Blends containing liquid crystalline polymers: Preparation and properties of melt-drawn fibers,unidirectional prepregs,and composite laminates

This paper discusses the effect of melt drawing on the mechanical properties and morphology of liquid crystalline polymer (LCP) and thermoplastic polymer blends. Extruded fibers and films of LCP/polymer blends were melt drawn to develop uniaxial orientation of the dispersed LCP phase. The longitudinal modulus increased with increasing draw. The increase in modulus was due to higher aspect ratio of the LCP fibrils and improved molecular orientation of the LCP chains within the fibrils. Laminated composites were prepared using the extruded sheets as prepregs. The mechanical properties and the coefficient of thermal expansion (CTE) of the prepreg and the laminates agreed well with predictions from conventional composite lamination theories.     

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.     

Prepregs and laminates of polyetherimide-reinforced by a thermotropic LCP

Unidirectional sheets (prepregs) of blends of polyetherimide (PEI) with a liquid crystalline polymer (LCP) are prepared. The mechanical properties of prepregs at directions of 0°, 45°, and 90° to the machine direction are investigated as a function of draw ratio and LCP concentration. The results show that drawing significantly increases the tensile strength and modulus of prepregs in the machine direction and only slightly decreases these properties in the transverse direction. An increase in the LCP content greatly enhances the tensile strength and modulus in the machine direction but decreases these properties in the 45° and 90° directions. The strain at break of prepregs decreases with LCP content in all directions tested. An abrupt drop in the tensile strength, modulus, and strain at break of prepregs occurs in the 45° and 90° directions when LCP content reaches 40%. Prepregs are used to manufacture unidirectional and quasi-isotropic laminates. Unidirectional laminates show mechanical properties close to those of the corresponding prepregs. The tensile modulus of quasi-isotropic laminates exhibits a continuous increase with increasing LCP content while the tensile strength increases with an LCP content up to 30%, then it decreases rapidly. The morphology of LCP in prepregs is observed to change from disperse to continuous at LCP contents of 40 and 50%. This effect is found to be responsible for the large decrease in tensile strength of prepregs in the 45° and 90° directions and quasi-isotropic laminates at higher LCP concentration. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:329–340, 1997     

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.     

Self-reinforced polypropylene/LCP prepregs and laminates

Polypropylenes (PPs) of various molecular weights were mixed with a thermotropic liquid crystal polymer (LCP) to prepare unidirectional sheets (prepregs), quasi-isotropic and unidirectional laminates. The mechanical properties and the morphology of the prepregs and the laminates at 0° and 90° with respect to the machine direction were investigated as a function of draw ratio, LCP concentration and molecular weight of the PP. The results for prepregs and laminates showed that both drawing and LCP concentration generally enhanced modulus and tensile strength in machine direction. The morphology of LCP changed from spherical or ellipsoidal droplets to elongated fibrils as the draw ratio increased. The diameter of LCP fibrils decreased with increasing molecular weight of the PP matrix, indicating more effective droplet breakup and better mixing in the case of high molecular weight PP.     

Liquid crystalline polymer/fluoropolymer blends: Preparation and properties of unidirectional “prepregs” and composite laminates

Extruded films of liquid crystalline polymer (LCP)/fluoropolymer blends were melt drawn to develop uniaxial orientation of a microfibrillar dispersed LCP phase. The anisotropy of the films increased with increasing draw and LCP content in the blend. Laminated composite plates were prepared using the extruded sheets as prepreg. The mechanical properties and coefficient of thermal expansion (CTE) of the prepreg and laminates agreed well with predictions from composite lamination theories. The potential for replacing glass fiber reinforced fluoropolymers with LCP/fluoropolymer blends in applications such as microwave circuit boards is discussed.     

Microstructure and tensile properties of injection molded thermoplastic polyurethane with different melt temperatures

The use of injection molding technology to prepare heterogeneous interlayer film of laminated glass holds strong applicable potential. This article aims to investigate the effects of melt temperature and melt flow on the microstructure evolution and tensile properties of thermoplastic polyurethane (TPU) specimens during the injection molding process. The tensile properties of the TPU specimens show dependency on the melt temperature and melt flow direction. The results of birefringence indicate that melt flow and lower melt temperature induce higher stretching deformation of the molecular chain network. Small-angle X-ray scattering analysis approves that besides the melt temperature and flow direction, the testing position on the cross section of the specimen has great influence on the microstructure of the TPU sheet. Further analysis and conclusions can be made using wide-angle X-ray scattering method. The above results demonstrate that both the tensile properties and microstructure of the injection molded TPU specimens tend to be isotropic with the increase of melt temperature. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48891.     

