Processing and properties of polyimide melt blends containing a thermotropic liquid crystalline polymer

Several polymer blend compositions of LaRC-TPI 1500 and New TPI 450 (Mitsui Toatsu) with Xydar SRT 900 LCP (Amoco Performance Products) were extrusion processed. In addition to binary blends containing one TPI with an LCP, ternary blends consisting of an alloy containing both TPIs as the matrix were also processed. By varying the ratio of the polyimides in the matrix, the blends' thermal behavior could be tailored. This paper addresses both processing issues and film properties of these blends. Rheological and thermal studies were conducted on both blends made in a torque rheometer and on biaxially oriented film produced with a counter-rotating annular die. These biaxial blend films were further characterized by measuring tensile and electrical properties. For 70/30 New TPI/Xydar equal biaxial films of 50 μm thickness, a modulus of 3.8 GPa and a stress at break of 100 MPa were measured. For near uniaxial blend films (±3°) a modulus of 14.5 GPa and a strength of 220 MPa in the machine direction (MD) were measured. The transverse direction (TD) properties were still higher than the neat New TPI. The electrical properties of these blends were outstanding. The dissipation factor was typically less than 0.01 for most blend compositions. Similarly, the dielectric constant was typically less than 3 up to temperatures as high as 300°C.     

Polyblends containing a liquid crystalline polymer

Polyblends of a liquid crystalline thermotropic polymer (LCP) and an amorphous polyamide (PA) were prepared by melt blending. The blends' rheological behaviour was found to be very different from that of the individual components and very significant viscosity reductions were observed for blends consisting of only 5% LCP. The blends viscosity was always much lower than that of the parent polymers. The tensile mechanical behaviour of LCP/PA blends is very similar to that of polymeric composites. The blends' two phase morphology was found to be affected by their compositions. The LCP phase changed gradually with increasing LCP content from ellipsoidal particles to rod-like and fibrillar structure. A good interphase adhesion was observed.     

Thermally induced phase separation in liquid crystalline polymer/polycarbonate blends

Thermally induced phase separation in liquid crystalline polymer (LCP)/polycarbonate (PC) blends was investigated in this study. The LCP used is a main‐chain type copolyester comprised of p‐hydroxybenoic acid and 6‐hydroxy‐2‐naphthoic acid. Specimens for microscopic observation were prepared by melt blending. The specimens were heated to a preselected temperature, at which they were held for isothermal phase separation. The preselected temperatures used in this study were 265, 290, and 300°C. The LCP contents used were 10, 20, and 50 wt %. These parameters corresponded to different positions on the phase diagram of the blends. The development of the phase‐separated morphology in the blends was monitored in real time and space. It was observed that an initial rapid phase separation was followed by the coarsening of the dispersed domains. The blends developed into various types of phase‐separated morphology, depending on the concentration and temperature at which phase separation occurred. The following coarsening mechanisms of the phase‐separated domains were observed in the late stages of the phase separation in these blends: (i) diffusion and coalescence of the LCP‐rich droplets; (ii) vanishing of the PC‐rich domains following the evaporation‐condensation mechanism; and (iii) breakage and shrinkage of the LCP‐rich domains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polycarbonate/liquid crystalline polymer blend: Crystallization of polycarbonate

The enhanced crystallization of polycarbonate in the blend of liquid crystalline polymer/polycarbonate/(ethylene-methyl acrylate-glycidyl methacrylate) copolymer (LCP/PC/E-MA-GMA) was studied by wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The LCP/PC/E-MA-GMA 5/95/5 blends annealed at 200 °C, for 2, 4, 6, and 10 h, present an obvious crystalline structure corresponding to PC crystallization. The PC crystal obtained shows two melting temperature, T_m1 of about 214 °C and T_m2 of about 231 °C, with a total heat of fusion of 29 J/g (annealing time = 10 h). The preliminary results indicate that amorphous PC can be induced to crystallization by the synergistic action of LCP dispersed phase and reactive compatibilizer.     

主链型液晶高分子改善聚丙烯熔体高速挤出的流变行为

采用恒速型双毛细管流变仪研究了主链型热致液晶对无规共聚聚丙烯(PPR)熔体高速挤出流变性能的影响.PPR熔体螺纹状畸变是由口模入口区的应力集中效应和横向环流造成的;利用原位成纤法制备PPR/热致液晶聚合物(TLCP)试样,TLCP在拉伸场中明显取向,随拉伸速率增大,取向程度先增大后减小;取向的TLCP明显减弱熔体挤出物...     

