 and 25 wt % LCP content), and we show that the obtained droplet‐shape relaxation time (the time the deformed droplet took to regain its spherical form after the cessation of flow) allowed for the explanation of the morphological observations. In fact, the droplet‐shape relaxation time was higher for the blend with higher LCP content, for the higher experimentally accessible shear rates, and still increased at the highest shear rate, which explained the fibrils of the LCP dispersed phase observed in this blend, whereas for the lower LCP content blend, the droplet‐shape relaxation time reached a low‐value plateau for higher shear rates, which explained the absence of fibrillation in this blend. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Rheology,morphology and properties of LCP/Nylon 66 composite fibers

The rheology, morphology and properties of the composite systems of LCP, Vectra A^TM 950 and Nylon 66 were investigated. The viscocity ratio of LCP and matrix has strong influence on their morphology. For LCP blends, the viscosity ratio of LCP is a critical factor in determining the blend morphology. The optical micrographs show that the good fibrillation can be achieved when the viscocity of the dispersed LCP phase is less than that of the Nylon 66 matrix at 310°C. The dispersed LCP domains tend to be spherical or cluster‐like when the viscosity ratio of the disperesed LCP phase and the Nylon 66 matrix is more than 1 at 280°C. The scanning electron microscopy (SEM) and optical micrograph observations show that Nylon 66 is immiscible with LCP, and there are two distinct phases in the blends. The morphology of LCP phase changes with the composition. LCP exhibits a fine fibril dispersed phase in the Nylon 66 matrix in the low LCP concentration. With an increase in LCP concentration, the morphology of LCP phase is changed form a fine fibril dispersed phase to a perfectly aligned continuous fiber reinforced phase in the rich LCP concentration. The tensile moduli increase with LCP concentration, especially in the rich LCP concentration. The tensile strengths increase with LCP concentration only when LCP concentration is above 40 wt%. Compared to the pure Nylon 66 fiber, the 40 wt% LCP composite sample shows a 982.1% increase in tensile modulus and a 123.3% increase in tensile strength. The mechanical properties of composite fibers are below the rule of mixtures if the LCP concentration is low, but above the rule of mixtures if the LCP concentration is high.     

Influence of interactions on the mechanical,morphological and thermal properties of in situ ternary composites based on fluorocarbon elastomer,acrylic elastomer and liquid crystalline polymer blends

The mechanical, morphological and thermal properties of the binary and ternary blends of a fluorocarbon elastomer (FKM), an acrylic elastomer (ACM) and a liquid crystalline polymer (LCP) were investigated. The ternary blends were prepared by varying the amount of the LCP but fixing the ratio of the FKM and ACM. Addition of a third component, a polyacrylic rubber which interacted with the LCP, facilitated the structural development of the LCP phase by acting at the interface. The mechanical properties of the ternary blends were substantially improved because of both the fibril generation and adhesion of rubber particles on the LCP fibrils, which were attributed to the ACM interaction. Morphological investigations suggest that the fine fibrillation of the LCP domains is more apparent in the ternary blends than in the binary blends of FKM and LCP prepared under the same processing conditions. Thermogravimetric analysis (TGA) revealed an improved thermal stability of the FKM in the presence of the LCP for the binary blends, but a lower thermal stability for the ternary blends. Copyright © 2005 Society of Chemical Industry     

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     

Blends of a bottle grade polyethylene terephthalate copolymer and a liquid crystalline polymer. Part I: Injection molding morphology and rheological properties

Blends of a bottle grade polyethylene terephthalate copolymer (PET) with a liquid crystalline polymer (LCP) were prepared by injection molding. The thermal transitions, the morphology and the rheological properties of the pure components and of the blends were measured by dynamic mechanical analysis (DMTA), scanning electron microscopy (SEM) and capillary and parallel plates rheometry, respectively. The blends displayed only one T_g; the B60 and B80 compositions showed the highest LCP β‐transition, which has been correlated to good barrier properties. In all the blends a “skin‐core” type morphology was observed; the core region had two phases while the skin region showed only one fibrillar phase. The viscosity measurements gave an indication that the interface was strong, probably due to transterifications reactions that occurred during the tests. On creep recovery, the increasing addition of the LCP to the PET increased the blends elastic recovery. On stress growth, the highest stress overshoot was displayed by the pure LCP; this polymer actually presented two overshoots that were also observed in some of the blends at high shear rates.     