Manufacturing and characterisation of microfibrillar reinforced composites from liquid crystalline polymers and poly(phenylene ether)

Abstract

The purpose of the present study was to investigate the fibrillisation process of liquid crystalline polymers (LCPs) in an amorphous poly(phenylene ether) (PPE) matrix during melt blending and a subsequent drawing operation, as well as to analyse the relationship between morphology and mechanical properties of the fibrillar reinforced LCP/PPE blends. In order to understand the effect of the compatibility between the blend partners, an additional set of LCP/PEE blends, containing different amounts of a compatibiliser, was studied too. The processing steps included: (i) melt extrusion and continuous hot stretching for fibrillisation of the LCP component in the different LCP/PPE blends, and (ii) compression (CM) or injection moulding (IM) of the drawn blends at temperatures below the melting temperature (T_m) of the LCPs. Samples from each processing stage were characterised by means of scanning electron microscopy (SEM), wide and small angle X-ray scattering (WAXS and SAXS), and mechanical testing. SEM and WAXS showed that the as extruded blends were isotropic, but after hot stretching the LCP components became highly oriented, with a high aspect ratio and a diameter of the fibrils between 0·4 and 3 μm. The fibrillated structure of the LCPs in the blends could be preserved after the compression and injection moulding only at temperatures below T_m of the LCPs. Addition of a compatibiliser to the LCP/PPE blend did not remarkably improve the adhesion between the components, as a result of the large difference between the coefficients of thermal expansion of the blend partners, which leads to different shrinkage conditions of the LCP fibrils and the PPE matrix. The flexural modulus (E) of all IM blends increased stepwise with an increase in the weight (wt) fraction of the LCP. At the same time, the highest values for the flexural strength (σ) were obtained for the LCP/PPE blends containing 5 wt-% LCP.     

Advanced injection molding mold and molding process for improvement of weld line strengths and isotropy of glass fiber filled aromatic polyester LCP

An advanced injection molding tool for measurement of mechanical strength and anisotropy of liquid crystal polymers (LCP)/mineral filler composites was developed. The mold produces thin‐walled LCP specimens that can be used by water cutting technique for production of an injection molded flow direction test bar, a transverse‐to‐injection molded flow direction test bar, a test bar for knit line strength measurement, and a test bar for butt weld line strength measurement. This tool and its use for molding experiments were optimized by experimental research and by computational calculations based on experimental parameters obtained by molding of several LCP test materials. Different pressure profiles and different injection speeds were tested as well as application of mold overflow phenomenon in production of test specimens. It was observed that a pressure controlled X‐melt technique and on the other hand fast injection speeds with overflow in conventional molding methods gave the best strength and isotropy properties for the test specimens. Results indicate that the mold developed is useful for determination of anisotropic and weld line strength properties of LCP composites. When developing “isotropic LCP” by different possibilities of nanotechnology this tool significantly reduces time of LCP material and process development. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Crystallization and orientation behaviors in isotactic polystyrene and poly(2,6-dimethylphenylene oxide) blends

The crystallization and orientation behavior in the miscible iPS/PPO blends were studied aiming at producing oriented materials consisting of iPS crystals and amorphous PPO chains. Oriented films of iPS/PPO blends were prepared by drawing the melt-quenched blend films. The films were heat-treated under constraint at the drawing temperature so as to crystallize the molecular chains of iPS in the oriented state. The crystallinity and the crystal orientation in the drawn annealed films were studied by the wide-angle X-ray diffraction (WAXD), and the orientation behaviors of molecular chains were analyzed by polarized FTIR spectroscopy. WAXD diagrams show the presence of the highly oriented crystalline structure of iPS in the drawn annealed films of pure iPS and iPS/PPO=7/3 blend. The polarized FTIR spectra of drawn annealed films suggest that the molecular orientation of the amorphous chains of PPO and iPS is markedly relaxed by the heat treatment, although the orientation of iPS with 3₁ helical structure was retained during the oriented crystallization. It was concluded that the drawn annealed samples of the iPS/PPO=7/3 blend consist of highly oriented iPS crystals and nearly isotropic amorphous materials. The mechanical properties of the oriented iPS/PPO blends were measured not only in the stretching direction but also perpendicular to the stretching direction. It was shown that the ultimate strength in the perpendicular direction is 4-5 times higher in the drawn annealed film of iPS/PPO=7/3 blend than in the drawn annealed iPS. The improvement in the vertical strength in the blend is discussed in relation to the structural characteristics of the iPS/PPO blend.     