Post extrusion hot drawing of polycarbonate/liquid crystalline polymer blends

The post extrusion hot drawing of polycarbonate/liquid crystalline polymer (PC/LCP) blends, over the entire composition range, was studied. The extruded filament morphology and elastic modulus were followed as a function of blends composition, initial phase morphology, and draw ratio (DR). Hot drawing was found to cause further orientation to the already existing partially oriented LCP phase at the die exit, as reflected by the increased blends modulus. The additional orientation depends on the initial filaments structure, the blend composition, and the DR. Moreover, the orientability of the LCP phase is much higher, similar to that of neat LCP, for blends in which the LCP forms the continuous phase. In low LCP content blends, a critical DR was identified, beyond which the LCP fibrils undergo fragmentation and voids at the fibrils/matrix interface are formed, resulting in a decrease in the drawn filament modulus.     

Elastic modulus of in-situ composites of a liquid crystalline polymer and polycarbonate

In this paper, we model the elastic modulus of in-situ composite fibers from polymer blends where a fibrous liquid crystalline polymer (LCP) phase is induced by drawing. We propose a composite model to account for the change of the elastic moduli of the reinforcing LCP phase with the draw ratio of the composite fibers. We envisage the LCP phase as a composite of a perfectly oriented chain aggregate and a randomly oriented chain aggregate which are connected in series. We then derive equations for the longitudinal and the transverse elastic moduli of the composite fibers based on the well-known Halpin-Tsai equation and the composite model of the reinforcing LCP phase. Using this approach, we are able to make a number of predictions including the transverse elastic modulus and mechanical anisotropy. Our results show that theoretical predictions of the longitudinal elastic modulus agree fairly well with experimental results for polycarbonate/Vectra composites. The proposed modulus equations will be useful in providing guidelines for fabrication and applications of this new class of polymeric materials.     

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

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

Effect of compatibilization in injection‐molded polycarbonate and liquid crystalline polymer blend

The effect of compatibilizing polycarbonate (PC) and LC5000, a thermotropic liquid crystalline polymer consisting of 80/20% of hydroxybenzoic acid and poly(terephthalate) with a laboratory synthesized compatibilizer was studied. The compatibilizer was synthesized by transesterification of PC and LC5000 with the aid of a catalyst. The effect of compatibilization was investigated by studying the mechanical and morphological properties of injection‐molded plaques with different thicknesses. Substantial improvement was observed in the mechanical properties after compatibilization. Significant enhancement in the fibrillation was also observed in the samples after addition of compatibilizer. The surface finish of the compatibilized samples was smooth and homogenous as compared to the uncompatibilized samples. The skin‐core phenomenon in the tensile fractured surfaces was less obvious in the former samples, indicating better adhesion and homogeneity. These morphological studies showed that the mechanical properties enhancement lay in improved fibrillation and interfacial adhesion between the dispersed and major phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 568–575, 2002; DOI 10.1002/app.10308     

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

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

Impact tests on filled and unfilled thermotropic liquid crystalline polymer injection mouldings

Summary Charpy and falling weight impact tests have been carried out on filled and unfilled thermotropic liquid crystalline mouldings between room temperature and 140 °C. There is progressive embrittlement on filler addition in both types of test, and a maximum in absorbed energy as a function of temperature is observed, corresponding to the glass transition temperature near 100 °C.     

The structure of filled and unfilled thermotropic liquid crystalline polymer injection moldings

Studies of the microstructure and orientation in thermotropic liquid crystalline polymer injection moldings have been carried out using a variety of techniques to reveal the complex hierarchical structure. The effect of particle filler on the level of molecular orientation in the flow direction appears relatively weak, but at high filler contents, there is a marked disruption of coarse structure in the matrix. © 1993 John Wiley & Sons, Inc.     

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     

Effects of chemical reactions on the properties of polycarbonate/liquid crystalline polymer blends

Effects of chemical reactions on the properties of the polycarbonate (PC)/liquid crystalline polymer (LCP) blends are considered here. Not only thermal and rheological behaviors, but also morphology and molecular weight change are investigated. Reactive blends were prepared in a cylindrical flask at 300°C with varying processing time in the presence of a catalyst by the melt-phase reactions. For comparison, physical blends, in which chemical reactions were minimized, were also prepared at 300°C in a twin-screw extruder. It seems that transesterification and repolymerization did not occur, but depolymerization reaction took place slightly in PC/LCP physical blends. In reactive blends, however, transesterification and repolymerization as well as depolymerization reaction took place simultaneously. The depolymerization reaction occurred mainly at an early stage of processing; whereas, repolymerization reaction becomes especially dominant after some time (more than 30 min) in the presence of the catalyst, which had a great impact on its molecular weight. Also, chemical reactions changed the glass transition temperature and morphology as well as rheological behavior, which resulted in the enhanced miscibility in reactive blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2123–2133, 1999     

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.     

