Thermotropic liquid crystalline polymer (Rodrun LC5000)/polypropylene in situ composite films: rheology, morphology, molecular orientation and tensile properties

In situ composite films were prepared by a two-step method. First, polypropylene and thermotropic liquid crystalline polymer (TLCP), Rodrun LC5000 (80 mol% p-hydroxy benzoic acid (HBA)/20 mol% polyethylene terephthalate (PET)), were melt blended in a twin-screw extruder and then fabricated by extrusion through a mini-extruder as cast film. Rheological behavior of the blends, morphology of the extruded strands and films, and tensile properties of the in situ composite films were investigated. Rheological behavior of the blends at 295 °C studied using a plate-and-plate rheometer revealed a substantial reduction of the complex viscosity with increasing TLCP content, and all specimens exhibited shear thinning behavior. Over the angular frequency range of 0.6-200 rad/s, the viscosity ratio (dispersed phase to matrix phase) was found to be very low, in the range of 0.03-0.07. Morphologies of the fracture surfaces of the blend extrudates and the film surfaces etched in permanganic solution were investigated by scanning electron microscope (SEM). The TLCP droplets in the extruded strands were seen with a progressive deformation into fibrillar structure when TLCP content was increased up to 30 wt%. In the extruded films, TLCP fibrils with increasing aspect ratio (length to width) were observed with increasing TLCP concentration. Orientation functions of each component were determined by X-ray diffraction using a novel separation technique. It was observed that the Young's modulus in machine direction of the extruded film was greatly improved with increasing TLCP loading, due to the increase in fiber aspect ratio and also molecular orientation.     

Irradiation of highly oriented polyethylene fibers in the atmosphere of some vinyl monomers: Effect on compressive strength

Highly oriented polyethylene fibers have been modified by γ‐irradiation in the presence of some vinyl monomer vapors, followed with further annealing in the atmosphere of the same monomer. Two types of vinyl monomers that are known to produce polymers with different glass transition temperatures, namely methyl methacrylate and vinyl acetate, were studied for their effect on the compressive strength of the fiber. It was found that a significant improvement in compressive strength, measured by tensile recoil test, was obtained. The level of improvement was affected by heat treatment and the presence of monomer during irradiation. Modification with vinyl acetate was found to be more effective than methyl methacrylate. These facts suggest that the improvement in compressive strength was attributable to several factors, including structural relaxation, the presence of graft copolymer, and energy dissipation ability of the graft copolymer. It is speculated that lateral integrity of the fiber is one of the key factors that prevents sliding of microfibril and possibly lateral or circumferential expansion of the fiber to accommodate kink band. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2494–2502, 2001     

Fiber–matrix interactions in aramid‐short‐fiber‐reinforced thermoplastic polyurethane composites

The mechanical and dynamic mechanical properties of thermoplastic polyurethane (TPU) elastomers reinforced with two types of aramid short fibers, m‐aramid (Teijin‐Conex) and copoly(p‐aramid) (Technora), were investigated in this study with respect to the fiber loading. In general, both types of composites exhibited very similar stress–strain behaviors, except that Technora–TPU was stronger than Conex–TPU. This was primarily due to the intrinsic strength of the reinforcing fibers. Both types of fibers reinforced TPU effectively without any surface treatment. This could be attributed to good fiber–matrix interactions, which were revealed by the broadening of the tan δ peak in dynamic mechanical analysis. Furthermore, the morphologies of cryogenically fractured surfaces of the composites and extracted fibers, investigated with scanning electron microscopy, revealed possible polar–polar interactions between the aramid fibers and TPU matrices. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1059–1067, 2003     

In situ modulus enhancement of polypropylene monofilament through blending with a liquid‐crystalline copolyester

An immiscible blend of poly(propylene) (PP) with a thermotropic liquid‐crystalline polymer (TLCP, trade name Rodrun LC5000), a copolyester of 80/20 mol ratio of p‐hydroxy benzoic acid and polyethylene terephthalate was prepared in a twin‐screw extruder. The blend extrudate was fabricated as monofilament by using a single‐screw extruder equipped with a fiber line. The as‐spun filament was drawn at 120°C to enhance molecular orientation. Morphology, thermal, tensile, and dynamic mechanical properties of both as‐spun and drawn monofilaments were investigated. Almost continuously long TLCP fibers dispersed in PP matrix were obtained in the composite as‐spun monofilaments. The maximum modulus was found in 15 wt % TLCP/PP composite as‐spun filament, an increase of about 2.4 times that of the as‐spun neat PP. For the drawn filaments, the 10 wt % TLCP/PP composite showed a maximum modulus, an increase of about 1.5 times that of the drawn neat PP. The increase in the moduli was attributed not only to the reinforcement by TLCP fibrils with very high aspect ratio but also to the increases in PP crystallinity and molecular orientation through the drawing process. A remarkable improvement in the dynamic mechanical properties of the composite monofilaments was observed, especially in the high‐temperature region. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90:1337–1346, 2003     