Self‐reinforced polypropylene/LCP extruded strands and their moldings

Polypropylenes (PP) of various molecular weights were mixed with a thermotropic liquid crystal polymer (LCP) and strands were prepared by extrusion and stretching. The strands were subsequently pelletized and then injection molded at temperatures below the melting point of LCP. The mechanical properties and the morphology of the strands and injection‐molded specimens were investigated as a function of draw ratio, LCP concentration, and PP molecular weight. The results for strands show that an increase in the draw ratio, LCP concentration and matrix molecular weight in general enhance the modulus and tensile strength. However, the tensile properties of injection‐molded specimens are found to be reduced compared with those of the original strands, in particular at high LCP concentration. The morphology of LCP changes from spherical or ellipsoidal droplets to elongated fibrils in the strands as the draw ratio increases, but this aligned LCP fibrillar morphology was not transferred to the injection‐molded specimens because of the disorientation of fibrils during injection molding. Compatibilization of PP/LCP blends was also studied by using various polymers. Maleic anhydride and acrylic acid modified PPs improved the tensile properties modestly, but maleic anhydride modified EPDM reduced the tensile properties.     

Hierarchical structure in LCP/PET blends

The structural hierarchy in injection molded blends of poly(ethylene terephthalate) (PET) and a commercial liquid crystal polymer (LCP), two immiscible polymers, was characterized at various blend compositions. The macroscopic core and skin have a gradient structure and are subdivided into ordered and disordered layers. The sublayers consist of rodlike domains at 25% LCP. The domains become thinner, longer, and more fibril-like with increasing LCP concentration. The interconnection between the LCP domains also becomes more significant at higher LCP concentrations. The highest degree of orientation in the injection direction is at the mold surface and the lowest at the sample center. The LCP orientation reflects the elongational and fountain flow in the mold and increases with increasing LCP concentration. Schematic structural models were used to illustrate the levels of structure in these blends. A minimum exists in the tensile strength, elongation at break, and impact strength with varying blend composition at approximately 50% LCP. The tensile strength of the LCP-rich blends is significantly lowered by the presence of a weldline or an angle between the stress and orientation directions. The unique mechanical properties of the LCP depend on the formation of a highly oriented and highly connected hierarchical structure that does not exist in blends with 75% or less LCP.     

Barrier properties of injection molded blends of liquid crystalline polyesters (Vectra) and high‐density polyethylene

Blends of an extrusion‐grade high‐density polyethylene and two liquid crystalline copolyesters (LCP; Vectra A950 and Vectra RD501) were prepared by melt mixing and injection molding, and the morphologies and oxygen permeabilities of the blends were assessed. Scanning electron microscopy revealed that the LCP was present in the blends as mixed oriented bands and small spheres at low LCP contents (4–9 vol%), whereas blends with more than 18 vol% LCP showed LCP lamellae of macroscopic lateral size (mm). Scanning electron microscopy revealed a two‐dimensional continuity of the LCP domains in the disc plane due to radial shear deformation and circumferential stretching of the melt leaving the central gate of the disc‐shaped cavity. The oxygen permeability, diffusivity and solubility decreased with increasing LCP content of the blends. The decrease in permeability with respect to polyethylene was significant (46%–55%) already at 9 vol% LCP. At 27 vol% LCP, the decrease with respect to polyethylene, was 92% for the Vectra A950 blend and 98% for the Vectra RD501 blend. These blends showed a greater decrease in diffusivity (86%–92%) than in solubility (39%–76%) with respect to polyethylene, which showed the very pronounced effect of the LCP lamellae on the geometrical impedance factor. Microvoids were present in all the blends despite the use of a very high injection pressure (180 MPa) but their impact on the oxygen permeability was negligible for the Vectra RD501 blends and relatively small for the Vectra A950 blends.     

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.     

Energy‐based predictive criterion for LCP fibrillation in LCP/thermoplastic polymer blends under shear

This article relates the fibrillation of liquid crystalline polymer (LCP) under shear in its blend with a thermoplastic polymer (TP) to the relative rate of energy utilization in the LCP and TP phases. The development of a criterion based on the energy relationship for predicting LCP fibrillation in the blend is discussed. The formation of LCP fibers in the blends of LCP with polycarbonate (PC), polyethylene naphthalate (PEN), high‐density polyethylene (HDPE), polypropylene (PP), and silica‐filled polypropylene (PP) was studied to validate the criterion and to demonstrate its applicability. For all the blends, viscosity data were obtained by using a capillary rheometer, which was subsequently used to estimate the rate of energy utilization in the LCP and the matrix phases. The predictions based on the proposed criterion were verified through the morphological investigations carried out on the extrudates obtained from the same capillary experiments. The energy‐based criterion was easy to implement, could account for the effect of variable LCP concentration and fillers in the blend, and could provide reliable predictions for a variety of LCP/TP blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3314–3324, 2003     

Structure and properties of polyblends of a thermotropic liquid crystalline polymer with an alloy of polyamide-6 and ABS

