Structure and properties of molded polyblends containing liquid crystalline polymers

The relationship between the microstructure developed during injection molding of liquid crystalline polymers (LCPs) containing blends and their mechanical properties, was studied. A wholly aromatic copolyester LCP was melt blended in various levels with polycarbonate (PC), poly(butylene terephthalate) (PBT), Nylon 6 (N-6), and amorphous nylon (AN). In all cases the LCP was the minor component. The resulting injection molded structure had a distinct skin core morphology, where elongated fibrous LCP particles comprised the skin layer and spherical and ellipsoidal ones composed the core section. The highest elongation and the finest diameter LCP fibrils were obtained with AN/LCP system, followed by PC/LCP. PBT/LCP blends showed a coarser morphology, while N-6/LCP system did not correlate with the tensile moduli of the injection molded specimens. AN/LCP blends demonstrated the highest moduli values, consistent with the highest orientations observed using electron microscopy, followed by PC/LCP, PBT/LCP, and N-6/LCP. Finally, tensile strength levels were correlated with both orientation levels and interfacial adhesion between the polyblend components. AN/LCP that exhibited the highest orientation and good adhesion appearance gave the highest tensile strength values followed by PC/LCP, PBT/LCP, and N-6/LCP polyblends.     

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.     

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.     

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.     

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     

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     

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.     

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.     

Effect of ABS grafting degree and compatibilization on the properties of PBT/ABS blends

Blends of PBT/ABS and PBT/ABS compatibilized with styrene‐acrylonitrile‐glycidyl methacrylate (SAG) copolymer were prepared by melt blending method. Grafting degree (GD) of ABS influences the morphology and mechanical properties of PBT/ABS blends. ABS can disperse in PBT matrix uniformly and PBT/ABS blends fracture in ductile mode when ABS grafting degree is more than 44.8%, otherwise, agglomeration takes place and PBT/ABS blends fracture in brittle way. On the other hand, the grafting degree of ABS has no obvious influence on the morphology of PBT/ABS blends and PBT/ABS blends fracture in ductile mode when SAG is incorporated since the compatibilization effect. However, PBT/SAG/ABS blends display much lower impact strength values comparing with PBT/ABS when the blends fracture in ductile way. Side reactions in PBT/SAG/ABS blends were analyzed and which were the main reason for the decrease of impact strength of PBT blends. Tensile tests show that the tensile strength and tensile modulus of PBT blends decrease with the increase of ABS grafting degree due to the higher effective volume. PBT/SAG/ABS blends display much higher tensile properties than PBT/ABS blends since the compatibilization effect. POLYM. COMPOS., 28:484–492, 2007. © 2007 Society of Plastics Engineers     

Effects of processing conditions on the mechanical performance of maleic anhydride compatibilized in-situ composites of polypropylene with liquid crystalline polymer

Maleic anhydride compatibilized blends of isotactic polypropylene (PP) and thermotropic liquid crystaline polymer (LCP) were prepared either by the direct injection molding (one-step process), or by twin-screw extrusion blending, after which specimens were injection molded (two-step process). The morphology and mechanical properties of these injection molded in situ LCP composites were studied by means of scanning electron microscopy (SEM), Izod impact testing, static tensile, and dynamic mechanical measurements. SEM observations showed that fine and elongated LCP fibrils are formed in the maleic anhydride compatibilized in situ composites fabricated by means of the one-step process. The tensile strength and modulus of these composites were considerably close to those predicted from the rule of mixtures. Furthermore, the impact behavior of LCP fibril reinforced composites was similar to that of the glass fiber reinforced polymer composites. On the other hand, the maleic anhydride compatibilized blends prepared from the two-step process showed lower mechanical performance, which was attributed to the poorer processing behavior leading to the degradation of PP. The effects of the processing steps, temperatures, and compatibilizer addition on the mechanical properties of the PP/LCP blends are discussed.     

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%.     

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.     

Toughening modification of PBT/PC blends with PTW and POE

New toughened poly(butylene terephthalate) (PBT)/bisphenol A polycarbonate (PC) blends were obtained by melt blending with ethylene–butylacrylate–glycidyl methacrylate copolymer (PTW) and ethylene‐1‐octylene copolymer (POE) in a twin‐screw extruder. The mechanical properties of PBT/PC blends were investigated. The presence of PTW or POE could improve the mechanical properties except for the tensile strength and flexural properties of the PBT/PC blends. However, a combination use of PTW and POE had a strong synergistic effect, leading to remarkable increases in the impact strength, elongation at break, and Vicat temperature and some reduction of the tensile strength and flexural properties. The relationship between mechanical properties and morphology of the PBT/PC/PTW/POE blends was studied. The morphology was observed by scanning electron microscopy and the average diameter of dispersed phase was determined by image analysis, and the critical interparticle distance for PBT/PC was determined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 54–62, 2006     

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 processing parameters on the mechanical properties of in situ compatibilized polybutylene terephthalate/acrylonitrile–butadiene–styrene blends

