Rheology and physical properties of ternary blends containing a thermotropic liquid crystalline copolyester

Ternary blends of polyarylate (PAR) U-Polymer 100, thermotropic liquid crystalline copolyester (LCP) Vectra A950, and a block copolyesterether Hytrel 7246 were investigated in terms of rheological properties, morphology, and mechanical properties. The PAR/Hytrel blend exhibited melting point depression and gave a unique single T_g over the entire range of blend compositions. Addition of Hytrel to the PAR/LCP blend decreased both dynamic viscosity and storage modulus over the normal processing temperature range. Further, it notably reduced the voids between the LCP domains and the matrix, and improved the mechanical properties. The optimum usage level of Hytrel proved to be 2 phr.     

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.     

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

Blends of a poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate) were prepared in a twin-screw extruder. Specimens for thermal properties were investigated by means of an instron capillary rheometer (ICR) and scanning electron microscopy (SEM). The blend viscosity showed a minimum at 10 wt% of LCP and increased with increasing LCP content above 10 wt% of LCP. Above 50% of LCP and at higher shear rate, phase inversion occured and the blend morphology was fibrous and similar to pure LCP. The ultimate fibrillar structure of LCP phase appeared to be closely related to the extrusion temperature. By employing a suitable deformation history, the LCP phase may be elongated and oriented such that a microfibrillar morphology can be retained in the solid state. Thermal properties of the LCP/PEN blends were studied using DSC and a Rheovibron viscoelastomer. These blends were shown to be incompatible in the entire range of the LCP content. For the blends, the T_g and Tm were unchanged. The half time of crystallization for the LCP/PEN blends decreased with increasing LCP content. Therefore, the LCP acted as a nucleating agent for the crystallization of PEN. The dimensional and thermal stability of the blends were increased with increasing LCP content. In studies of dynamic mechanical properties, the storage modulus (E′) was improved with increasing LCP content and synergistic effects were observed at 70 wt% of LCP content. The storage modulus for the LCP/PEN 70/30 blend is twice that of PEN matrix and exceeded pure LCP.     

Rheology and morphology of polyester/thermoplastic flour blends

Two maize flours (standard and waxy grades) were plasticized in an internal mixer with a constant amount of water and two glycerol contents. The resulting thermoplastic flours (TPFs) were characterized in dynamic oscillatory shear and creep/recovery rheometry. They displayed two different behaviors: the viscoelastic behavior of a high‐molecular‐weight polymer for the first one and a gel‐like behavior for the second one. The TPFs were then mixed with a copolyester [poly(butylene adipate–terephtalate)]. All of the blends contained the same volume fractions and were prepared with the same mixing conditions. The morphology and rheological behavior of each blend were characterized. Different morphologies, ranging from cocontinuous to nodular, were observed. In fixed mixing conditions, the blend morphology was shown to be governed by the rheological behavior of the starchy phase and the plasticizer content. The gel‐like behavior of the second TPF seemed to prevent droplet coalescence; this led to a very fine dispersion. The rheological behavior of each blend appeared to be linked to both the morphology and the rheological behavior of the two phases. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40222.     

Impact-modified blends of compatibilized polyamide-6 with liquid crystalline copolyester

Compatibilized blends of polyamide-6 (PA6) and thermotropic liquid crystalline polymer (LCP) modified with various high-impact polypropylene (HIPP) contents were injection-molded. These blends were compatibilized with maleic anhydride-grafted polypropylene (MAP). The effects of impact modification on the morphology, impact, static, and dynamic mechanical properties were investigated. The results showed that the HIPP addition leads to an improvement of the Izod impact strength of the blends significantly while it reduced the tensile strength and stiffness properties. An attempt was made to correlate the structure of the PA6(MAP)/HIPP/LCP blends from the scanning electron microscopic observations with the measured mechanical properties. This work provides a way to produce a tough in situ composite. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1611–1619, 1998     

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.     

