A study on the ternary blends of polyphenylenesulfide,polysulfone, and liquid crystalline polyesteramide

Ternary blends of poly(p-phenylenesulfide) (PPS), thermotropic liquid crystalline polyesteramide (LCP), and polysulfone (PSF) were investigated in terms of processing characteristics, blend morphology, and physical properties. In the incompatible PPS/LCP blends, LCP imparted a nucleating effect to the crystallization of PPS. Up to 10wt% LCP content, the tensile properties of PPS/LCP blends were enhanced with increasing LCP content, but they deteriorated if the LCP content exceeded 20wt%. Addition of a third component, PSF, to the 90/10 PPS/LCP blend promoted development of rodlike or threadlike fibrillar structure and orientation of the deformed LCP domains, which led to improvement of tensile strength up to 20%.     

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.     

Miscibility and mechanical properties of poly(ether imide)/poly(ether ether ketone)/liquid crystalline polymer ternary blends

This paper is concerned with a novel ternary blend composed of poly(ether imide) (PEI), poly(ether ether ketone) (PEEK) and a liquid crystalline polymer (LCP; HX4000, Du Pont). Different compositions were prepared by extrusion and injection moulding. Dynamic mechanical thermal analysis and the observation of the fracture surfaces, before and after annealing, allowed determination of the cold crystallization temperatures and miscibility behaviour of these systems. PEEK/PEI blends are known from previous studies to be miscible at all compositions. In this case it was observed that the PEEK/HX4000 blend was miscible up to 50 wt% HX4000 but partially miscible above this value. The PEI/HX4000 blends were found to be partially miscible in the whole concentration range. As a result, some ternary blend compositions exhibited only one phase, while others exhibited two phases. The measurement of the tensile properties showed that ternary blends with high modulus can be obtained at high LCP loadings, while compositions with high ultimate tensile strength can be obtained with high loadings of PEI or PEEK.     

Studies on blends of a thermotropic liquid crystalline polymer and polybutylene terephthalate

Summary Structure-property relationships of blends of a thermotropic polyester-type main-chain LCP and polybutylene terephthalate (PBT) were investigated. LCP was melt blended with three different PBTs and the blends were processed by injection moulding or extrusion. Mechanical and thermal properties of the blends were determined and the blend structure was characterized by scanning electron microscopy (SEM). LCP acted as mechanical reinforcement for PBT and improved also its dimensional and thermal stability. The stiffness of PBT increased with increasing LCP content, but at the same time the blends became more brittle. In extrusion the orientation of LCP phases could be further enhanced by additional drawing, which led to significant improvements in strength and stiffness at LCP contents of 20–30 wt.-%.     

Characterization of thermotropic liquid crystalline polyester/polysulfone blends

The morphology, rheology, and mechanical properties of blends of polysulfone (PSF) with up to 65% of a wholly aromatic liquid crystalline polymer (LCP) were investigated. In injection molded specimens a skin-core morphology was observed with the LCP minor phase oriented in the skin and globular in the core. Scanning electron microscopy of fractured surfaces showed sharp phase boundaries, suggesting low interfacial adhesion. The neat PSF and blends with low amounts of LCP exhibited a low shear Newtonian plateau not observed in the blends with high LCP levels. The addition of LCP to PSF resulted in an increase in stiffness, a small increase in tensile strength, and a significant improvement in processability.     

Polysulphone and poly(phenylene sulphide) blends: 2. Mechanical behaviour

This paper reports the mechanical behaviour of injection moulded blends of polysulphone (PSF) and poly(phenylene sulphide) (PPS). The blends prepared by melt-extrusion and subsequent injection moulding are phase separated. Depending on moulding conditions, thermal history, and composition, tensile behaviour ranged from brittle to ductile, with or without cold drawing. Cold drawing was observed in compositions as-moulded with up to 50% by weight PPS. Upon annealing for 2h at 160°C, ductile failure was maintained for blends containing up to 35% by weight PPS. All other compositions failed in brittle fashion. Flexural strength and modulus, before and after annealing, exhibited negative deviation from the rule of mixtures. All the blends were found to be notch sensitive.     

