Preparation and properties of self-reinforced polypropylene/liquid crystalline polymer blends

The mechanical properties of self-reinforced liquid crystalline polymer/polypropylene (LCP/PP) blends strongly depend on the viscosity ratio of the blend components in the melt. This ratio was determined for PP blends with different commercial LCPs (Vectra A950 and Vectra B950), by means of capillary rheometry, under conditions representative for the blending process during extrusion. It was found that optimal mechanical properties were achieved when the LCP/PP viscosity ratio at 285°C ranges between 2 and 4 at a shear rate of 800–1000s⁻¹. The LCP/PP viscosity ratio appears to be shear stress dependent. This creates the option of fine tuning the LCP droplet deformation process by means of the extrusion rate. This shear stress dependence is more pronounced for PP blends with Vectra B950 than for blends with Vectra A950.     

Engineering properties of compatibilized polypropylene/liquid crystalline polymer blends

Polypropylene (PP) and Vectra A950, a thermotropic liquid crystalline polymer (LCP), blends were prepared in a single‐screw extruder with the variation in Vectra A950 content in presence of fixed amount (2%, with respect to PP and LCP mixture as a whole) of ethylene‐acrylic acid (EAA) copolymer as a compatibilizer. Mechanical analysis of the compatibilized blends within the range of LCP incorporations under study (2–10%) indicated pronounced improvement in the moduli, ultimate tensile strength (UTS), and hardness. Fourier transform infrared (FTIR) spectroscopy studies revealed the presence of strong interaction through H‐bonding between the segments of Vectra A950 and the compatibilizer EAA. Morphological studies performed by scanning electron microscopy (SEM) manifested the development of fine fibrillar morphology in the compatibilized PP/Vectra A950 blends, which had large influence on the mechanical properties. Differential scanning calorimetry studies showed an initial drop of the melting point of PP in the presence of EAA followed by enhancement of the same in presence of Vectra A950. TGA showed an increase in the thermal stability for all blends with respect to matrix polymer PP. Rheological studies showed that a very small quantity of Vectra A 950 was capable of reducing the melt viscosity of PP particularly in the lower shear rate region and hence facilitated processibility of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological hybrid effect in dually filled polycarbonate melt containing liquid crystalline polymer

Polycarbonate (PC)/liquid crystalline polymer (LCP) blends dually filled with glass fiber and nano‐SiO₂ were prepared by melt blending, with the use of a commercial Vectra A130 as the source of LCP and glass fiber. In these dually filled PC/LCP melts, rheological hybrid effect occurred, confirmed by the melt viscosity of the quadruple polymer blends decreased with increasing nano‐silica loading, influenced by the minor LCP phase in the blend. The drastic viscosity reduction closely correlates with the deformation and fibrillation of LCP droplets in the system. The LCP fibrillation was controlled jointly by the thermodynamic and hydrodynamic driving forces. Finally, the dually filled PC/LCP melt had decreased viscosity lower than those of pure PC, silica‐filled PC, and PC/Vectra A130 blends, and furthermore had decreased glass fiber breakage, shown by larger average aspect ratio than that in PC/Vectra A130 blends. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Characterization of thermotropic liquid crystalline polyester/polycarbonate blends: Miscibility,rheology, and free volume behavior

Miscibility, rheology, and free volume properties of blends of thermotropic liquid crystalline polymers (TLCPs) (Vectra A950) and polycarbonate (PC) are studied in this work. Despite the unusual increase in T_g of the PC phase, the blends are found to be generally immiscible. Transesterification may occur during blending and be the cause of the increase of T_g of the PC phase and the partial miscibility of the blends at high TLCP concentrations. With regard to the melt rheology of these materials, according to a three‐zone model, dynamic moduli of Vectra A950 show plateau‐ and transition‐zone behavior, while PC exhibits terminal‐zone behavior. The blends show only terminal‐zone behavior at low Vectra A950 contents (≤50%) and terminal‐ and plateau‐zone behavior at higher Vectra A950 contents. The relaxation time of Vectra A950 is much longer than PC and the blends have relaxation times greater than additivity. Both the complex and steady shear viscosities of the blends increase with the addition of Vectra A950. This is attributed to interfacial association, which retards the reorientation and alignment of the Vectra A950 phase in the molten state. The Cox–Merz rule holds true for PC but not for Vectra A950 and the blends. Free volume properties on an angstrom scale evaluated by positron annihilation lifetime spectroscopy (PALS) indicate that Vectra A950 has smaller, fewer free volume cavities than PC and the variation of free volume behavior in the blends can be explained in terms of blend miscibility. The measured densities of the blends agree well with the free volume fractions of the blends determined from PALS. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2319–2330, 2000     

