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     

Phase behavior and properties of in situ‐reinforcing elastomer composites based on thermoplastic elastomers and thermotropic liquid crystalline copolyester

In situ reinforcing composites based on two elastomer matrices very different in melt viscosity, styrene–(ethylene butylene)–styrene triblock copolymer (Kraton G1650) and styrene–(ethylene propylene) diblock copolymer (Kraton G1701), and a thermotropic liquid crystalline polymer (TLCP), Rodrun LC3000, were prepared using a twin‐screw extruder. The rheological behavior, morphology, mechanical and thermal properties of the blends containing various LC3000 contents were investigated. G1650 was found to have much higher shear viscosity than G1701. All neat components and their blends exhibited shear thinning behavior. Melt viscosity of the blends gradually decreased with increasing LC3000 contents. Despite a large difference in melt viscosity of the two matrices, the results showed that the fibrillar morphology was obtained for both as‐extruded strands of LC3000/G1650 and LC3000/G1701 with up to 30 wt % LC3000. At 40 wt % LC3000 or more, the lamellar structure was observed for both types of blends because of the coalescence of liquid TLCP threads that occurred during extrusion. The addition of LC3000 into both elastomer matrices enhanced the tensile modulus considerably whereas the extensibility remarkably decreased. The results obtained from thermogravimetric analysis suggested that an addition of LC3000 into both elastomer matrices improved the thermal resistance significantly in air, but not in nitrogen. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1610–1619, 2006     

Self‐reinforcing elastomer composites based on polyolefinic thermoplastic elastomer and thermotropic liquid crystalline polymer

In situ reinforcing elastomer composites based on Santoprene thermoplastic elastomer, a polymerized polyolefin compound of ethylene–propylene–diene monomer/polypropylene, and a thermotropic liquid crystalline polymer (TLCP), Rodrun LC3000, were prepared using a single‐screw extruder. The rheological behavior, morphology, mechanical, and thermal properties of the blends containing various LC3000 contents were investigated. All neat components and their blends exhibited shear thinning behavior. With increasing TLCP content, processability became easier because of the decrease in melt viscosity of the blends. Despite the viscosity ratio of dispersed phase to the matrix phase for the blend system is lower than 0.14, most of TLCP domains in the blends containing 5–10 wt % LC3000 appeared as droplets. At 20 wt % LC3000 or more, the domain size of TLCP became larger because of the coalescence of liquid TLCP threads that occurred during extrusion. The addition of LC3000 into the elastomer matrix enhanced the initial tensile modulus considerably whereas the extensibility of the blends remarkably decreased with addition of high TLCP level (>.20 wt %). The incorporation of LC3000 into Santoprene slightly improved the thermal resistance both in nitrogen and in air. Dynamic mechanical analysis results clearly showed an enhancement in dynamic moduli for the blends with 20–30 wt % LC3000. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of compatibilizers on mechanical properties and morphology of in-situ composite film of thermotropic liquid crystalline polymer/polypropylene

An in-situ composite film of a thermotropic liquid crystalline polymer (LC3000)/polypropylene (TLCP/PP) was produced using the extrusion cast film technique. The compatibilizing effect of thermoplastic elastomers, styrene-ethylene butylene-styrene (SEBS), maleic anhydride grafted SEBS (MA-SEBS), and maleic anhydride grafted polypropylene (MA-PP) on the mechanical properties and morphology of the TLCP/PP composite films was investigated. It was found that SEBS provided a higher value of tensile modulus than MA-SEBS, which in turn was higher than MA-PP, despite the expected stronger interaction between the MA chain and TLCP. The observation of the morphology under optical and scanning electron microscopes suggested that all three compatibilizers helped improve the dispersion of the TLCP fibers and increased the fiber aspect ratio to a different extent. The fractured surface of the specimens showed more fiber breakage than pull-out when a compatibilizer was added, which suggested the improvement of interfacial adhesion. The surface roughness of fibers with an added elastomeric compatibilizermay also provide mechanical interlocking at the interface. It is suggested that the increase in the viscosity ratio of TLCP/PP due to the added elastomeric compatibilizer, SEBS and MA-SEBS, compared with the thermoplastic compatibilizer, MA-PP, is more effective in improving the composite mechanical properties.     