Mechanical properties and morphology of liquid crystalline copolyester-amide and amorphous polyamide blends

Blends of an amorphous polyamide (PA) and a liquid crystalline copolyesteramide (LCP), poly(naphthoate-aminophenoterephthalate) were prepared in a twin-screw extruder. Specimens for mechanical testing were prepared by injection molding. Morphological, thermal, mechanical, and rheological properties were investigated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffractometry, capillary rheometry, and a tensile tester, respectively. The tensile mechanical behavior of the LCP/PA blends was found to be affected by their compositions and specimen thickness. Tensile testing revealed that the tensile mechanical behavior of the LCP/PA blends was very similar to that of polymeric composite and the tensile strength of the LCP/PA (50/50) blend was approximately two times of the value of PA homopolymer and exceeded that of pure LCP. The morphology of the LCP/PA blends was also found to be affected by their compositions. SEM studies revealed that the liquid crystalline polymer (LCP) formed finely dispersed spherical domains in the PA matrix and the inclusions were deformed into fibrils from the spherical droplets with increasing LCP content. It has been found that droplet and fiber formations lead to low and high strength material, respectively. In particular, at specific LCP content (50 wt%), the tensile strength of the LCP/PA blend exceeded that of pure LCP. The improvement in tensile properties is likely due to the reinforcement of the PA matrix by the fibrous LCP phase as observed by SEM. A distinct shell-core morphology was found to develop in the injection molded samples of these blends. This is believed to have a synergistic effect on the tensile properties of the LCP/PA blends. The rheological behavior of the LCP/PA blends was found to be very different from that of the parent polymers and significant viscosity reductions were observed for the LCP/PA (50/50) blend. Based upon DSC, these blends have shown to be incompatible in the entire range of concentrations.     

In‐situ reinforcement of PBT/ABS blends with liquid crystalline polymer

Ternary in‐situ poly(butylene terephthalate) (PBT)/poly(acrylonitrile‐butadienestyrene) (ABS)/liquid crystalline polymer(LCP) blends were prepared by injection molding. The LCP used was a versatile Vectra A950, and the matrix material was PBT/ABS 60/40 by weight. Maleic anhydride (MA) copolymer and solid epoxy resin (bisphenol type‐A) were used as compatibilizers for these blends. The tensile, dynamic mechanical, impact, morphology and thermal properties of the blends were studied. Tensile tests showed that the tensile stregth of PBT/ABS/LCP blend in the longitudinal direction increased markedly with increasing LCP content. However, it decreased sharply with increasing LCP content up to 5 wt%; thereafter it decreased slowly with increasing LCP content in the transverse direction. The modulus of this blend in the longitudinal direction appeared to increase considerably with increasing LCP content, whereas the incorporation of LCP into PBT/ABS blends had little effect on the modulus in the transverse direction. The impact tests revealed that the Izod impact strength of the blends in longitudinal direction decreased with increasing LCP content up to 10 wt%; thereafter it increased slowly with increasing LCP. Dynamic mechanical analyses (DMA) and thermogravimetric measurements showed that the heat resistance and heat stability of the blends tended to increase with increasing LCP content. SEM observation, DMA, and tensile measurement indicated that the additions of epoxy and MA copolymer to PBT/ABS matrix appeared to enhance the compatibility between PBT/ABS and LCP.     

Structure and mechanical properties of poly(sulfone of bisphenol A)/poly(butylene terephthalate) blends

Blends of poly(sulfone of bisphenol A) (PSU) with poly(butylene terephthalate) (PBT) were obtained by direct injection moulding across the composition range. The two components of the blends reacted slightly in the melt state, producing linear copolymers. The slight changes observed in the two glass transition temperatures indicate that the copolymers were present in the two amorphous phases of the blends. The observed reactions and the high viscosity of the matrix of the PSU‐rich compositions led to a very fine morphology which could not be attained in the PBT‐rich compositions due to the low viscosity of the matrix and the direct injection moulding procedure used. This procedure is fast and economically advantageous, but leads to poor mixing. The different morphologies influenced neither the modulus nor the yield stress, which tended to follow the rule of mixtures. However, the low fracture properties of the PBT‐rich compositions contrasted with the ductility behaviour, and even the impact strength of the PSU‐rich blends, which also tended to be proportional to the blend composition. Copyright © 2004 Society of Chemical Industry     

Structure and properties of amorphous polyamide/liquid crystalline polyester blends