Reinforced poly(ether sulfone) materials by blending with a semiaromatic liquid crystalline copolyester

Blends based on poly(ether sulfone) (PES) and a semiaromatic liquid crystalline copolyester (R5) were obtained by injection molding across the entire composition range. The blends showed two pure amorphous phases. The fibrillar structure of the skin led to enhancements in the stiffness. The break properties, however, decreased at low LCP contents, due to the expected lack of adhesion between the phases. The increase in the modulus at increasing LCP content led to improvements in tensile strength. The notch sensitivity of PES decreased after the addition of low LCP levels, giving rise to enhancements of almost 600% in the notched impact strength. The unusually enhanced performance of the 20/80 blend, which has been seen previously in another thermoplastic/LCP blend, suggests that the dispersed PES phase in this blend may act as rubber particles do in rubber toughened thermoplastics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 52–59, 2004     

Rheology and morphology of some thermoplastic blends with a liquid crystalline copolyester

Liquid crystalline polymers (LCPs) are known for their high performance properties. However, owing to their high cost, research efforts are much oriented to their use as reinforcements for different thermoplastics. In this study, we investigated the morphology, mechanical and dynamic rheological properties of blends of a 60/40 para hydroxybenzoic acid–ethylene terephthalate copolyester LCP (PHB/PET) with poly(butylene terephthalate) (PBT), poly(hexamethylene terphthalate) (PHMT), and polycarbonate (PC). Addition of up to 30 wt% of LCP to the different thermoplastics was performed in a Haake Rheomix mixer at 300°C. The dynamic rheological properties of the blends showed significant changes upon the addition of LCP, but no improvement in the mechanical properties was observed. The rheological properties of the blends below the nematic transition temperature of the LCP (210°C) were similar to those of solid filled thermoplastics. At 270°C, at which the LCP is in the nematic phase, the viscosity of LCP blends with PC blends decreased, whereas that obtained with PBT blends was increased. This is interpreted as being due to the differences in viscosity and interfacial tension between the components and to a possible reaction between the LCP and the thermoplastics.     

Effect of ethylene/propylene ratio on reinforcing characteristics of liquid crystalline polymer (LCP) in EPDM-LCP composites

Abstract

Two ethylene/propylene diene monomer (EPDM) polymers were blended with a liquid crystalline polymer (LCP) at concentrations of 10, 20, 30 and 40 wt-%. The effects of ethylene/propylene (EP) ratio on the in situ fibrillation, and hence the reinforcing characteristics, of the LCP in EPDM-LCP blends were studied. The fibre forming capacity of the LCP depended on the viscosity of the EPDM rubber. Under high temperature processing conditions (at 300°C), the high EP ratio EPDM, which had the higher viscosity, facilitated the fibrillation of the LCP. Further melt processing at 100°C, followed by curing at 150°C, decreased the reinforcing effects of the LCP owing to breakage of the fibrils under the high shear stresses developed in the high viscosity matrix. However, this degradation of fibre lengths depended on the LCP concentration. After curing, the more viscous EPDM formed blends with higher stiffnesses and strengths than those obtained from the low viscosity EPDM. Both the nucleation and growth of crystal domains in the EPDM matrix were promoted by small amounts of LCP. Again the effects were more pronounced in the EPDM with the higher EP ratio.     

