Reinforcement of mechanical properties of a poly(ethylene terephthalate) and polycarbonate blend by the addition of thermotropic liquid crystalline polymer

Mechanical properties of the ternary blends of poly(ethylene terephthalate) (PET), polycarbonate (PC), and thermotropic liquid crystalline (TCLP, Vectra A950) were investigated. The ternary blends were prepared by varying the amount TLCP but fixing the ration of PET and PC. The fiber fallen freely through the capillary die had the highest initial modulus (1.46 GPa)/tensile strength (73 MPa) when 10% of TLCP was added. Above this TLCP content, however initial modulus and tensile strength decreased. The scanning electron microscope (SEM) micrographs of the TLCP phase which was extracted by dissolving PET/PC matrix from the blend showed the fine fibrils formed at 5 and 10% of TLCP, while the aggregated TLCP phases at 20 and 30% of TLCP. It was suggested that the decrease of the mechanical properties of the resulting blend was caused by the aggregation of TLCP phase above 10% of TLCP. A high draw ratio gave a rise to the formation of highly oriented fibrils of TLCP phase in the PET/PC matrix and the improvement of mechanical properties of the ternary blend.     

PET/PTT共混体系的相容特性及力学性能研究

通过熔融共混法制备了聚对苯二甲酸乙二醇酯(PET)与聚对苯二甲酸醇酯(PTT)的共混物,采用差示扫描量热仪、动态热机械分析仪、万能电子试验机等对共混体系的热性能、动态力学性能及拉伸性能进行了测试。测得PET/PTT共混体系只有1个玻璃化转变温度(Tg)和损耗峰,表明在非晶区完全相容,其中纯PET的Tg为84℃,纯PTT的Tg低于50℃; 而双重熔融峰及热结晶峰宽化现象的出现表明,共混体系在晶区是部分相容,各组分倾向于分别进行有序化排列、单独结晶,其中纯PET的熔点为256℃,纯PTT的熔点为229 ℃;共混体系的拉伸模量和拉伸强度随PTT含量的增加呈上升趋势;但当共混比例接近时体系的拉伸模量和拉伸强度有所下降,共混比为5/5时的拉伸模量和拉伸强度分别低达1098MPa和51MPa。     

Structure and properties of blend fibers from poly(ethylene terephthalate) and liquid crystalline polymer

The structure and properties of the as-spun fibers of poly(ethylene terephthalate) (PET) blends with a thermotropic liquid crystalline polymer (LCP), Vectra A900, were studied in detail. The DSC results indicate that the LCP component may act as a nucleating agent promoting the crystallization of the PET matrix from the glassy state but which inhibits its crystallization from the melt due to the existence of an LCP supercooled mesophase. The effect of the drawdown ratio on the orientation of the as-spun blend fibers is highly composition-dependent, which is mainly associated with the formation of LCP fibrils during melt spinning. The modulus of the as-spun blend fibers has a significant increase as the content of LCP reaches 10%, while the tensile strength has a slightly decreasing tendency. The mechanical properties of the as-spun blend fibers could be well improved by heat treatment because of a striking increase in the crystallinity of the PET matrix. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 217–224, 1997     

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.     

Chain orientation in melt-extruded samples of vectra A,vectra B,and blends in relation to the mechanical properties

The profile of molecular orientation within injection-molded tensile bars of the liquid crystalline copolyesters Vectra A, Vectra B, and Vectra C, as well as blends of these polymers, was investigated by means of wide-angle X-ray scattering (WAXS) using synchrotron radiation (HASYLAB, Hamburg). The local variation of chain orientation was resolved into steps of 100 μm. An even higher resolution was obtained by using the microfocus camera (focal spot 2 μm) at the European Synchrotron Radiation Facility (ESRF) in Grenoble. In Vectra A and in the blend of Vectra A and Vectra B, a smooth variation of the orientation was found being almost zero at the surface and showing its maximum at a distance of 0.6 mm from the surface. The orientation in Vectra B was rather fluctuating. The average chain orientation in the blend samples processed under the same conditions was higher than in samples of the pure liquid crystalline copolyesters. The mechanical properties of the different layers within the injection moldings were determined by cutting the samples into slices and measuring the stress-strain curves. For specimens of comparable orientation, it turned out that the blend samples had the largest values of Young's modulus and tensile strength. The synergism of orientation and mechanical strength was also found for different blend compositions, as well as in blends of Vectra B and Vectra C. Annealing the injection moldings above the melting point resulted in a rapid relaxation of the orientation, whereas the chain alignment persisted at lower temperatures. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 531–545, 1998     

A study on blends of liquid crystalline copolyesters with polycarbonate. III. Mechanical properties of compatibilized blends

Blends of liquid crystalline poly(oxybenzoate-co-oxynaphthalate) (Vectra A950) and polycarbonate (PC) were prepared by adding a compatibilizer to the two polymers in a melt-blending process. The compatibilizer was based on controlled transesterification between synthesized poly(oxybenzoate-co-terephthalate) (40/60) and PC. The compatibilizer exhibited birefringence, and its thermal property was analyzed by differential scanning calorimetry. The maximum increase in tensile modulus and tensile strength of these compatibilized Vectra blends were 24% and 54%, respectively, as compared with those of binary Vectra blend without compatibilizer resulting from an injection-molding process. The tensile properties of the compatibilized Vectra blends decreased once the concentration of the compatibilizer exceeded 2 phr. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1527–1533, 1997     

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     

Modification of the processing window of a thermotropic liquid crystalline polymer by blending with another thermotropic liquid crystalline polymer