Studies on morphology,mechanical, thermal,and dynamic mechanical behavior of extrusion blended polypropylene and thermotropic liquid crystalline polymer in presence of compatibilizer

Polypropylene was melt blended in a single screw extruder with thermo tropic Vectra B‐950 liquid crystalline polymer (copolyester amide) in different proportions in presence of 2% of EAA, ethylene‐acrylic acid copolymer (based on PP) as a compatibilizer. The mechanical properties of such compatibilized blends were evaluated and compared in respect of their Young's Modulii, Ultimate tensile strength, percent elongation at break, and toughness to those of Pure PP. The Morphology was studied by using a polarizing light microscope (PLM) and Scanning electron microscope (SEM). The Thermal characterization of these blends were carried out by differential scanning calorimeter (DSC).The mechanical properties under dynamic conditions of such compatibilized blends and pure PP were studied by dynamic mechanical analyzer (DMA). Mechanical analysis (Tensile properties) of the compatibilized blends displayed improvements in Modulii and ultimate tensile strength (UTS) of PP matrix with the incorporation of 2–10% of LCP incorporation. The development of fine fibrillar morphology in the compatibilized PP/LCP blends had large influence on the mechanical properties. Differential scanning calorimeter (DSC) studies indicated no remarkable changes in the crystalline melting temperature of the blends with respect to that of pure PP. However, an increase in the softening range of the blends over that of PP was observed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Barrier properties of blends based on liquid crystalline polymers and polyethylene

Blends of an extrusion‐grade polyethylene and two different liquid crystalline polymers of Vectra type were prepared by melt mixing using poly(ethylene‐comethacrylic acid) as compatibilizer. Oxygen and water vapor permeability, transparency and welding strength of compression molded and film blown specimens were studied. The compression molded blends showed gas permeabilities conforming to the Maxwell equation assuming low permeability liquid crystalline polymer spheres in a high permeability polyethylene matrix. One of the liquid crystalline polymers with suitable rheological properties formed a more continuous phase in the film blown blends and a substantial decrease in oxygen and water vapor permeability was observed in these blends. The compression molded blends with 50% liquid crystalline polymer and some of blow molded blends showed very high gas permeabilities. It is believed that voids forming continuous paths through the structure were present in these samples. The blends showed significantly higher opacity than pure polyethylene.     

Studies on the engineering properties of LCP‐Vectra B 950/PP blends with the variations of EAA content

Polypropylene (PP) was melt blended with Vectra B‐950 [a thermotropic liquid crystalline polymer (LCP)], in a single screw extruder in presence of different doses of ethylene acrylic acid (EAA) copolymer, as modifier. The effect of incorporation in different proportions of EAA at a fixed dose of 5% LCP, on mechanical, thermal, morphological, and rheological properties of such blends was studied and the same were compared with that of pure PP and amongst themselves. Mechanical analysis (tensile properties) of the prepared blends exhibited improvements in ultimate tensile strength (UTS), modulus, toughness, hardness, and impact strength of PP matrix with the incorporation of EAA. The improvement in mechanical properties is associated with the formation of LCP fibrils as evidenced by scanning electron microscopy (SEM). A strong interaction through H‐bonding between the segments of Vectra B‐950 and EAA was established by FTIR study. Differential scanning calorimetry (DSC) studies indicated substantial increase in melting point of the blends, and thermogravimetric analysis (TGA) showed that the thermal stability of PP was improved with the addition of LCP and EAA. Rheological properties showed that LCP and EAA drop down the melt viscosity of PP and thus facilitate processibility of blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Barrier Properties of Blends Based on Liquid Crystalline Polymers and Poly(ethylene terephthalate)