Thermomechanical properties of radiation-modified blends of polyethylene with liquid crystalline copolyester

The results of investigation of gamma irradiated blends of high-density polyethylene (PE) with thermotropic polymer liquid crystal (PLC) are presented. The PLC used was a copolyester of 40% poly(ethylene terephthalate) with 60% p-(hydroxy-benzoic acid). The PLC content in the blends was 0, 5, and 10 wt%. The constituents were blended with the use of a single screw extruder. The specimens were prepared by compression molding. The irradiation of the samples was performed by a Co⁶⁰ γ-radiation source in inert atmosphere (argon) up to absorbed relatively low doses (up to 200 kGy; 1 Mrad = 10 kGy). The morphological, thermal, and mechanical properties were investigated for irradiated and unirradiated samples. The influence of gamma irradiation and addition of PLC on the temperature dependence of the elastic modulus as well as the effect of a “form memory” of the materials examined are discussed. It was found that an addition of the PLC affects substantially the stress-strain relationship in tension at temperatures above the melting point of PE for the irradiated samples. The features of thermomechanical behavior of the PE + PLC blends, previously irradiated and oriented, at isometrical heating and cooling were also established. The results obtained testify that the addition of PLC to PE makes it possible to improve considerably the thermosetting properties of the heat-shrinkable polymeric products.     

Phase transformations in a thermotropic liquid crystalline copolyester and its blends with polyether sulfone

Mesophase transitions in a thermotropic liquid crystalline polymer comprising p-hydroxybenzoic acid (PHB) and polyethylene terephthalate (PET) in a copolymer ratio of 60/40 were studied by means of optical microscopy, light scattring, and wide-angle X-ray diffraction (WAXD). According to time-resolved light scattering and optical microscopic studies, at about 250°C, a mesophase transition was evident in which Schlieren texture developed with elapsed time. This transition has been identified as a solid crystal-nematic mesophase transition associated with the melting of PHB-rich crystals. It is concluded that the copolymer sequence may not be random. An isotropic, amorphous blend of PHB-PET/polyether sulfone (PES) was prepared by solvent casting from hexafluoro-2-propanol solution. However, this homogeneous blend appears to be kinetically entrapped during solvent removal. Thermally induced phase separation takes place upon heating slightly above the glass transition temperature of PES. Morphology development within phase-separated domains has been qualitatively examined by light scattering and optical microscopy.     

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.     

Transport properties of methanol in blends of a liquid crystalline copolyester and polyethersulfone

Data for the diffusivity and solubility of methanol in blends of polyethersulfone (PES) and a liquid crystalline copolyester (polyhydroxy-benzoic acid (73 mol%)-co-hydroxy-naphthoic acid (27 mol%)) (LCP) are reported. Samples taken from injection molded and compression molded specimens over a wide composition range were studied by gravimetry (sorption and desorption), dielectric spectroscopy, differential scanning calorimetry and scanning electron microscopy. The sorption of methanol in PES led to the formation of an ordered phase. The sorption curves were S-shaped and they could be described by a diffusion model assuming a concentration-dependent diffusivity and time-dependent boundary conditions. The solubility of methanol in the blends was strictly proportional to the PES content. The zero-concentration-diffusivity decreased strongly with increasing LCP content and it was dependent on the morphology. Injection molding yielded samples with a fibrillar LCP phase with a greater continuity of the PES component and a high diffusivity (in relative terms). Compression molding led to samples with a more continuous LCP component even at low LCP contents and a low diffusivity.     

Stability of blends of thermotropic liquid crystalline polymers with thermoplastic polymers

Breakup of fibers of a thermotropic liquid crystalline polymer (TLCP) above the melting temperature in various ordinary polymers has been studied by capillary instability experiments on single TLCP fibers and by annealing experiments on extruded TLCP/thermoplast blends. The TLCP was an aromatic copolyester, Vectra A900, the matrix polymers were PP, PS, PC, PEL PES, and PEBT. Both types of experiments show that the fiber/matrix morphology is, in general, highly unstable in the molten state. The TLCP fibers break up into droplets by a combination of Rayleigh distortions, end-pinching and retraction, depending on the system and shape of the fiber. Fibers of a thickness of ～1 μm can break up in a few seconds. Breakup times of fibrous blends and individual fibers are in agreement provided size effects are accounted for. Rayleigh distortions develop exponentially in time up to relative distortions of 0.5 to 0.6. Breakup occurs within a range of wave numbers rather than at one distinct dominant wave number, which is shown to be the consequence of relatively large initial distortions. Apparent values for the interfacial tensions calculated with Tomotika's theory turned out to be of the correct order of magnitude, ranging from 7 mN/m for Vectra/PES to 24 mN/m for Vectra/PP and to yield correct values of the interfacial tensions of PP/PS, PP/PC, and PS/PC using Antonow's rule.     