Liquid crystalline copolyester/polyethylene in situ composite film: Rheology,morphology, molecular orientation,and tensile properties

A thermotropic liquid crystalline copolyester (TLCP) was blended with low density polyethylene using a corotating twin screw extruder and then fabricated by extrusion through a miniextruder as cast film. Rheological behavior, morphology, and tensile properties of the blends were investigated. Melt viscosities of neat components and blends measured by using plate‐and‐plate and capillary rheometers at 240°C, in the shear rate range 1–10⁴ s^?1, showed similar shear thinning effect. The viscosity values measured by the two techniques in the overlapping range of shear rate are found to be identical, which is in accord with the Cox–Merz rule. Addition of TLCP slightly reduces the matrix melt viscosity. TLCP dispersed phase in the extruded strand appeared in the form of spherical droplets. These droplets were elongated into fibrils with high aspect ratio (length to width) at the film extrusion step. As a result, the Young's modulus in machine direction (MD) of the composite film was greatly enhanced. At 20 wt % of TLCP, the MD Young's modulus was found to be about 16‐fold increase compared to that of the neat polyethylene film. However, the elongation at break sharply dropped with the increase of TLCP content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 561–567, 2002; DOI 10.1002/app.10307     

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     

Effects of fillers,maleated ethylene propylene diene diene rubber,and maleated ethylene octene copolymer on phase morphology and oil resistance in natural rubber/nitrile rubber blends

The phase morphology and oil resistance of 20/80 NR/NBR blends filled with different types of fillers and copolymers were investigated. In the case of filler effect, N220, N330, and N660 carbon blacks with different particle sizes were used. Additionally, the blends filled with nonblack‐reinforcing fillers, that is, precipitated and silane‐treated silica, were investigated. To study the compatibilization effect, maleated ethylene propylene diene rubber (EPDM‐g‐MA) and maleated ethylene octene copolymer (EOR‐g‐MA) were added to the blends. The results revealed that the addition of filler, either carbon black or silica, to the blend caused a drastic decrease in NR dispersed phase size. Carbon blacks with different particle sizes did not produce any significant difference in NR dispersed phase size under the optical microscope. Silica‐filled blends showed lower resistance to oil than did the carbon black–filled blends. In addition, it was determined that neither EOR‐g‐MA nor EPDM‐g‐MA could act as a compatibilizer for the blend system studied. The oil resistance of the blends with EPDM‐g‐MA is strongly affected by the overall polarity of the blend. In the case of EOR‐g‐MA, the oil resistance of the blends is significantly governed by both overall polarity of the blend and phase morphology. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1156–1162, 2003     

Thermotropic liquid‐crystalline copolyester (Rodrun LC3000)/thermoplastic elastomer (SEBS) in situ composites: II. Mechanical properties and morphology of monofilaments in comparison with extruded strands

Monofilaments of in situ composites were prepared from an immiscible blend of a thermotropic liquid‐crystalline polymer (TLCP), Rodrun LC3000, and a thermoplastic elastomer, styrene–(ethylene butylene)–styrene (SEBS), by a melt spinning process. Mechanical properties and the morphology of the composite monofilaments were investigated and compared with those of the extruded strands previously reported. The stresses at all tensile strains of the composite monofilaments were much higher than those of the extruded strands. The tensile strengths of both extruded strands and monofilaments were comparable, but the elongation at break of monofilaments dropped considerably. The tension sets of composite monofilaments were slightly higher than those of extruded strands. All composite monofilaments with TLCP content of ≤15 wt % exhibited good elastic recovery under the applied strain up to 200%. The dynamic mechanical storage modulus at 25°C of 10 wt % TLCP composite monofilament increased fourfold compared with that of the composite extruded strand and fivefold compared with that of the neat SEBS monofilament. The dramatic enhancement in the mechanical properties of in situ composite monofilaments is due to the formation of finer and longer TLCP fibrils (length‐to‐width ratio > 100) than those formed in the extruded strands. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 518–524, 2003     

Natural rubber and butadiene rubber blend using diblock copolymer of isoprene–butadiene as compatibilizer

Blends of natural rubber (NR) and butadiene rubber (BR) have been studied with or without diblock copolymers of isoprene–butadiene (BIR). It was found that NR/BR blends displayed the optimal properties at about 4 wt % of BIR from the tensile measurements of NR/BR blends. Increase of molecular weight of BIR resulted in the decrease of tensile properties, but had no significant effect on their hardness. Abrasion resistance of rubber blends containing BIR was about 30% higher than that without BIR. The molecular weight of BIR did not show a remarkable effect on the abrasion index. Differential scanning calorimetry and dynamic mechanical analyses of rubber blends suggested a two-phase structure even in the presence of BIR. © 1993 John Wiley & Sons, Inc.