The effect of the viscosity ratio of dispersed phase to matrix on the rheological,morphological, and mechanical properties of polymer blends containing a LCP

The effect of the viscosity ratio of the dispersed LCP phase to the polystyrene/poly(phenylene oxide) (PS/PPO) thermoplastic matrix on the rheological, morphological, and resultant mechanical properties of the LCP blends was investigated. The viscosity of PS/PPO is largely dependent on the blend composition, so that different levels of viscosity ratios of dispersed LCP phase to PS/PPO thermoplastic matrix are obtained by using PS/PPO premixtures of different blend ratios as a thermoplastic matrix. When the viscosity of the LCP dispersed phase is lower than that of the thermoplastic matrix, finely distributed fibril structure of LCP is obtained. Tensile modulus of injection molded specimens show a positive deviation from the additive rule when the viscosity ratio (η_LCP/η_matrix) is smaller than unity. These improvements in tensile modulus are attributed to the formation of finely distributed LCP fibrils. © 1996 John Wiley & Sons, Inc.     

Mechanical properties and morphology of LCP/ABS blends compatibilized with a styrene–maleic anhydride copolymer

A co‐polyester liquid crystalline polymer (LCP) was melt blended with an acrylonitrile–butadiene–styrene copolymer (ABS). LCP fibrils are formed and a distinct skin/core morphology is observed in the injection moulded samples. At higher LCP concentration (50 wt%), phase inversion occurs, where the dispersed LCP phase becomes a co‐continuous phase. While the tensile strength and Young's modulus remain unchanged with increasing LCP content up to 30 wt% LCP, a significant enhancement of the modulus at 50 wt% LCP is observed due to the formation of co‐continuous morphology. The blend modulus is lower than the values predicted by the rule of mixtures, suggesting a poor interface between the LCP droplets and ABS matrix. A copolymer of styrene and maleic anhydride (SMA) was added in the LCP/ABS blends during melt blending. It is observed that SMA has a compatibilizing effect on the blend system and an optimum SMA content exists for mechanical properties enhancement. SMA improves the interfacial adhesion, whereas excess of SMA reduces the LCP fibrillation. Copyright © 2003 Society of Chemical Industry     

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.     

The effect of composition on thermal,mechanical, and morphological properties of thermotropic liquid crystalline polyester with alkyl side-group and polycarbonate blends

A thermotropic liquid crystalline polymer (LCP) with an alkyl side-group was synthesized. Blends of the LCP with polycarbonate (PC) were prepared by coprecipitatton from a common solvent. The rheological behavior of the LCP/PC blends was found to be very different from that of PC, and significant viscosity reductions were observed in the temperature range of 200–230°C. Blends of different LCP compositions were extruded with different draw ratio from a capillary rheometer. The ultimate tensile strength showed a maximum at a 10 wt% LCP composition in the blends. It decreased for compositions greater the 10 wt% LCP, whereas the initial modulus increased with increasing LCP content. The morphology of the blends was found to be affected by their compositions. Scanning electron microscopy (SEM) studies revealed finely dispersed spherical LCP domains in the PC matrix. The SEM micrographs also showed a poor adhesion between the two phases.     

Influence of processing history on the properties of a thermotropic copolyester/polycarbonate blend

Relationships between the rheological, morphological, and tensile properties of an immiscible blend of 25 wt% of a thermotropic liquid crystalline polymer (LCP) with polycarbonate are presented. The shear viscosity of the blend is intermediate between the two constituent materials, and indicates immiscibility in the melt. Extrudate swell behavior is examined and found to be closely related to that of polycarbonate. The morphology of the dispersed LCP phase varies between droplets and oriented fibrils, and is highly correlated with changes in tensile properties. Fibrils are associated with increased tensile modulus, and their development is favored in the elongation flow fields present in the spinline and in the die convergence section. In all cases, blend stiffness is less than that predicted for a continuous fiber-reinforced composite. Enhanced tensile modulus is associated with both extrusion from shorter length dies and increases in spinline draw ratio, with the latter proving the most important in fibril formation.     