Characterization and processing of blends of polyethylene terephthalate with several liquid crystalline polymers

Blends of an engineering thermoplastic, poly(ethylene terephthalate) (PET), and two liquid crystalline polymers (LCPs) viz., copolyesters of PET and parahydrox-ybenzoic acid (PHB) in 40/60 mole percent (LCP60) and in 20/80 mole percent (LCP80) were prepared. A blend of LCP60 and LCP80 in 50/50 weight percent (LCP60-80) was blended with PET. Both flat films and rods were extruded and their properties examined. The morphology of the films investigated using Scanning Electron Microscopy (SEM) revealed that the LCP phase remained as dispersed droplets in the PET matrix. In spite of the lack of fibrillation in these films, the mechanical properties were enhanced to some extent with a maximum at 10 weight percent of the LCP phase. However, in the case of the rods thin fibrils of the LCP phase of the order of 1 μm in diameter were observed provided the composition of the LCP was 20 weight percent or greater. This success In achieving fibrillation is through to be due to the extensional flow fields present at the entrance of the capillary die and the fact that a short L/D ratio die was used. Differential Scanning Calorimetry (DSC) thermograms of the extruded films indicated that the LCP phase may act as a nucleating agent for the crystallization of PET. Rheology of the blends revealed that the complex viscosity of the blends is not much different from that of pure PET. This is attributed to the partial miscibility of the two components. Based on the DSC results and residence times in the extruder, it is concluded that no significant transesterification reactions appear to have: taken place in the blends. The rheology is studied further with respect to the cooling behavior of the pure components and factors important to the fibrillation of the LCP phase and the formation of in-situ reinforced composites are discussed.     

Structure and properties of polyblends of a thermotropic liquid crystalline polymer with an alloy of polyamide-6 and ABS

The relationship between the microstructure and corresponding mechanical properties developed during injection molding of blends containing a liquid crystalline polymer (LCP) as the minor component and an engineering polymer system has been studied. A wholly aromatic copolyester LCP (Vectra A950) was melt blended at different compositions with a thermoplastic matrix consisting of a commercial compatibilized blend of polyamide-6 and ABS (Triax 1180). These blends were prepared under two different sets of injection molding conditions. In the first case, a higher melt temperature, higher barrel temperature, lower injection pressure, lower mold temperature, and shorter residence time in the mold were used during injection molding, as compared with the second case. The mechanical properties of the blends were superior to those of the base polymer. In the second case, the resulting injection-molded specimens had a distinct skin–core morphology where elongated fibrils of LCP constituted the skin layer. The mechanical properties of the blends processed under the second set of processing conditions were superior to those of the first, though the trends in both cases were the same. To study the effects of process variables the 15% LCP blend and the second set of processing conditions were taken as the base. Samples were injection-molded by varying one parameter at a time. It was seen that the properties of the blend were increased by maintaining a lower barrel temperature, greater injection pressure, lower injection speed, higher mold temperature, and a greater residence time in the heated mold. Thus it was found that the processing conditions played a vital role in determining the mechanical properties and morphology of the polyblends. © 1996 John Wiley & Sons, Inc.     

PC／EP／LCP共混物的相容性与力学性能

在ＰＣ／ＬＣＰ二元共混物中加入少量的低分子量环氧树脂以改善共混体系的相容性和ＬＣＰ的成纤维力,从而提高共混物的力学。结果表明,在ＰＣ／ＬＣＰ共混中加入２％的ＥＰ时,共混物力学性能得到大幅度提高。     

Influence of processing conditions on the morphological and mechanical properties of compatibilized PP/LCP blends

