Fiber reinforcement and fracture resistance of PC/PBT/LCP ternary in situ composite

The microstructures, mechanical properties, and fracture toughness of LCP (Vectra B950) reinforced PC/PBT blend with a 60/40 weight ratio have been studied. LCP of varying concentrations were investigated as rigid fillers in matrices of multiphase polymer blends. In this study, differences in microstructures and morphology between samples of two thicknesses (4 mm thick and 6 mm thick) and two geometries (dumbbell and rectangular) were compared using scanning electron microscopy (SEM). Given identical processing conditions, fibrous LCP structures were evident in the 4-mm-thick injection molded, dumbbell-shaped samples, whereas the 6-mm-thick rectangular samples displayed spherical dispersion of LCP aggregates that embrittled the preblended ductile matrix. Tensile properties of the dumbbell specimens showed superior strengthening and stiffening whereby the tensile strength increased twofold and the modulus increased fourfold. Plane strain fracture toughness was slightly enhanced as the LCP content increased because of the fiber strengthening effect but the overall fracture performance of the in situ composites was relatively poor compared with PC/PBT. Experimental results were compared with those predicted in composite theory. Simplified micromechanics equations were developed to describe the tensile moduli of injection molded LCP reinforced blends that exhibited a strong skin-core morphology.     

Characterization of thermotropic liquid crystalline polyester/polysulfone blends

The morphology, rheology, and mechanical properties of blends of polysulfone (PSF) with up to 65% of a wholly aromatic liquid crystalline polymer (LCP) were investigated. In injection molded specimens a skin-core morphology was observed with the LCP minor phase oriented in the skin and globular in the core. Scanning electron microscopy of fractured surfaces showed sharp phase boundaries, suggesting low interfacial adhesion. The neat PSF and blends with low amounts of LCP exhibited a low shear Newtonian plateau not observed in the blends with high LCP levels. The addition of LCP to PSF resulted in an increase in stiffness, a small increase in tensile strength, and a significant improvement in processability.     

Morphological development during injection molding of self‐reinforcing composites. I: Experimental results

The correlation between structure development during injection molding and the modulus of injection molded PET/LCP blends were studied. Process parameters such as injection speed and mold and melt temperatures were varied to determine the effect of these parameters on the tensile modulus and structure development of the blends. The skin/core structure in the cross section of injection molded samples was observed with both optical and scanning electron microscopy techniques. Injection molding experiments show that the thickness of the skin layer increases with decreasing injection speed and decreasing melt and mold temperatures. The trends in morphological developments in the injection molded specimens correlate with the measured tensile moduli.     

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.     

Blends of thermotropic liquid crystalline polyesters and poly(butylene terephthalate): Thermal,mechanical, and morphological properties

Blends of poly(butylene terephthalate) (PBT) with three different thermotropic liquid crystalline polyesters (TLCPs) were prepared. The first TLCP (HBH-6) consists of diad aromaticester type mesogenic units and the hexamethylene spacers along the main chain, and the second (TB-S6) is a wholly aromatic polyester TLCP having alkoxy side groups on the terephthaloyl moiety. The last (TR-4,6) is an LC copolymer comsisting of triad aromatic ester type mesogenic units and two differents spacers; tetramethylene and hexamethylene units. Blends of TLCP with PBT were melt spum at different LCP contents and differnt draw ratios to produce monofilaments. For the HBH-6/PBT and TB-S6/PBT blends, the ultimate tensile strength showed a maximum value at the 5 wt% level of LCP in the blends, and then it decreased when the LCP content was increased up to 20%. On the other hand, the initial modulus monotonically increased with increasing LCP content in all cases. The blends with TB-S6 showed the highest tensile properties of the three blends systems. This can be ascribed to the highest rigidity of the polymer chain, which still carries relatively long alkoxy substituents that promote sufficient adhesion between the LCP and PBT matrix. When compared with the PBT fiber itself, the fibers obtained from the 5% TB-S6/PBT blends exhibited an improvement in tensile strength by > 25% and in tensile modulus by ～ 200%.     

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.     

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.     

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.     