Factors influencing microstructure formation in polyblends containing liquid crystalline polymers

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

Correlation of viscosity ratio,morphology, and mechanical properties of polyamide 12/natural rubber blends via reactive compatibilization

Natural rubber (NR)-modified polyamide 12 (Nylon12/NR) was produced by melt blending Nylon12 and NR in the presence of polystyrene/maleated natural rubber (PS/MNR) copolymer as a reactive compatibilizer. The influence of compatibilizer loading on viscosity ratio, morphology, and mechanical properties of the blends was investigated. As a consequence of the reactive blend between Nylon12 and maleated NR in PS/MNR, the formation of amide and succinimide linkages was set at rubber-Nylon12 interfaces. Thus the dispersion of rubber particles was improved, and the particle coalescence was prevented so that the fine morphology with good interfacial adhesion was stabilized. This also resulted to enhance the blend viscosity and to lower viscosity ratio. The data revealed strong correlation between low viscosity ratio and fine spherical morphology of the compatibilized blends. An optimum PS/MNR compatibilizer content was at 7 phr to produce good dispersion of small rubber domains (size ≤0.3 μm) in Nylon12 matrix. Thermal properties by DSC revealed that crystallization temperature of Nylon12 was lowered by the presence of NR and crystallinity of Nylon12 was slightly affected by the PS/MNR content. An enhancement of mechanical properties, especially the impact energy was observed without suffering the tensile and flexural properties. Compared to the neat Nylon12, the compatibilized blends showed an increase in impact energy by a factor of 5. This large enhancement is successfully interpreted in term of the toughening effect by rubber phase of suitable dispersed size and the interparticle distance.     

Rheological and physical properties of in situ composite based on liquid crystalline polymer and poly(ethylene 2,6‐naphthalate) blends

The in situ composites based on poly(ethylene 2,6‐naphthalate) (PEN) and liquid crystalline polymer (LCP) were investigated in terms of thermal, rheological, and mechanical properties, and morphology. Inclusion of LCP enhanced the crystallization rate and tensile modulus of the PEN matrix, although it decreased the tensile strength in the PEN‐rich phase. The orientation effect of this blend system was composition and spin draw ratio dependent, which was examined by Instron tensile test. Further, the addition of dibutyltindilaurate (DBTDL) as a reaction catalyst was found to increase the viscosity of the blends, enhance its adhesion between the dispersed LCP phases and matrix, and led to an increase of mechanical properties of two immiscible blends. Hence DBTDL is helpful in producing a reactive compatibilizer by reactive extrusion at the interface of this LCP reinforced polyester blend system. The optimum catalyst amount turned out to be about 500 ppm, when the reaction proceeded in the 75/25 PEN/LCP blend system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2448–2456, 1999     

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     

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 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.     

The effect of viscosity ratio on the phase inversion of polyamide 66/polypropylene blends

The rheological properties of the blend components are an important parameter in the formation of a blend morphology. The effect of viscosity ratio on the morphology of polyamide 66/polypropylene blends was studied, with primary attention to the phase-inversion behavior and the average particle size of the dispersed phase. The relationship between the mechanical properties and the phase-inversion composition was investigated as well. Noncompatibilized and compatibilized blends having five different viscosity ratios were prepared by twin-screw extrusion. Maleic anhydride-grafted polypropylene was used as the compatibilizer to increase the adhesion between the two polymers and to stabilize the blend morphology. Investigation of the morphology of the blends by microscopy (SEM and TEM) showed that the smaller the viscosity ration (η_PA/η_PP) the smaller was the polyamide 66 concentration at which the phase inversion took place and that polyamide 66 became the continuous phase. The results are in accord with the model of Jordhamo. The compatibilizer induced a sharp reduction of particle size, but did not have a major effect on the phaseinversion point. The tensile and impact properties of the compatibilized blends were found to correlate with the phase inversion. An improvement in the mechanical properties was observed when polyamide 66 provided the matrix phase. © 1994 John Wiley & Sons, Inc.     