Comparative study on phase and properties between rPET/PS and LCP/PS in situ microfibrillar-reinforced composites

Microfibrillar-reinforced composites based on two dispersed phases, liquid crystalline polymer (LCP) and recycled poly(ethylene terephthalate) (rPET), and polystyrene (PS) were prepared using extrusion process. The rheological behavior, morphology, and thermal stability of LCP/PS and rPET/PS blends containing various dispersed phase contents were investigated. All blends and LCP exhibited shear thinning behavior, whereas Newtonian fluid behavior was observed for rPET. The incorporation of both LCP and rPET into PS significantly improved the processability. The potential of rPET as a processing lubricant by bringing down the melt viscosity of the blend system was as good as LCP. The elongated LCP domains were clearly observed in as-extruded strand. Although the viscosity ratio of rPET/PS system was lower than that of LCP/PS system, most rPET domains appeared as small droplets. An addition of LCP and rPET into PS matrix improved the thermal resistance in air significantly. The obtained results suggested the high potential of rPET as a processing aid and thermally stable reinforcing-material similar to LCP. The mechanical properties of the LCP-containing blends were mostly higher than those of the corresponding rPET-containing blends when compared at the same blend composition.     

Improvement of interfacial adhesion of poly(m‐phenylene isophthalamide) short fiber–thermoplastic elastomer (SEBS) composites by N‐alkylation on fiber surface

A composite of short‐fiber, poly(m‐phenylene isophthalamide), and thermoplastic elastomer styrene (ethylene–butylene) styrene (SEBS), was investigated. The fiber surface was modified by N‐alkylation (heptylation and dodecylation) to improve their compatibility with a less polar SEBS matrix. Observation of fiber‐surface morphology by SEM revealed surface roughness after N‐alkylation. Nearly complete coating of the polymer matrix on the fiber was observed on a fractured surface of the composite, which is evidence for the improvement of fiber–matrix adhesion. It was found that the modulus of the composites grew with increasing fiber loading to approximately the same extent for both unmodified and modified fiber composites. Tensile strength of the modified fiber composites was found to improve significantly over that of the unmodified fiber composite. This suggests that the presence of the alkyl group on the fiber surface is responsible for an improvement of interfacial adhesion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2414–2422, 1999     

Photoinitiated grafting of methyl methacrylate on highly oriented polyethylene: Effect of draw ratio on grafting

Modification of highly oriented polyethylene was performed using a photoinitiated grafting technique. The samples were first coated with photoinitiator and then exposed to methyl methacrylate vapor under UV light (λ > 290 nm) at 60°C. The extent of grafting was studied as a function of draw ratio. It was found that the extent of grafting decreased significantly as the draw ratio was increased. Control samples of undrawn samples with different thermal histories suggested that there was another factor in addition to crystallinity that influences the extent of grafting. It is proposed that amorphous orientation or taut-tie molecules reduce the photoinitiation process. Gravimetric and attenuated total reflectance-IR measurements indicated that the grafting reaction can occur below the sample surface (or internal grafting) and that the proportion of surface grafting increases with increasing draw ratio. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 465–470, 1998     

Reinforcing performance of recycled PET microfibrils in comparison with liquid crystalline polymer for polypropylene based composite fibers

Recycled polyethylene terephthalate (rPET) used as an alternative reinforcing additive for polypropylene (PP) based composite fibers, compared with liquid crystalline polymer (LCP), was investigated. Both PP-LCP and PP-rPET composites were prepared as fiber using hot drawing process. The effects of draw ratios and compatibilizer dosages on morphology in relation to tensile properties of both types of the composite systems were studied. The variation of draw ratios resulted in much change of stress–strain behavior in compatibilized rPET composite system owing to the obvious difference in morphological change of rPET dispersed phase upon drawing. Tensile strength and extensibility of both composites system were significantly improved with compatibilizer loading. The tensile strength of compatibilized rPET-composite fibers was higher than that of the compatibilized LCP system. The obtained results demonstrated the high potential of rPET as a well-defined reinforcing material for PP based composite fiber under the improved interfacial adhesion promoted by compatibilizer.     

In situ microfibrillar‐reinforced composites of isotactic polypropylene/recycled poly(ethylene terephthalate) system and effect of compatibilizer

Recycled poly(ethylene terephthalate) from waste bottles (hereafter, rPET) was used as an reinforcing material for isotactic polypropylene (iPP) based on the concept of in situ microfibrillar‐reinforced composites (iMFCs). Microfibers of rPET were successfully generated during melt‐extrusion and subsequent drawing and preserved in the final injection‐molded specimens. The effects of draw ratio, initial size of ground rPET flakes, and rPET content on morphological appearance of the extrudates and the as‐formed rPET fibers and mechanical properties of the as‐prepared iMFCs were investigated. The results showed that diameters of the as‐formed rPET fibers decreased with increasing draw ratio, and the initial size of ground rPET flakes did not affect the final diameters of the as‐formed rPET fibers nor the mechanical properties of the as‐prepared iMFCs. Flexural modulus, tensile modulus, and tensile strength of iPP/rPET iMFCs were improved by the presence of rPET microfibers and further improvement could be achieved by the addition of maleic anhydride‐grafted iPP (PP‐g‐MA), which was used as the compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1173–1181, 2006