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.     

Thermal properties of blends of poly(ethylene terephthalate) and a liquid crystalline copolyester

Summary A thermotropic liquid crystal copolyester (CHQ/BP/TA/IA; 40/10/40/10) (LCP), and melt blends of poly (ethylene terephthalate) (PET) with LCP have been studied for thermal transition and crystallization behaviour. The LCP has a mesophase transition (KM) in the temperature range of 295–315°C. The endothermic peak showing mesophase to Isotropic (MI) transition is observed around 420°C. These transitions are supported by hot stage polarizing microscopy. In blends of PET/LCP, the mesomorphic transition is observed at temperature around 314°C, along with the melting transition of PET around 274°C. The dynamic calorimetric measurements reveal that the two polymers are at least partially miscible.     

Rheological properties of a liquid crystalline copolyester

Rheological studies of an experimental liquid crystalline (LC) copolyester were carried out using a capillary rheometer and a cone and plate rheometer. Rheological characteristics of the polymer in the nematic state were observed. The nematic melt was found to be pseudoplastic and the degree of pseudoplasticity varied with shear rate. Melt viscosity was found to decrease with shear rate. Negative die swelling was observed at the exit of the capillary rheometer at temperatures marginally above the solid-nematic transition temperature of the polymer and was also found to be a function of shear rate. The dynamic mechanical properties of the polymer were studied as a function of temperature. The activation energies of flow and of dynamic mechanical deformation were calculated.     

Orientation distribution and layerlike morphology in extrusion-molded sheets of a liquid crystalline copolyester amide

Fracture surface morphology and orientation distribution in the extrusion-molded sheets of a thermotropic liquid crystalline copolyester amide were investigated by scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD), and polarized Fourier transform infrared (FTIR) microspectroscopy. The layerlike morphology consisting of two outer layers and a central layer between them was observed on the fracture surface. The microscopic orientation functions in the extrusion-molded sheets were evaluated from the polarized FTIR microspectra that were measured in the microscopic domain 40 μm wide using a redundantly apertured infrared microscope. The microscopic orientation function in the outer layer was shown to be higher than that in the central layer. The effects of the draw-down ratio and extrusion temperature on the orientation distribution and the layerlike morphology are discussed. © 1993 John Wiley & Sons, Inc.     

Zone drawn NEW-TPI thermoplastic polyimide and its blends with Xydar liquid crystalline polymer

In this work we report the effects of single stage zone drawing on the properties of NEW-TPI thermoplastic polyimide homopolymer, and its blends with Amoco's Xydar liquid crystalline polymer. Zone drawing was performed first on homopolymer NEW-TPI films to determine the effect of load weight, heater speed, and drawing temperature on the attainable draw ratio. Degree of crystallinity and chain orientation increase as the draw ratio increases for NEW-TPI. Blends of NEW-TPI/Xydar compositions 90/10 and 70/30 were studied next. In blends, the Xydar component is not molecularly dispersed, and is initially preferentially oriented along the machine direction during the film processing stage. Xydar acts as a nucleation site and lowers the temperature for crystallization of the NEW-TPI from the rubbery amorphous state. Zone drawing was performed either parallel or perpendicular to Xydar's initial preferred orientation direction. Blends with lower Xydar fraction could be zone-drawn to higher ratios. Zone drawing perpendicular to Xydar's initial orientation direction also resulted in increased draw ratio. Dynamic mechanical properties of the zone drawn materials were studied. In homopolymer NEW-TPI, dynamic modulus increased by a factor of two to 4.0 GPa in zone drawn films, largely as a result of the formation of oriented crystallites. In the blends, the modulus parallel to Xydar's initial orientation direction was greater than that in the transverse direction. Depending upon composition and test direction, zone drawing increased the dynamic moduli of the blends from 1.5 up to 2.7 times, in the temperature range from 150°C to 300°C.     