Amorphous polyamide (AP)/liquid crystalline polyester (VA) blends were obtained by extrusion‐injection molding (EI) throughout the whole composition range. The phase behavior, chemical nature and morphology of the blends were studied, and the mechanical properties discussed and compared with those of the 10 and 30% VA blends obtained by direct injection molding (DI). The blends showed two almost pure slightly reacted amorphous phases. The apparently higher reaction level of the EI blends, although small, led to a more homogeneous, fine and fibrillated morphology, attributed to a lower interfacial tension. Significant synergisms in the modulus of elasticity (up to 25%) and in the tensile strength (up to 40%) were seen in EI blends. The similar values of both specific volume and orientation in the blends and in the pure components suggest that the contribution to the modulus of the dispersed VA rigid particles is greater than that due to the proportion of VA in the blend. The 10% VA DI blend showed a similar behavior in these two properties, indicating that the DI procedure is preferred, provided that only stress‐related properties are sought. At 30% VA content, the moduli of elasticity were similar by the two molding processes, but the clearly lower tensile strength and lower ductility of the easier DI procedure, means that the more complex, but more effective, EI procedure is the one of choice for high performance materials.     

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

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

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     

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.     

Electron beam processing of nylon 6 and hydrogenated nitrile rubber (HNBR) blends: 1. Development of high strength heat‐ and oil‐resistant thermoplastic elastomers

The effects of electron beam irradiation on the morphology, mechanical properties and heat and hot oil resistance of a thermoplastic elastomeric blend of 50/50 nylon 6 and HNBR rubber were investigated. The morphology of the blend was studied by scanning electron microscopy, with special reference to the effects of processing via injection moulding and the radiation dose. Irradiation of extruded pellets at low doses and subsequent injection moulding improved the blend morphology, thereby enhancing the mechanical properties. The tensile strength of the blend increased with radiation dose. The irradiated blends had excellent hot oil resistance and the tensile strength of the blends did not change much after ageing at 150 °C for 72 h. Incorporation of 10 phr SRF black to the blend greatly improved the tension set property. Copyright © 2005 Society of Chemical Industry     

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.     

In situ composite: Phenolphthalein polyethersulfone—thermotropic liquid crystalline polymer blends

Phase behavior, thermal, rheological and mechanical properties plus morphology have been studied for a binary polymer blend. The blend is phenolphthalein polyethersulfone (PES-C) with a thermotropic liquid crystalline polymer (LCP), a condensation copolymer of p-hydroxybenzoic acid with ethylene terephthalate (PHB-PET). It was found that these two polymers from optically isotropic and homogeneous blends by means of a solvent casting method. The homogeneous blends undergo phase separation during heat treatment. However, melt mixed PES-C/PHB-PET blends were heterogeneous based upon DSC and DMA analysis and SEM examination. Addition of LCP in PES-C resulted in a marked reduction of melt viscosity and thus improved processability. Compared to pure PES-C, the charpy impact strength of the blend containing 2.5% LCP increased 2.5 times. Synergistic effects were also observed for the mechanical properties of blends containing < 10% LCP. Particulates, ribbons, and fibrils were found to be the typical morphological units of PHB-PET in the PES-C matrix, which depended upon the concentration of LCP and the processing conditions.     

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

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

Fibrillation of liquid crystalline polymer in polysulfone promoted by increased system elasticity via adding nano-silica

Ternary blends composed of a liquid crystalline polymer (LCP), nano-SiO₂ and polysulfone (PSF) were prepared by melt blending. Very long and perfectly oriented LCP fibrils were in situ formed in capillary flows by adding 5 vol% of nano-SiO₂ to binary PSF/LCP blend. Dynamic rheology analysis indicated that the sharp increase of elasticity was caused by higher content of nano-SiO₂. Then the entrance angle was decreased and elongational stress increased when the polymer melt flowed through the abrupt contraction, which resulted in the fibrillation of LCP in PSF/LCP/nano-SiO₂ system.     

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.     

Structured polymer blends: 2. Processing of polypropylene/EDPM blends: controlled rheology and morphology fixation via electron beam irradiation

Electron beam irradiation has been used to improve the processability of polypropylene/ethylene-propylenediene monomer (PP/EPDM) blends (controlled rheology) in combination with fixation of morphology by inducing crosslinks in the dispersed EPDM phase. An optimum morphology for impact toughening has been obtained via extrusion-blending high molecular weight PP with EPDM. Upon irradiation before subsequent processing (injection moulding) this morphology is fixated, whereas the viscosity of the blend decreases as a result of chain scission of the PP matrix. Impact strength and elongation at break of these irradiated blends are better than those of blends of low molecular weight PP with EPDM, which possess comparable overall viscosity.