The mechanism of skin-core morphology formation in extrudates of polycarbonate/liquid crystalline polymer blends

The mechanism of skin/core morphology development and LCP (liquid crystalline polymer) fibril formation in polycarbonate/LCP blends was studied. A certain minimum concentration of the LCP phase must be present for the formation of continuous LCP fibrils in the extrudates. A skin-core morphology characterizes the PC/LCP extrudates. Short LCP fibrils are formed in the capillary converging entrance section, through the elongation of LCP domains and their coalescence. Continuous fibrils were formed in the skin of extrudates emerging from cylindrical capillaries, through the coalescence of the short fibrils, provided the shear stresses are high enough and the LCP viscosity is equal or lower than that of PC. Increasing capillary length enhances the LCP lateral migration and fibrils formation. The high interfacial tension stabilizes the LCP fibrils. In the core region the short fibrils recoil or breakup, resulting in spherical or elongated droplets. Long and continuous fibrils cannot be formed in a zero length capillary, even at high flow rates.     

Structure development during flow of polyblends containing liquid crystalline polymers

The microstructure development during capillary flow of polyblends containing Liquid Crystalline Polymers (LCPs) was studied. In the present investigation the wholly aromatic LCP constituent was the minor phase suspended in polycarbonate (PC), poly(butyleneterephthalate) (PBT) or Nylon 6 (N-6), in addition to previously studied amorphous nylon matrix Experimental results showed that the viscous forces acting at the components' interface are predominating the elongational deformation and the resulting structure development of the LCP phase. In cases where the viscosity of the suspending matrix was higher than the LCP one (PC, amorphous nylon) scanning electron micrographs indicated that fibrillar structure developed. In cases where the viscosity of the matrix polymers was lower than the LCP suspended phase, fibrous structures developed only at very high shear rates. Due to velocity rearrangement effects at the capillary exit a skin core morphology was observed. Since the polymers viscosity depends both on shear rate and temperature, the in situ composite structure development depends on the specific processing methods and conditions that the LCP containing polyblends experience.     

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

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

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     

The morphology and rheology of polymer blends containing a liquid crystalline copolyester

The morphology of blends of polycarbonate and nylon 6,6 with a copolyester of 60 mole percent p-hydroxybenzoic acid/40 mole percent poly(ethylene terephthalate) was characterized under different processing conditions. In particular, single-screw extrusion, steady simple shear flow, and flow through a capillary were studied to determine what conditions were necessary for the development of a fibrillar morphology of the liquid crystalline polymer (LCP). Results indicate that some extensional flow is required for the coalescence and extension of the particulate LCP phase. The viscosity of the blends was determined both in a cone-and-plate geometry of a Rheometrics Mechanical Spectrometer at low shear rates and in the Instron Capillary Rheometer at higher rates. In general, only a small (10 or 30 percent) weight fraction of LCP was required to reduce the viscosity of the thermoplastics to that of the polymeric liquid crystal. An attempt was made to correlate the structure of the blends seen under the scanning electron microscope with the observed rheology. Not all aspects of the morphology were possible to explain in terms of the viscous properties of the blends.     

Effect of nano‐silica filler on the rheological and morphological properties of polypropylene/liquid‐crystalline polymer blends

A fumed hydrophilic nano‐silica‐filled polypropylene (PP) composite was blended with a liquid‐crystalline polymer (LCP; Rodrun LC5000). The preblended polymer blend was extruded through a capillary die; this was followed by a series of rheological and morphological characterizations. The viscosity of the PP matrix increased with the addition of the hydrophilic nano‐silica. At shear rates between 50 and 200 s^?1, the composite displays marked shear‐thinning characteristics. However, the incorporation of LC5000 in the PP composite eliminated the shear‐thinning characteristic, which suggests that LC5000 destroyed the agglomerated nano‐silica network in the PP matrix. Although the viscosity ratio of LCP/PP was reduced after the addition of nano‐silica fillers, the LCP phases existed as droplets and ellipsoids. The nano‐silicas were concentrated in the LC5000 phase, which hindered the formation of LCP fibers when processed at high shear deformation. We carried out surface modification of the hydrophilic nano‐silica to investigate the effect of modified nano‐silica (M‐silica) on the morphology of the PP/LC5000 blend system. Ethanol was successfully grafted onto the nano‐silica surface with a controlled grafting ratio. The viscosity was reduced for PP filled with ethanol‐M‐silica when compared to the system filled with untreated hydrophilic nano‐silica. The LC5000 in the (PP/M‐silica)/LC5000 blend existed mainly in the form of fibrils. At high shear rates (e.g., 3000 s^?1), the LC5000 fibril network was formed at the skin region of the extrudates. The exclusion of nano‐silica in the LC5000 phase and the increased viscosity of the matrix were responsible for the morphological changes of the LCP phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1484–1492, 2003     