Rheology of phase separated blends of two thermotropic liquid crystalline copolyesters

The melt rheology of phase separated blends of two thermotropic liquid crystalline polymers (LCPs) have been studied. The two components are a random copolyesters consisting of 73 mol% 4-hydrobenzoic acid (HBA) and 27 mol% 6-hydroxy-2-napthoic acid (Vectra A900 of Hoechst Celanese Corp.) and a poly(ethylene terephalate-co-4-oxybenzoate) containing 60 mol% HBA units (PET/60HBA of Eastman Kodak Corp.). Most striking is the effect of adding 10% PET/60HBA to Vectra A900: The viscosity at 290°C drops by a factor of 4 and the terminal zone of the relaxation time spectrum is shifted to much shorter times. This is an interesting effect that could be used for LCP processing even if its origin is not yet understood. Differential scanning calorimetry measurements support the hypothesis that the blend is phase separated and that no transestification reaction occurs during the experiments.     

Toughening of polyethylene terephthalate/amorphous copolyester blends with a maleated thermoplastic elastomer

The toughening of polyethylene terephthalate (PET)/amorphous copolyester (PETG) blends using a maleic anhydride grafted mixture (TPEg) of polyethylene‐octene elastomer and a semicrystalline polyolefin plastic (60/40 by weight) was examined. The TPEg was more effective in toughening PETG than PET, although the dispersion qualities of the TPEg particles in PET and PETG matrices were very similar. At the fixed TPEg content of 15 wt %, replacing partial PET by PETG resulted in a sharp brittle‐ductile transition when the PETG content exceeded the PET content. Before the transition, PET/PETG blends were not toughened with the TPEg of 15 wt %, whereas after the transition, the PET/PETG blends with 15 wt % of TPEg, similar to the PETG/TPEg (85/15) binary blend, maintained a super‐tough level. The impact‐fractured surfaces of the PET/PETG/TPEg blends were also evaluated. When PETG content was lower than PET content, the ternary blend showed a brittle feature in its impact‐fractured surface, similar to the PET/TPEg (85/15) binary blend. While PETG content exceeded PET content, however, the impact‐fractured surface of the ternary blend was very similar to that of PETG/TPEg (85/15) binary blend, exhibiting intensive cavitation and massive matrix shear yielding, which were believed to be responsible for the super‐tough level of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 797–805, 2003     

Thermotropic liquid‐crystalline copolyester/thermoplastic elastomer in situ composites. I. Rheology,morphology, and mechanical properties of extruded strands

A thermotropic liquid‐crystalline polymer (TLCP), a copolyester with a 60/40 molar ratio of p‐hydroxy benzoic acid and poly(ethylene terephthalate), was blended with a styrene/ethylene butylene/styrene thermoplastic elastomer with a twin‐screw extruder. The rheological behavior, morphology, and mechanical properties of the extruded strands of the blends were investigated. The rheological measurements were performed on a capillary rheometer in the shear rate range of 5–2000 s^?1 and on a plate‐and‐plate rheometer in the frequency range of 0.6–200 rad s^?1. All the neat components and blends exhibited shear thinning behavior. Both the shear and complex viscosities of all the blends decreased with increasing TLCP contents, but the decrease in the shear viscosity was more pronounced. The best fibrillar morphology was observed in the extruded strands of a blend containing 30 wt % TLCP, and a lamellar structure started to form at 40 wt % TLCP. With an increasing concentration of TLCP, the tensile modulus of the blends was greatly enhanced, whereas the tensile strength was almost unchanged. The elongation at break of the blends first slightly decreased with the addition of TLCP and then sharply dropped at 40 wt % TLCP. The tension set measured at 200% deformation slightly increased with increasing TLCP contents up to 30 wt %, over which the set value was unacceptable for a thermoplastic elastomer. A remarkable improvement in the dynamic mechanical properties of the extruded strands was observed in the blends with increasing amounts of TLCP. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2676–2685, 2003