Thermal and mechanical properties of injection molded blends of a liquid crystalline polymer and poly(butylene terephthalate)

The microstructure and the thermal and mechanical properties of injection molded samples of different blends of Vectra (LCP) and poly(butylene terephthalate) (PBT) have been studied. Differential scanning calorimetry and hot-stage polarized light microscopy showed that the crystallization of PBT was unaffected by the presence of LCP. X-ray diffraction showed that the PBT component was always unoriented in the injection molded samples. Blends with less than 28 vol% LCP exhibited the same stiffness and the same coefficient of linear thermal expansion as PBT. Blends containing more than 38 vol% LCP contained an oriented LCP phase and had a stiffness in accordance with the upper-bound composite equation. The coefficients of linear thermal expansion for these blends were close to that of pure LCP.     

Blends of a PPO–PS alloy with a liquid crystalline polymer

Blends of a PPO–PS alloy with a liquid crystalline polymer have been studied for their dynamic properties, rheology, mechanical properties, and morphology. This work is an extension of our previous work on PPO/LCP blends. The addition of the LCP to the PPO–PS alloy resulted in a marked reduction in the viscosity of the blends and increased processibility. The dynamic studies showed that the alloy is immiscible and incompatible with the LCP at all concentrations. The tensile properties of the blends showed a drastic increase with the increase in LCP concentration, thus indicating that the LCP acted as a reinforcing agent. The tensile strength, secant modulus, and impact strength of the PPO–PS/LCP blends were significantly higher than that of PPO/LCP blends. Morphology of the injection molded samples of the PPO–PS/LCP blends showed that the in situ formed fibrous LCP phase was preserved in the solidified form. A distinct skin–core morphology was also seen for the blends, particularly with low LCP concentrations. The improvement of the mechanical properties of the blends is attributed to these in situ fibers of LCP embedded in the PPO–PS matrix. The improvement in the properties of PPO–PS/LCP over PPO/LCP is also attributed to the addition of the PS which consolidates the matrix. © 1995 John Wiley & Sons, Inc.     

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.     

Properties of ternary in situ polycarbonate/polybutylene terephthalate/liquid crystalline polymer composites

Ternary in situ polycarbonate (PC)/polybutylene terephthalate (PBT)/liquid crystalline polymer (LCP) composites were prepared by injection molding. The liquid crystalline polymer used was a versatile Vectra A950. The matrix of composite was composed of PC/PBT 60/40 by weight. A solid epoxy resin (bisphenol type‐A) was used as a compatibilizer for the composites. Dynamic mechanical analysis (DMA) showed that epoxy resin was effective to improve the compatibility between PC and PBT, and between PC/PBT and LCP, respectively. Tensile tests revealed that the stiffness of composites shows little change with the LCP content up to 10 wt %. Above this concentration, the stiffness tended to increase with increasing LCP content. Furthermore, the tensile strengths appeared to increase with increasing LCP content, and their values were close to those predicted from the rule of mixtures. Scanning electron microscopic examination showed that LCP ribbons and short fibrils were developed in the composites containing LCP content ≤10 wt %. However, fine and elongated fibrils were formed in the skin and core sections of the composites when the LCP content reached 25 wt % and above. Thermogravimetric analysis indicated that the thermooxidative stability of the PC/PBT 60/40 blend tended to improve with increasing LCP content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1827–1835, 1999     

Study on in situ reinforcing and toughening of a semiflexible thermotropic copolyesteramide in PBT/PA66 blends

Ternary in situ composites based on poly(butylene terephthalate) (PBT), polyamide 66 (PA66), and semixflexible liquid crystalline polymer (LCP) were systematically investigated. The LCP used was an ABA30/PET liquid crystalline copolyesteramide based on 30 mol % of p‐aminobenzoic acid (ABA) and 70 mol % of poly(ethylene terephthalate) (PET). The specimens for thermal and rheological measurements were prepared by batch mixing, while samples for mechanical tests were prepared by injection molding. The results showed that the melting temperatures of the PBT and PA66 phases tend to decrease with increasing LCP addition. They also shifted toward each other due to the compatibilization of the LCP. The torque measurements showed that the ternary blends exhibited an apparent maximum near 2.5–5 wt % LCP. Thereafter, the viscosity of the blends decreased dramatically at higher LCP concentrations. Furthermore, the torque curves versus the PA66 composition showed that the binary PBT/PA66 blends can be classified as negative deviation blends (NDBs). The PBT/PA66/LCP blends containing up to 15 wt % LCP were termed as positive deviation blends (PDBs), while the blends with the LCP ≥25 wt % exhibited an NDB behavior. Finally, the tensile tests showed that the stiffness and tensile strength of ternary in situ composites were generally improved with increasing LCP content. The impact strength of ternary composites initially increased by the LCP addition, then deteriorated when the LCP content was higher than 10 wt %. The correlation between the mechanical properties and morphology of the blends is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1975–1988, 2000     