Effect of viscosity ratio and processing conditions on the morphology of blends of liquid crystalline polymer and polypropylene

The effect of viscosity ratio and processing conditions on LCP/PP blend morphology was studied. The viscosity ratio (η_LCP/η_PP) was varied from 0.1 to 3.6 by using five different polypropylene grades as the matrix and two LCPs as the dispersed phase (20 wt %). The most spontaneous fiber formation was achieved when the viscosity ratio was between 0.5 and 1. In addition to shear forces, elongational forces are important in achieving a highly fibrillar structure and significant mechanical reinforcement. The lubricating effect induced by the low viscosity of LCP was most pronounced for the blends exhibiting a fibrillar morphology. The morphologies of blends produced by different mixing equipment differed only slightly. The greatest variation in the mixing efficiency was found for blends whose components had totally dissimilar melt viscosities. The slight differences in morphology due to melt blending in dissimilar equipment were decreased after injection molding, whereas the differences in morphology due to dissimilar viscosity ratios were still evident in the injection molded blends. Thus, the viscosity ratio at processing in the actual processing conditions is of great importance. © 1994 John Wiley & Sons, Inc.     

Comparative study on phase and properties between rPET/PS and LCP/PS in situ microfibrillar-reinforced composites

Microfibrillar-reinforced composites based on two dispersed phases, liquid crystalline polymer (LCP) and recycled poly(ethylene terephthalate) (rPET), and polystyrene (PS) were prepared using extrusion process. The rheological behavior, morphology, and thermal stability of LCP/PS and rPET/PS blends containing various dispersed phase contents were investigated. All blends and LCP exhibited shear thinning behavior, whereas Newtonian fluid behavior was observed for rPET. The incorporation of both LCP and rPET into PS significantly improved the processability. The potential of rPET as a processing lubricant by bringing down the melt viscosity of the blend system was as good as LCP. The elongated LCP domains were clearly observed in as-extruded strand. Although the viscosity ratio of rPET/PS system was lower than that of LCP/PS system, most rPET domains appeared as small droplets. An addition of LCP and rPET into PS matrix improved the thermal resistance in air significantly. The obtained results suggested the high potential of rPET as a processing aid and thermally stable reinforcing-material similar to LCP. The mechanical properties of the LCP-containing blends were mostly higher than those of the corresponding rPET-containing blends when compared at the same blend composition.     

Effect of LCP and rPET as reinforcing materials on rheology,morphology, and thermal properties of in situ microfibrillar‐reinforced elastomer composites

Microfibrillar‐reinforced elastomer composites based on two dispersed phases, liquid crystalline polymer (LCP) and recycled poly(ethylene terephthalate)(rPET), and styrene‐(ethylene butylene)‐styrene (SEBS) were prepared using extrusion process. The rheological behavior, morphology, and thermal stability of SEBS/LCP and SEBS/rPET blends containing various dispersed phase contents were investigated. All blends and LCP exhibited shear thinning behavior, whereas Newtonian fluid behavior was observed for rPET. The incorporation of both LCP and rPET into SEBS significantly improved the processability by bringing down the melt viscosity of the blend system. The fibrillation of LCP dispersed phase was clearly observed in as‐extruded strand with addition of LCP up to 20–30 wt %. Although the viscosity ratio of SEBS/rPET system is very low (0.03), rPET domains mostly appeared as droplets in as‐extruded strand. The results obtained from thermogravimetric analysis suggested that an addition of LCP and rPET into the elastomer matrix improved the thermal resistance significantly in air but not in nitrogen. The simultaneous DSC profiles revealed that the thermal degradation of all polymers examined were endothermic and exothermic in nitrogen and in air, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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.     

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.     

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.