Abstract

Blends of poly(ethylene terephthalate) (PETP) and two different thermotropic liquid crystalline (LC) polymers of the Vectra-type were prepared by melt mixing. Oxygen and water vapor permeability, light transmission and welding properties were measured on compression-molded and film-blown specimens. SEM showed that the LC polymers were the disperse phase with a good phase adhesion to the PETP matrix in the majority of the compression-molded blends. The 50/50 blend based on the low melting point LC polymer showed possibly a continuous LC polymer phase. The film-blown specimens showed LC polymer spheres at low LC polymer content. Above a certain LC polymer content (10-30% LC polymer), fibrous and ellipsoidal LC polymer particles was the dominant morphological feature of the blends. Density measurements showed that the void content in the blends was low. The compression-molded blends based on the high melting point LC polymer showed permeabilities conforming to the Maxwell equation assuming low permeability (LC polymer) spheres in a high permeability (PETP) matrix. The compression-molded blends based on the low melting point Vectra showed lower permeabilities than predicted by the Maxwell equation, particularly at high LC polymer content. The film-blown blends showed extensive scattering in the permeability data. The blend with 30% low melting LC polymer exhibited a 96% lower oxygen permeability than PETP. This was due to a reduction in both oxygen diffusivity and solubility. Ellipsoidal and fibrous LC polymer particles increased the diffusional path and lowered the diffusivity. The transparency of the compression-molded samples was lost already at 1% LCP. The blends showed welding properties superior to those of PETP.     

Injection molding of PC/PBT/LCP ternary in situ composite

A liquid crystalline polymer (LCP), Vectra B950, reinforced polycarbonate (PC) 60 wt%/polybutylene terephthalate (PBT) 40 wt% blend was studied using the injection molding process. Morphology and mechanical properties of ternary in situ LCP composites were investigated and compared with binary polycarbonate/Vectra B950 LCP composites. Good in situ fibrillation of LCP was observed in the direct injection-molded LCP composites. Preliminary results of this work indicate that addition of PBT improves skin-core distribution of LCP microfibrils in the matrix and also enhances adhesion between the matrix and Vectra B950, which contains terephthalic acid. The PC/PBT/LCP ternary system also exhibits lower viscosity than the PC/PBT blend and pure LCP. In a ternary system with 30 wt% of Vectra B950, tensile modulus and strength increase approximately threefold and twofold, respectively. The rule of mixtures (ROM) for continuous reinforcement can accurately represent the strengthening effects for the ternary LCP in situ composites. Generally, LCP reduces the ductility and impact strength of the thermoplastic blends; however, the relative loss is less in the ternary system than in the binary system.     

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     

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.     

Thermal and mechanical properties of injection molded liquid crystalline polymer/amorphous polymer blends

Injection molded samples of binary blends of Vectra (LCP) and the three amorphous polymers polyethersulfone (PES), polycarbonate (PC), and aromatic poly(ester carbonate) (APEC) have been subjected to morphological and rheological characterization, and coefficients of linear thermal expansion and Young's moduli have been determined. The Young's modulus of the PES/LCP blends exhibited a near lower-bound behavior that could be predicted by the one-adjustable-parameter equations of Halpin-Tsai (ζ = 0.18) and Takayanaga (b = 0.23), whereas the coefficients of linear thermal expansion followed the Takayanaga equation with a value of b = 0.50. The chain orientation of the LCP component was essentially constant in all PES/LCP blends with a Herman's orientation parameter of 0.39 ± 0.03. Transesterification reactions led to randomization of the constituents of the PC/LCP and APEC/LCP blends. The effect was more pronounced in the PC/LCP blends. The introduction of the LCP into the PC/LCP blends led to no reduction in melt viscosity and no self-reinforcement. APEC/LCP exhibited self-reinforcement in blends with a content greater than 27 vol% LCP, and especially the blend with 67 vol% LCP. The self-reinforcement was caused by the presence of an oriented LCP phase, confirmed by X-ray diffraction, and by improved interfacial bonding, presumably resulting from the transesterification reactions occurring at the phase boundaries.     