Compatibilization by sulfonate ionomers in polyblends with thermotropic liquid crystalline polymers

It is shown by differential scanning calorimetry (DSC) measurements that lightly sulfonated polystyrene (SPS) is partially miscible with polysulfone (PSF), polycarbonate (PC), polyetherimide (PEI), and a thermotropic liquid crystalline polymer (LCP). Fourier transform infrared analysis confirms that the miscibility of SPS and PSF, and of SPS and PC, comes from the ion–dipole interaction between the sulfonate groups of SPS and the polar groups of PSF and PC, respectively. After the addition of SPS to LCP/PSF, LCP/PC, and LCP/PEI blends, this specific interaction leads to the compatibilization of SPS in these blends, which is revealed by inward glass transition temperature shifts of component polymers in DSC and dynamic mechanical analysis thermograms and by a much finer dispersion of the minor LCP phase in these matrix polymers. The utilization of SPS as the compatibilizer results in a stronger interfacial adhesion between LCP and matrix phases and improves the mechanical performances of LCP/PSF, LCP/PC, and LCP/PEI blends as well. Compared with ternary LCP/PSF, LCP/PC, and LCP/PEI blends with polystyrene as an inert third component, the ternary LCP/SPS/PSF, LCP/SPS/PC, and LCP/SPS/PEI blends have significantly enhanced tensile strengths and moduli, with acceptable processabilities at the same time. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2141–2151, 1998     

Electrical conductivity of polymer blends containing liquid crystalline polymer and carbon black

This paper presents results of a study of melt‐processed immiscible polymer blends of high impact polystyrene (HIPS), liquid crystalline polymer (LCP) and carbon black (CB). Relationships between composition, electrical resistivity and morphology of the blends produced by Brabender mixing followed by compression molding, extrusion through a capillary rheometer, extrusion through a single‐screw extruder and injection molding were investigated. The LCP phase morphology in the blends was found sensitive to the processing conditions. A blend composition of at least 20 wt% LCP and 2 phr CB is necessary to preserve the conductivity of filaments produced over a wide range of shear rates. Enhancement of conductivity of blends containing CB and 30 wt% or more LCP was observed, under processing at 270°C and increasing levels of shear rate. An important role of the skin region in determining the resisitivy of injection molded samples was found. A good agreement between resistivity values of extruded or injection molded blends with resistivity values of filaments produced at similar conditions by a capillary rheometer was shown. Hence, the study of shear rate effect on resistivity of capillary rheometer filaments may serve as a predictor of resistivity behavior in real processing procedures. Polym. Eng. Sci. 44:528–540, 2004. © 2004 Society of Plastics Engineers.     

Compatibilization of poly(ethylene terephthalat)/liquid crystal polymer blends by means of bisphenol a polycarboate

A compatibilization method that consists of the addition of minor amounts of a commercial thermoplastic, which interacts or reacts with both the matrix and the dispersed liquid crystalline polymer (LCP) of thermoplastic/LCP blends, has been tested in the case of poly(ethylene terephthalate)/Vectra A950 (PET/VA) blends by means of the addition of bisphenol A polycarbonate (PC). The smaller particle size, rougher surface of the fibers and higher ductility of the PET/VA blends of a 30% of the PET substituted by PC clearly showed the suitability of PC as a compatibilizer. The moduli of elasticity of the compatibilized and uncompatibilized blends were similar. This was due to the less‐developed fibrillation of the compatibilized blends, a consequences of their smaller particle size and decreased matrix viscosity. These changes counteracted the effects of improved interfacial adhesion. The improved adhesion led to higher ductility and tensile and impact strengths in most of the compatibilized blends.     