Rheology of blends of a thermotropic liquid crystalline polymer with polyphenylene sulfide

Blends of thermotropic liquid crystalline polymer (LCP) and polyphenylene sulfide (PPS) were studied over the entire composition range using Rheometrics Stress Rheometer, capillary rheometer, and differential scanning calorimeter. There is no molecular scale mixing or chemical reaction between the components, as evidenced by melting and crystallization points in the PPS phase. From the strain scaling transients test at low‐rate, LCP and the blends require approximately 60 strain units to obtain steady stale shearing results. The large recoveries in the strain recovery test, magnitude 3 to 3.3 strain unit, are likely the results of texture present in LCPs. With increasing PPS content in LCP/PPS blends, the total recovery declines. Scaling of the transient strain rate remains, but the magnitude of the transients is reduced. At low‐rate, when the LCP is added to the PPS, the pure melts have similar visosity: 500 Pa · s for LCP and 600 Pa · s for PPS, but the viscosity of the blends goes through a maximum with concentration that is nearly three times the viscosity of the individual melts. At high‐rate, a significant depression of the viscosity is observed in the PPS‐rich compositions and this may be due to the fibrous structure of the LCP at high shear rates.     

Enhanced fibrillation of LCP by CaCO3 whisker in polysulfone matrix through increasing elongational stress

Induced by different fillers, various hydrodynamic effects enhance the fibrillation of liquid crystalline polymer (LCP) in in situ hybrid composites. Through choosing CaCO₃ whisker as the filler and polysulfone (PSF) as the matrix, the effect of the filler size and the affinity between components on the morphological evolution of LCP droplets has been investigated. In contrast to the spherical or ellipsoidal droplets of LCP formed in binary PSF/LCP blends, the fibrillation of LCP was promoted by the introduction of whisker particles in all ternary blends at shear rates studied. The analysis of the flow field indicated that the predominant factors promoting the fibrillation of LCP were the vortex enhanced and elongational stress increased by the whisker in the converging flow area at the entrance of capillary, rather than the viscosity ratio and capillary number.     

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.     

Novel approach to fibrillation of LCP in an LCP/PP blend

A novel concept of improving shear‐induced fibrillation of liquid crystalline polymer (LCP) in LCP/thermoplastic blend systems was introduced. Silica fillers (SiO₂) were added to an LCP/polypropylene (PP) system to serve as a viscosity thickening agent and to improve the fibrillation of the LCP phase. The formation of LCP fibrils was found to enhance with the incorporation of 5–15 wt % of fillers. The presence of LCP fibrils improved the flow properties of the LCP/PP/SiO₂ composites. It was evident from the rheological and morphological studies that the addition of silica led to an increase of the aspect ratio of the LCP fibrils, which, in turn, should improve their effectiveness as reinforcements and/or toughening agents. Substantial improvement in LCP aspect ratio was achieved by the introduction of hydrophobic SiO₂ fillers in the PP/LCP blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2070–2078, 2002     

Self-Reinforced composites of two thermotropic liquid crystalline polymers

Blends of two thermotropic liquid crystalline polymers (LCP) based on 6-oxy-2-naphthoyl and p-oxybenzoyl moieties and p-oxybenzoyl, terephthaloyl and hydroquinone moieties have been studied. The blends were prepared by melt mixing using a twin screw extruder. Thermal, rheological, mechanical, and morphological studies were carried out. Based on the dynamic mechanical thermal analysis and the morphological observations, the blends are found to be immiscible. The viscosity ratios of pure LCP melts exceed values of 10 over a wide range of shear rates, with the viscosity of the blends lying between those of the pure components. The prepared blends are shown to be self-reinforced composites in which one LCP enhances the molecular orientation of the other. Studies of the injection molded bars by scanning electron microscopy indicate a complicated hierarchical morphology with microfibrils of submicron level in diameter, bundled, and intertwined into fibrils of a substantially larger diameter. Due to self reinforcement, impact and tensile properties of the blends show significant synergism when compared to those of the pure LCP components. The properties obtained are remarkably higher than those known for any high performance engineering thermoplastics.     