Morphology evolution of a liquid crystalline polymer confined by highly packed glass beads in polycarbonate

Very long and perfectly oriented fibrils of a liquid crystalline polymer (LCP) were in situ formed in capillary flows by adding large amounts of glass beads (GB) to a polycarbonate (PC)/LCP blend. Thermodynamically the different interfacial tensions between the components made GB migrate to the LCP phase. Then the high content of GB spheres produced a confined condition, so that the LCP droplets passed through the simultaneously formed micro-capillaries, followed by being stretched into fibrils and stabilized consequently.     

Rheological behavior of highly filled polymer melts

The rheological behavior of highly filled polymer melts has been examined. At concentrations near the maximum packing fraction, strain-dependent behavior was observed at strains as low as 1 percent. Selected surface treatments were shown to reduce particle agglomeration. This produced composite melts with lower viscosities and higher maximum loadings. While η* – ω plots provide information on the shear strength of the interparticle network, G′ – ω plots show evidence of phase separation.     

Characterization of liquid crystalline polyester polycarbonate blends

Mechanical and rheological properties of blends of a thermotropic liquid crystalline polyester with a polycarbonate have been investigated. The blends are fibrillar in character and exhibit great hardness and toughness due to high degree of molecular orientation which develops during the melt blending and processing steps. Increases of the Young modulus by 100 percent are observed for blends containing only 10 percent of liquid crystalline polymer, LCP. Time-dependent behavior of the blends was investigated by performing solid state relaxation measurements and the relaxation modulus was also found to increase by the addition of LCP. The effect is relatively small in the glassy zone of viscoelastic response, but increases through the transition and viscous flow regions. The melt viscosity of the polycarbonate is slightly shear thinning whereas that of the unblended LCP increases rapidly with decreasing shear rate at low shear rate. This suggests the presence of yield stresses as confirmed by measurements on the Rheometics RSR in the stress sweep mode. The melt viscosity of the blends was found to be similar to that of the unblended polycarbonate, but more shear-thinning and less viscous. Preliminary results of scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) are also presented.     

Transient shear flow properties of carbon fiber–filled liquid crystalline polymer

Unsteady flow of filled polymer systems can cause some difficulties in their processing, such as injection or extrusion molding, in which flow in the molten state is involved. In order to determine the optimum conditions and thus improve the performance of the end products, it is necessary to understand the transient/unsteady flow behavior of these systems. In a previous work, we found remarkable non‐Newtonian properties and shear thickening flow behavior of liquid crystalline polymers (LCP) and their filled systems. This article deals with the dependence of transient flow properties, including shear thickening, of pure and carbon fiber‐filled LCP upon the shear rate and shear strain history; the effect of the filler content is also discussed. The results indicate that the abnormal flow behavior of the tested materials may be caused by gradual disintegration of the domain structure formed in LCP (materials exhibit apparent yield stress) and then continual orientation of molecules under shear flow. The shear thickening behavior of the materials seems to disappear with increasing fiber content. This behavior suggests that it is necessary to measure the flow properties under a sufficient ramp point delay time and equilibration time in order to obtain reliable data under stable conditions. POLYM. COMPOS., 26:470–476, 2005. © 2005 Society of Plastics Engineers.     

Rheological properties of liquid crystalline copolyesters

Copolyesters were synthesized by modifying poly(ethylene terephthalate) (PET) with p-acetoxybenzoic acid (PAB) and hydroquinone diacetate/tetrasubstituted (tetramethyl, tetrachloro, and tetabromo) terephthalic acid (HQTS). It was found that the copolyesters containing 33 mol% or higher concentrations of (PAB+HQTS) from mesomorphic liquid crystalline structures. Rheological properties of copolyesters formed of PET, modified with PAB and hydroquinone diacetate/tetramethyl terephthalic acid (HQTM), were measured using a cone-and-plate rheometer. It was found that the copolyesters in the mesomorphic state exhibit yield values at a low shear rate (or at a low shear stress), and negative values of first normal stress difference were observed for certain compositions of (PAB+HQTM), over the range of shear rates (or shear stresses) tested.