Blends of low‐density polyethylene and liquid crystalline polymer

Blends of low‐density polyethylene (LDPE) and a glass‐filled thermotropic liquid crystalline polymer (LCP‐g) have been prepared by melt mixing techniques. The thermal transitions, dynamic behavior, morphology and crystalline properties of the blends have been measured by DSC, DMTA, SEM and XRD respectively. The crystallinity decreased with increase in LCP‐g content in the blends. At higher levels of LCP‐g, crystal growth is favored in the PE phase. From DSC, it is found that the thermal stability of the blends increased with the LCP‐g content. The variation of storage modulus, loss modulus and stiffness as a function of blend ratio suggested the phase inversion at the 40–50% level of LCP‐g in the blend. SEM studies revealed that with the increase in LCP‐g content, the flow of the matrix was restricted.     

Reactive blending of poly(ethylene terephthalate) with a liquid crystalline copolyester and polyhydroxyether

Poly(ethylene terephthalate) modified with a dianhydride (PET–anhydride) was melt‐blended with a liquid crystalline copolyester (Vectra A) in the presence of a small amount of a liquid crystalline polyhydroxyether. The mechanical properties of a blend consisting of PET–anhydride/Vectra A/polyhydroxyether were drastically improved compared to blends without polyhydroxyether or without anhydride. Melt‐spun fibers of PET–anhydride/Vectra A/polyhydroxyether in a 80/20/0.75 weight ratio displayed a much higher tensile modulus (17 GPa) and tensile strength (214 MPa) than did a 80/20 PET–anhydride/Vectra A blend (4 GPa and 60 MPa, respectively). A similar increase in modulus and strength was found for a 90/10/0.75 relative to a 90/10 blend. The tensile moduli of the blends can well be described by the Tsai–Halpin equation. A better fibril formation was observed, which was attributed to an improved viscosity ratio. Reactions between the various functional groups during melt processing were indicated by viscosity measurements. The polyhydroxyether may act as a reactive compatibilizer which improves the interfacial adhesion, chemically and/or physically. WAXD recordings of both blends showed a crystalline and highly oriented Vectra phase. The PET phase was unoriented and amorphous in a PET/Vectra blend and semicrystalline and weakly oriented in a PET/Vectra/polyhydroxyether blend. Postdrawing of the various blend fibers to λ = 4 increased the modulus by about 40% and the tensile strength by more than 100%, mainly through orientation of the PET phase. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1107–1123, 1999     

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.     

Rheological and physical properties of polyarylate/LCP blend systems

A polyarylate Unitika U-Polymer 100 (PAR) was melt blended with a thermotropic liquid crystalline polymer (LCP) Vectra A950, and the processingmorphology-properties relations were investigated. Inclusion of LCP slightly reduced T_g of PAR. The PAR/LCP blend with the LCP content higher than 50 wt% exhibited a noticeable yield stress, particularly in the vicinity of crystal-to-nematic transition temperature (T_cn). LCP lowered the blend viscosity above T_cn and seemed to play a role as processing aid. The tensile strength of the blends was increased with increasing spin draw ratio and level of LCP, and the spinning temperature influenced tensile strength. The relaxation behavior under dynamic shear and resultant blend morphology based on WAXD and SEM analyses are discussed as well.     

In situ reinforcement of poly(butylene terephthalate) and butyl rubber by liquid crystalline polymer