The relationship between the microstructure and corresponding mechanical properties developed during injection molding of blends containing a liquid crystalline polymer (LCP) as the minor component and an engineering polymer system has been studied. A wholly aromatic copolyester LCP (Vectra A950) was melt blended at different compositions with a thermoplastic matrix consisting of a commercial compatibilized blend of polyamide-6 and ABS (Triax 1180). These blends were prepared under two different sets of injection molding conditions. In the first case, a higher melt temperature, higher barrel temperature, lower injection pressure, lower mold temperature, and shorter residence time in the mold were used during injection molding, as compared with the second case. The mechanical properties of the blends were superior to those of the base polymer. In the second case, the resulting injection-molded specimens had a distinct skin–core morphology where elongated fibrils of LCP constituted the skin layer. The mechanical properties of the blends processed under the second set of processing conditions were superior to those of the first, though the trends in both cases were the same. To study the effects of process variables the 15% LCP blend and the second set of processing conditions were taken as the base. Samples were injection-molded by varying one parameter at a time. It was seen that the properties of the blend were increased by maintaining a lower barrel temperature, greater injection pressure, lower injection speed, higher mold temperature, and a greater residence time in the heated mold. Thus it was found that the processing conditions played a vital role in determining the mechanical properties and morphology of the polyblends. © 1996 John Wiley & Sons, Inc.     

In situ reactive compatibilized noryl/LCP blends

This article reveals that the already known improved properties of the thermoplastic–liquid crystalline polymer (LCP) blends can be further improved substantially over the corresponding noncompatibilized counterparts by using a reactive in situ type compatibilizer, the styrene–glycidyl methacrylate (SG) copolymer. This SG copolymer has been demonstrated in this article to be an effective reactive compatibilizer to improve the processability, heat deflection temperature, and mechanical properties of Noryl/LCP blends. The epoxy functional groups of the SG copolymer can react with the end groups of PPO (in Noryl) and LCP. The in situ-formed SG–g–LCP copolymer tends to reside along the interface of Noryl–LCP and reduces the interfacial tension during melt processing. The resultant LCP fibers in the Noryl matrix of the compatibilized blends have a higher aspect ratio because the fibers become finer, longer, and tend to form lamellate domains with a greater interphase contact area than those from the noncompatibilized blends. The compatibilized blends also improve the interphase adhesion between Noryl and LCP. The presence of ethyl triphenylphosphonium bromide catalyst promotes the grafting reaction to improve blend compatibilization. © 1995 John Wiley & Sons, Inc.     

A method of forming composite structures using in situ-formed liquid crystal polymer fibers in a thermoplastic matrix

A new high speed and potentially economical method of creating a composite material and structures therefrom is tested. The method consists of spinning composite fibers from a melt blend of a thermoplastic with a liquid crystal polymer (LCP). Discontinuous fibrils of the LCP are formed in situ during the spinning process. These composite fibers are aligned and placed in a mold and heated to melt the thermoplastic matrix, but not the fibrils. A finished composite structure reinforced by the LCP fibrils is obtained when the thermoplastic phase is consequently consolidated. Our experiments show the proposed process is reasonable for an easily processed polystyrene matrix. High modulus fibrils with essentially infinite L/D ratios are readily produced in the extrusion process using 40 wt% of a wholly aromatic poly(ester-co-amide) LCP from Celanese. The integrity and alignment of the LCP fibrils is retained in the molding step. Mechanical tests show that the fibers produced by high shear rate processing have a stiffness approaching 23 GPa and match an axial rule-of-mixtures theory. The use of polystyrene resulted in brittleness. Molded composite plates exhibit slightly lower stiffness and significantly lower strength than individual fibers.     

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.     

Investigation of tensile behavior and molecular structure of the thermoplastic polyurethane sheets injection molded at different mold temperatures

This paper aims to investigate the influence of the mold temperature on the mechanical responses at different ambient temperature and molecular structure of the injection molded TPU sheets. The tensile properties of the TPU sheets prepared at different mold temperatures were obtained at different ambient temperatures. As the mold temperature increases, both the elongation at break and tensile strength of the specimens increase. The specimens show yield behavior during stretching at −30 and −50°C. The microstructure of the TPU sheets was characterized by DMA, AFM, and birefringence. The results show that the higher mold temperature can reduce the aggregation of hard domains because of the higher mobility of the hard segments. In-situ SAXS and WAXS measurements were carried out at −30°C test temperature to exhibit the evolution of the microstructure during stretching. When the specimens are prepared at 40°C mold temperature, the hard domains are destroyed and difficult to orient along the stretching direction. In contrast, the hard domains begin to be deformed and oriented along the stretching direction above the yield strain when the specimens molded at higher mold temperature. The above microstructure evolution is consistent with the tensile behavior of the TPU specimens.