The main aim of this work is to study the influence of the application of different processing conditions on the morphological and mechanical properties of thermoplastic/LCP blends, in which the viscosity ratios are inferior to unity and decrease with increasing temperature. The way the microstructure evolves along the extruder determines the final morphology and thus, the mechanical performance of the systems. In the present case, the mechanical properties are related with the degree of fibrillation in the final composites. The best degree of fibrillation was obtained for low screw speeds and temperatures and for intermediate outputs. The use of high screw speeds and processing temperatures results in a decrease of the viscosity ratio, in the former case via an increase in the viscous dissipation, at the regions of higher shear rates (kneading‐elements). The application of a lower processing temperature is advantageous for deformation, break‐up, and fibrillar formation because of the higher viscosity ratios and higher shear stresses involved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

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     

Novel reinforced polymers based on blends of polystyrene and a thermotropic liquid crystalline polymer

A thermotropic liquid crystalline polymer (LCP), when added to polystyrene (PS), can function as both a processing aid and a reinforcing filler. Thermal, rheological, and mechanical properties of the pure components and blends containing up to 10 percent LCP are reported. The LCP used is immiscible with PS, and when an extensional component of flow is present during processing, the LCP forms an elongated fibrous phase oriented in the flow direction. This oriented phase lubricates the melt, substantially lowering the viscosity. When the processed blend is cooled, the dispersed fibrous LCP phase is preserved in the solidified material. The LCP microfibers behave like short reinforcing fibers to improve the mechanical properties of the blend; for example, at an LCP concentration of 4.5 percent, the modulus is increased about 40 percent vs. pure PS.     

In situ composite: Phenolphthalein polyethersulfone—thermotropic liquid crystalline polymer blends

Phase behavior, thermal, rheological and mechanical properties plus morphology have been studied for a binary polymer blend. The blend is phenolphthalein polyethersulfone (PES-C) with a thermotropic liquid crystalline polymer (LCP), a condensation copolymer of p-hydroxybenzoic acid with ethylene terephthalate (PHB-PET). It was found that these two polymers from optically isotropic and homogeneous blends by means of a solvent casting method. The homogeneous blends undergo phase separation during heat treatment. However, melt mixed PES-C/PHB-PET blends were heterogeneous based upon DSC and DMA analysis and SEM examination. Addition of LCP in PES-C resulted in a marked reduction of melt viscosity and thus improved processability. Compared to pure PES-C, the charpy impact strength of the blend containing 2.5% LCP increased 2.5 times. Synergistic effects were also observed for the mechanical properties of blends containing < 10% LCP. Particulates, ribbons, and fibrils were found to be the typical morphological units of PHB-PET in the PES-C matrix, which depended upon the concentration of LCP and the processing conditions.     

Structure and mechanical properties of polysulfone‐based in situ composites

Composites based on the polysulfone of bisfenol A (PSF) and a liquid‐crystalline copolyester (Rodrun 5000) were obtained by two processing methods, (1) direct injection moulding (DI) and (2) extrusion followed by injection moulding (PI), across the whole composition range. The blends were immiscible and showed two pure amorphous phases. The inferior mechanical properties of PI blends, and their more difficult processing, meant that the PI procedure is not suitable in these blends. The generally linear relationship of the Young's modulus of the DI blends is due to the counteracting effects of the large orientation of the skin and its low thickness. The improvement in notched impact strength of PSF on the addition of small amounts of LCP indicated an important reduction in its notch sensibility. The tensile strength behaviour was close to linearity, with the exception of the 20/80 blend in which it was synergistic. This had been seen in previous thermoplastic/LCP blends, and depicts a behaviour reminiscent of rubber‐toughened blends. Copyright © 2004 Society of Chemical Industry     

Rheology and impact characteristics of compatibilized polypropylene-liquid crystalline polymer composites