Ternary in situ butyl rubber (IIR)/poly(butylene terephthalate) (PBT) and liquid crystalline polymer (LCP) blends were prepared by compression molding. The LCP used was a versatile Vectra A950, and the matrix material was IIR/PBT 50/50 by weight. Morphological, thermal, and mechanical properties of blends were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), differential scanning calorimetry, and thermogravimetric analysis (TGA). Microscopy study (SEM) showed that formation of fibers is increasing with the increasing amount of LCP A950. Microscopic examination of the fractured surface confirmed the presence of a polymer coating on LCP fibrils. This can be attributed to some interactions including both chemical and physical one. The increased compatibility in polymer blends, consisting of IIR/PBT, by the presence of LCP A950 may be explained by the adsorption phenomena of the polymer chains onto the LCP fibrils. SEM and AFM images provided the evidence of the interaction between IIR/PBT and the LCP. Dynamic mechanical analyses (DMA) and TGA measurements showed that the composites possessed a remarkably higher modulus and heat stability than the unfilled system. Storage modulus for the ternary blend containing 50 wt% of LCP exhibits about 94% increment compared with binary blend of IIR/PBT. From the above results, it is suggested that the LCP A950 can act as reinforcement agent in the blends. Moreover, the fine dispersion of LCP was observed with no extensional forces applied during mixing, indicating the importance of interfacial adhesion for the fibril formation. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Spinnability and physical properties of in situ composite fibers based on thermotropic liquid crystalline polymer

In situ composite fibers based on poly(ethylene 2,6‐naphthalate) (PEN) and a thermotropic liquid crystalline polymer (Vectra A950) were prepared using a single‐screw extruder. The fibers were taken up at selected speeds. The spinnability, thermal behavior, mechanical properties, and morphologies of the PEN/Vectra A950 blend were investigated. The results showed that the PEN/Vectra A950 blends were partly miscible, and the miscibility increased with the increased concentration of Vectra in the blend. The DSC measurements indicated that Vectra enhanced the crystallization process of PEN by performing as a nucleating agent. The Instron tensile property study, coupled with scanning electron microscopy, revealed that the mechanical properties of the PEN matrix were significantly improved when Vectra existed as long and continuous fibrils. The laser Raman results showed that the Vectra orientation began to develop at take‐up speeds above 500 m/min. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 795–811, 2002     

In‐situ reinforcement of PBT/ABS blends with liquid crystalline polymer

Ternary in‐situ poly(butylene terephthalate) (PBT)/poly(acrylonitrile‐butadienestyrene) (ABS)/liquid crystalline polymer(LCP) blends were prepared by injection molding. The LCP used was a versatile Vectra A950, and the matrix material was PBT/ABS 60/40 by weight. Maleic anhydride (MA) copolymer and solid epoxy resin (bisphenol type‐A) were used as compatibilizers for these blends. The tensile, dynamic mechanical, impact, morphology and thermal properties of the blends were studied. Tensile tests showed that the tensile stregth of PBT/ABS/LCP blend in the longitudinal direction increased markedly with increasing LCP content. However, it decreased sharply with increasing LCP content up to 5 wt%; thereafter it decreased slowly with increasing LCP content in the transverse direction. The modulus of this blend in the longitudinal direction appeared to increase considerably with increasing LCP content, whereas the incorporation of LCP into PBT/ABS blends had little effect on the modulus in the transverse direction. The impact tests revealed that the Izod impact strength of the blends in longitudinal direction decreased with increasing LCP content up to 10 wt%; thereafter it increased slowly with increasing LCP. Dynamic mechanical analyses (DMA) and thermogravimetric measurements showed that the heat resistance and heat stability of the blends tended to increase with increasing LCP content. SEM observation, DMA, and tensile measurement indicated that the additions of epoxy and MA copolymer to PBT/ABS matrix appeared to enhance the compatibility between PBT/ABS and LCP.     

Structure and properties of blend fibers from poly(ethylene terephthalate) and liquid crystalline polymer

The structure and properties of the as-spun fibers of poly(ethylene terephthalate) (PET) blends with a thermotropic liquid crystalline polymer (LCP), Vectra A900, were studied in detail. The DSC results indicate that the LCP component may act as a nucleating agent promoting the crystallization of the PET matrix from the glassy state but which inhibits its crystallization from the melt due to the existence of an LCP supercooled mesophase. The effect of the drawdown ratio on the orientation of the as-spun blend fibers is highly composition-dependent, which is mainly associated with the formation of LCP fibrils during melt spinning. The modulus of the as-spun blend fibers has a significant increase as the content of LCP reaches 10%, while the tensile strength has a slightly decreasing tendency. The mechanical properties of the as-spun blend fibers could be well improved by heat treatment because of a striking increase in the crystallinity of the PET matrix. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 217–224, 1997