To evaluate mechanical properties of blends prepared by intermeshing corotating twin‐screw extrusion (ICTSE), it is usually necessary to injection mold specimens after the extrusion mixing process. At this study an alternative method is used to obtain testing specimens from ribbons extruded polybutylene terephthalate/acrylonitrile–butadiene–styrene blends, (PBT/ABS), compatibilized with methyl methacrylate–glycidyl methacrylate‐ethyl acrylate (MGE) by ICTSE, and then to correlate their mechanical properties with the processing parameters. Regarding to the extrusion process parameters, it has been noted that higher feed rates, lower screw speeds and narrower kneading blocks have reduced the ductile‐brittle transition temperature (DBTT) of the compatibilized PBT/ABS blends, thereby suggesting that the molecule integrity of blend polymeric components has been preserved and that a good dispersion of the ABS domains in the PBT matrix has been achieved. Injection molded PBT/ABS blends were obtained to compare to the extruded ribbons. The mechanical tests for both specimens have shown the same trends. The injection molded samples have presented poorer impact strength, tensile strain at break and tensile strength, when compared to the respective extruded samples. That behavior has been attributed to the high level of molecular orientation resulting from the injection molding process and mainly to PBT degradation during process. The PBT degradation could have increased its degree of crystallinity, which has been confirmed by DSC measurements. As result, the blend became more brittle, decreasing its Izod impact strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure and mechanical properties of fast cooled and annealed poly(phenylene sulfide)/Vectra A blends

Poly(phenylene sulfide) (PPS)/Vectra A blends were directly injection molded and obtained throughout the composition range both as molded, low crystallinity, and annealed highly crystalline materials. The blends were immiscible, but, contrary to an earlier work on PPS/Vectra A blends, they showed a clear fibrous morphology that was a consequence of the higher viscosity of the matrix compared with that of the Vectra A at the shear strain rate used. The mechanical properties of the annealed blends showed that when highly crystalline materials are sought, annealing post‐cold molding is a valid alternative to molding at high mold temperatures. The fracture properties of the as‐molded blends, such as ductility and tensile strength, were higher than in annealed blends, as a consequence of the higher deformability of the less crystalline structure. The presence of the LCP in the as‐molded low‐crystallinity PPS blends counteracts their intrinsic lower stiffness by means of a faster stiffness increase when Vectra A was added, compared with that which took place in annealed blends. These facts rendered the as‐molded PPS/Vectra A blends alternative materials to the usual highly crystalline ones.     

A gradient structure formed in injection‐molded polycarbonate in situ hybrid composites and its corresponding performances

Three polycarbonate (PC) composites that were reinforced, respectively, with liquid crystalline polymer (LCP), glass fibers, and both of them were prepared by a single injection‐molding process. The role of LCP in improving the processibility of the composites was characterized by torque measurement test. The transitions of LCP morphology in two‐ and three‐component composites were investigated by using polarizing optical microscopy and scanning electron microscopy. The micrographs showed a skin–core gradient structure in all three systems investigated, and the addition of glass fiber to the PC/LCP blend affected the morphological transition and content distribution of dispersed LCP phase through the thickness of the injection‐molded samples. These results were correlated well with the measurements of tensile mechanical properties and dynamic mechanical analysis. How to fully use the dispersed LCP phase in PC in situ hybrid composites was discussed for the thickness change of core layer and the heterogeneous distribution of more LCP in the core. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 625–634, 2004     

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.     

Effect of core-shell particles dispersed morphology on the toughening behavior of PBT/PC blends

Methyl methacrylate-co-styrene-co-glycidyl methacrylate grafted polybutadiene (PB-g-MSG) and styrene-co-glycidyl methacrylate grafted polybutadiene (PB-g-SG) core-shell particles were prepared to toughen poly (butylene terephthalate) (PBT) and polycarbonate (PC) blends. The compatibilization reaction between the epoxy groups of glycidyl methacrylate and the carboxyl groups of PBT induced the PB-g-SG particles dispersed in the PBT phase. On the other hand, the good miscibility between PMMA (the shell phase of PB-g-MSG) and PC induced the PB-g-MSG particles dispersed in the PC phase. The different phase morphology led to different toughening behavior. The PBT/PC/PB-g-MSG blends with the PC encapsulated morphology showed much lower brittle-ductile transition core-shell particles content (10-15 wt% or 15-20 wt%) compared with the PBT/PC/PB-g-SG blends (20-25 wt%). The difference between the toughening efficiency of the core-shell particles was due to the change of deformation mechanisms. In PBT/PC/PB-g-MSG blends, the cavitation of PB rubber phase led to the occurrence of shear yielding of the matrix. While in the PBT/PC/PB-g-SG blends, the debonding between PBT and PC interface induced the shear yielding of the matrix. The variation of the core-shell particles dispersed phase morphology also affected the crystallization properties and DMA results of the PBT/PC blends. Modification of the phase morphology provided an useful strategy to prepare PBT/PC blends with higher toughening efficiency.     

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.