Polypropylene-liquid crystalline polymer (PP/LCP) and maleic anhydride compatibilized PP/LCP blends were prepared using the extrusion technique followed by injection molding. The LCP employed was Vectra A950 which consists of 25 mol % of 2,6-hydroxynaphthoic acid and 75 mol % of p-hydroxybenzoic acid. The rheology, morphology, and impact behavior of compatibilized PP/LCP blends were investigated. The rheological measurements showed that the viscosity of LCP is significantly higher than that of the PP at 280°C. This implied that the viscosity ratio of the LCP to the polymer matrix is much larger than unity. Scanning electron microscopy (SEM) observations revealed that the LCP domains are dispersed mainly into elongated ellipsoids in the PP/LCP blends. However, fine fibrils with large aspect ratios were formed in the compatibilized PP/LCP blends containing LCP content ≥ 10 wt %. The development of fine fibrillar morphology in the compatibilized PP/LCP blends had a large influence on the mechanical properties. The Izod impact strength of the PP/LCP blends showed little dependence on the LCP concentrations. On the other hand, the impact strength of the compatibilized PP/LCP blends was dependent on the LCP concentrations. The correlation between the LCP fibrillar morphology and spherulitic structure with the impact properties of the compatibilized PP/LCP blends is discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 521–530, 1998     

Studies on morphology,mechanical, thermal,and rheological behavior of extrusion‐blended polypropylene and thermotropic liquid crystalline polymer

Polypropylene (PP) was melt‐blended in a single‐screw extruder with a thermotropic Vectra B‐950 liquid crystalline polymer (LCP) in different proportions. The mechanical properties of such blends were compared in respect of their Young's moduli, ultimate tensile strength (UTS), percent elongation at break, and toughness to those of pure PP. The thermal properties of these blends were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The morphology was studied by using a polarizing light microscope (PLM) and a scanning electron microscope (SEM) while the rheological aspects of the blends and the pure PP were studied by a Haake Rheowin equipment. Mechanical analysis (tensile properties) of the blends showed pronounced improvement in the moduli and the UTS of the PP matrix in the presence of 2–10% of LCP incorporation. TGA of all the blends showed an increase in the thermal stability for all the blends with respect to the matrix polymer PP, even at a temperature of 410°C, while PP itself undergoes drastic degradation at this temperature. DSC studies indicated an increase in the softening range of the blends over that of PP. Morphological studies showed limited mixing and elongated fibril formation by the dispersed LCP phase within the base matrix (PP) at the lower ranges of LCP incorporation while exhibiting a tendency to undergo gross phase separation at higher concentrations of LCP, which forms mostly agglomerated fibrils and large droplets. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 767–774, 2003     

Morphology and mechanical properties of liquid crystalline copolyester and polyester elastomer blends

Blends of a polyester elastomer (PEL) having a hard segment of polyester (PBT) and soft segment of polyether (PTMG) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate), were prepared in a twin-screw extruder. Specimens for mechanical testing were prepared by injection molding. The morphology of the LCP/PEL blends was characterized under different processing conditions. To determine what conditions were necessary for the development of a fibrillar morphology of LCP, we have studied the effect of processing method (extrusion and injection molding), injection molding temperature (below and above the melting point of LCP), and gate position in the mold (direct gate and side gate). SEM studies revealed that some extensional flow was required for the fibrillar formation of LCP and the fibrillar structure of LCP was controlled by the processing method. The morphology of the blends was found to be affected by their compositions and processing conditions. SEM studies revealed that finely dispersed spherical domains of LCP were formed in the PEL matrix and the inclusions were deformed in fibrils from the spherical droplets with increasing LCP content and injection temperature. The mechanical properties of the LCP/PEL blends were also found to be affected by their compositions and processing conditions. The mechanical properties of LCP/PEL blends were very similar to those of polymeric composite. An attempt was made to correlate the structure of the blends from the scanning electron microscope with the measured mechanical properties. All of the aspects of the morphology were possible to explain in terms of the mechanical properties of the blends. A DSC study revealed that the crystallization of PEL was accelerated by the addition of LCP in the matrix and a partial compatibility between LCP and PEL was predicted. The rheological behavior of the LCP/PEL blends was found to be very different from that of the parent polymers, and significant viscosity reductions were observed in the blend consisting of only 5 wt% of LCP.