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

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

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

Abstract

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

Morphology and rheology of polysulfone/Vectra-A950 blends

Blends of polysulfone (PSu) with a liquid crystalline copolyester (Vectra-A950; VA) have been prepared by melt mixing. Their morphology has been studied by scanning electron microscopy (SEM). Either blend specimens as obtained from the melt mixing or fibers drawn from the melt were used for the SEM analysis. Further information on the morphology of the blends was gained by extraction of the PSu phase with methylene chloride. Preliminary rheological characterization of the blends was made by measuring the viscosity curves at 290 and 300°C, with a capillary viscometer having a die of 1 mm diameter and L/D = 40. Finally, an attempt at improving the phase compatibility was made by synthesizing a copolyester, having the same structure of commercial VA, in the presence of preformed PSu and using the product as a possible compatibilizer. It was demonstrated that the blends are composed of two immiscible phase showing poor adhesion. The LCP droplets could, nevertheless, be deformed into oriented fibrils under elongational flow conditions. The LCP particles were shown to coalesce into large domains, and to migrate toward the outer layer of, e.g., extruded rods, under the influence of appropriate flow conditions, thus showing that there is a strong mutual influence between morphology and rheology of these materials. © 1995 John Wiley & Sons, Inc.     

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

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

Physical properties of blends of polycarbonate and a liquid crystalline copolyester

Blends of polycarbonate (PC) and poly(ethylene terephthalate-co-p-oxybenzoate) (PET/PHB60) were prepared by melt-blending. Physical and/or chemical interactions between the two phases of the system were studied by thermal analysis and infrared spectroscopy. Rheological measurements in shear flow were carried out both in the low and high shear rate regions in the temperature range of the existence of the mesophase. At low liquid crystalline polymer (LCP) content, the blends showed flow curves similar to those of the unfilled PC, while at higher LCP percentages the rheological behavior of the pure LCP was resembled. Moreover, in the whole shear range, the viscosity values of such blends were in between those of the pure polymers. The influence of the addition of 10% LCP on the mechanical properties of the PC was investigated. Fiber-spinning was performed under different experimental conditions, and it was found that opportune drawing conditions are necessary to improve the modulus of the matrix. Morphological analyses of the pure LCP and of the blends were related to the rheological and mechanical behavior of these systems. While the LCP exhibited an elevated dimensional stability, the inclusion of the LCP in PC matrix did not improve the dimensional stability of the blends.     

Studies of time effects in the flow of polymer melts using a biconical viscometer

The variation of viscosity of various polymer melts under constant shear rate conditions has been investigated using a biconical viscometer, a cone-plate viscometer, and a capillary rheometer. The validity of the biconical viscometer edge-zone correction was investigated. Comparisons between the three types of viscometer showed that sample fracture at the material boundary contributed to the decrease of viscosity with time of shearing occuring in the cone-plate viscometer. Polymer melts are subjected to hydrostatic pressure within the biconical viscometer and fracture appears to be prevented. Shear stress–shear rate–time relationships were obtained for the materials studied with the biconical viscometer at shear rates up to a few reciprocal seconds. There was good agreement with capillary data at high shear rates and cone-plate data at low shear rates. A recoverable decrease of viscosity with time of shearing was found to occur. Both the fractional decrease in viscosity and the time taken to recover the original viscosity become smaller as the temperature is increased.     

Capillary viscometry: A complete analysis including pressure and viscous heating effects

Capillary viscometers have been used extensively, because of their simplicity and reliability, to measure the viscosity of fluids over a wide range of shear rates. However, in capillary flow, the shear rate is not uniform throughout the capillary, a pressure gradient is established in the direction of flow, and the temperature of the fluid is nonuniform due to viscous dissipation. In the present work, a general, simple and practical method is proposed for correcting for the effects of pressure variation and viscous dissipation in determining the viscosity of polymer melts at high pressures. The method essentially involves the estimation of temperature, pressure, shear rate, and shear stress under a variety of experimental conditions at a predetermined point in the capillary. As such, it may be considered as a generalized extension of the classical Rabinowitsch-Mooney method for estimating true viscosity in capillary flow.     

Rheological behavior of liquefied α-cellulose with phenol

The steady rheological behavior of phenol-liquefied cellulose product (LCP) at varying liquefaction times was investigated at three testing temperatures. The LCP presented interesting rheological behavior. When liquefaction time was longer than 45?min, the LCP showed stronger shear-thinning behavior with increasing temperature, and the viscosity at high testing temperature was higher than that at low testing temperature at low shear rates. An experiment with a heating and cooling cycle indicated that LCP would form reversible association structures when temperature increased. The mechanism of the reversed rheological behavior of LCP may be attributed to the association of alkyl chain parts of liquefied cellulose when heating.     

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.