Mechanical performance of blends of thermotropic liquid crystalline polymer spheres‐dispersed polycarbonate

Liquid crystalline polymer (LCP) blends with a thermotropic LCP dispersed in the form of microspheres is studied to show the role of LCP spheres. Polycarbonate (PC), p‐hydroxybenzoic acid–poly(ethylene terephthalate) copolyester, and random styrene–maleic anhydride copolymer are used as the matrix, the dispersed phase, and the compatibilizer, respectively. A scanning electron microscopy observation shows the formation of LCP spheres with improved interfacial adhesion in the injection‐molded samples via compatibilization. The mechanical tests show increased modulus, elongation at break, and fracture‐absorbed energy of blends of LCP spheres‐dispersed PC. This shows an optimistic potential for the dispersed LCP phase, in spite of its morphology in the form of fibrils for reinforcing the matrix or in the form of microspheres for toughening the matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1493–1499, 2003     

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     

Mechanical properties and morphology of liquid crystalline copolyester-amide and amorphous polyamide blends

Blends of an amorphous polyamide (PA) and a liquid crystalline copolyesteramide (LCP), poly(naphthoate-aminophenoterephthalate) were prepared in a twin-screw extruder. Specimens for mechanical testing were prepared by injection molding. Morphological, thermal, mechanical, and rheological properties were investigated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffractometry, capillary rheometry, and a tensile tester, respectively. The tensile mechanical behavior of the LCP/PA blends was found to be affected by their compositions and specimen thickness. Tensile testing revealed that the tensile mechanical behavior of the LCP/PA blends was very similar to that of polymeric composite and the tensile strength of the LCP/PA (50/50) blend was approximately two times of the value of PA homopolymer and exceeded that of pure LCP. The morphology of the LCP/PA blends was also found to be affected by their compositions. SEM studies revealed that the liquid crystalline polymer (LCP) formed finely dispersed spherical domains in the PA matrix and the inclusions were deformed into fibrils from the spherical droplets with increasing LCP content. It has been found that droplet and fiber formations lead to low and high strength material, respectively. In particular, at specific LCP content (50 wt%), the tensile strength of the LCP/PA blend exceeded that of pure LCP. The improvement in tensile properties is likely due to the reinforcement of the PA matrix by the fibrous LCP phase as observed by SEM. A distinct shell-core morphology was found to develop in the injection molded samples of these blends. This is believed to have a synergistic effect on the tensile properties of the LCP/PA blends. The rheological behavior of the LCP/PA blends was found to be very different from that of the parent polymers and significant viscosity reductions were observed for the LCP/PA (50/50) blend. Based upon DSC, these blends have shown to be incompatible in the entire range of concentrations.     

Morphology and mechanical properties of liquid crystalline copolyester and poly(ethylene 2,6-naphthalate) blends

Blends of poly(ethylene 2,6-naphthalate) (PEN) 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 and mechanical properties were investigated by scanning electron microscopy (SEM) and an Instron tensile tester. SEM studies revealed that finely dispersed spherical domains of the liquid crystalline polymer (LCP) were formed in the PEN matrix, and the inclusions were deformed into fibrils from the spherical droplets with increasing LCP content. The morphology of the blends was found to be affected by their composition and a distinct skin-core morphology was found to develop in the injection molded samples of these blends. Mechanical properties were improved with increasing LCP content, and synergistic effects have been observed at 70 wt% LCP content whereas the elongation at break was found to be reduced drastically above 10 wt% of LCP content. This is a characteristic typical of chopped-fiber-filled composites. The improvement in mechanical properties is likely due to the reinforcement of the PEN matrix by the fibrous LCP phase as observed by scanning electron microscopy. The tensile and modulus mechanical behavior of the LCP/PEN blends was very similar to those of the polymeric composite, and the tensile strength and flexural modulus of the LCP/PEN 70/30 blend were two times the value of PEN homopolymer and exceeded those of pure LCP, suggesting LCP acts as a reinforcing agent in the blends.