This paper is concerned with properties and processing performance of two thermotropic liquid crystalline polymers (TLCPs) produced by DuPont (HX6000 and HX8000) with widely varying melting points and blends of these two TLCPs. This work was carried out in an effort to develop a TLCP suitable for generating poly(ethylene terephthalate) (PET) composites in which the melting point of the TLCP was higher than the processing temperature of PET. Strands of the neat TLCPs and a 50/50 wt % TLCP–TLCP blend were spun and tested for their tensile properties. It was determined that the moduli of the HX8000, HX6000, and HX6000–HX8000 blend strands were 47.1, 70, and 38.5 GPa, respectfully. Monofilaments of PET–HX6000–HX8000 (50/25/25 wt %) were spun with the use of a novel dual extruder process. The strands had moduli as high as 28 GPa, exceeding predictions made using the rule of mixtures and tensile strengths around 275 MPa. The strands were then uniaxially compression molded at 270°C. It was found that after compression molding, the modulus dropped from 28 GPa to roughly 12 GPa due to the loss of molecular orientation in the TLCP phase. However, this represents an improvement over the use of HX8000. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2209–2218, 1999     

Fabrication of High Performance PET/TLCP Fibers through the Synergistic Interfacial Enhancement and Compatibilization of Functional 1D and 2D Carbon Nanomaterials

The maleic anhydride functionalized graphene oxide (GO-MA) is fabricated by an efficient and solvent-free Diels–Alder reaction. Polyethylene terephthalate (PET)/thermotropic liquid crystal polyester (TLCP), PET/TLCP/GO-MA, PET/TLCP/aminated multi-walled carbon nanotubes (MWCNTs-NH₂), and PET/TLCP/GO-MA/MWCNTs-NH₂ composite fibers are systematically melt-spun. The structure and compatibilizing effects of GO-MA and MWCNTs-NH₂ on the mechanical, thermal, and crystallization properties of the composite fibers are indicated. The non-isothermal crystallization kinetics and X-ray diffraction (XRD) data show that TLCP and nanofillers can change the crystalline morphology of PET. The mechanical properties of the fibers rise with increasing TLCP content. The tensile strength 929 MPa and modulus 17.5 GPa of the fibers with 7 wt% TLCP and 0.25 wt% nanofillers (0.1 wt% GO-MA and 0.15 wt% MWCNTs-NH₂) are significantly higher than those with 7 wt% TLCP (tensile strength 622 MPa and modulus 16.1 GPa) and even higher than those with 15% TLCP (tensile strength 836 MPa, and modulus 18.0 GPa). When the GO-MA and MWCNTs-NH₂ co-exist, the anti-dripping phenomenon is improved. Therefore, the TLCP, GO, and MWCNTs synergistically strengthens the mechanical properties. This is promising for the industrial fabrication of high-strength fibers.     

Toughening of recycled poly(ethylene terephthalate)/glass fiber blends with ethylene–butyl acrylate–glycidyl methacrylate copolymer and maleic anhydride grafted polyethylene–octene rubber

The aim of this study was to improve the toughness of recycled poly(ethylene terephthalate) (PET)/glass fiber (GF) blends through the addition of ethylene–butyl acrylate–glycidyl methacrylate copolymer (EBAGMA) and maleic anhydride grafted polyethylene–octene (POE‐g‐MAH) individually. The morphology and mechanical properties of the ternary blend were also examined in this study. EBAGMA was more effective in toughening recycled PET/GF blends than POE‐g‐MAH; this resulted from its better compatibility with PET and stronger fiber/matrix bonding, as indicated by scanning electron microscopy images. The PET/GF/EBAGMA ternary blend had improved impact strength and well‐balanced mechanical properties at a loading of 8 wt % EBAGMA. The addition of POE‐g‐MAH weakened the fiber/matrix bonding due to more POE‐g‐MAH coated on the GF, which led to weakened impact strength, tensile strength, and flexural modulus. According to dynamic rheometer testing, the use of both EBAGMA and POE‐g‐MAH remarkably increased the melt storage modulus and dynamic viscosity. Differential scanning calorimetry analysis showed that the addition of EBAGMA lowered the crystallization rate of the PET/GF blend, whereas POE‐g‐MAH increased it. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Extruded blends of a thermotropic liquid crystalline polymer with polyethylene terephthalate,polypropylene, and polyphenylene sulfide

Structure–property relationships were investigated for blends of a polyester-type thermotropic liquid crystalline polymer (LCP) with polyethylene terephthalate (PET), polypropylene (PP), and polyphenylene sulfide (PPS). The polymers were melt blended in a twin-screw extruder and the blends were extruded to strands of different draw ratios. Tensile properties of the blends were determined as a function of LCP content and draw ratio and compared with the results of morphological and rheological analyses. In general, the strength and stiffness of the matrix polymers were improved with increasing LCP content and draw ratio. At a draw ratio of 11, the blends of PET/30 wt % LCP exhibited a tensile strength about three times and an elastic modulus nearly four times that of pure PET. All blends exhibited a skin/core morphology with thin fibrils in the skin region. The formation and the sizes of the fibril-like LCP domains in the matrices were found to depend on LCP content and the viscosity ratio of the blend components.     

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.     

Poly(ethylene‐co‐methacrylic acid)–lithium ionomer as a compatibilizer for poly(ethylene terephthalate)/linear low‐density polyethylene blends

Poly(ethylene terephthalate) (PET)/linear low‐density polyethylene (LLDPE) blends (75/25), with contents of poly(ethylene‐co‐methacrylic acid) partially neutralized with lithium (PEMA–Li) that were systematically changed from 0 to 45% relative to the LLDPE, were obtained by direct injection molding in an attempt to (1) ameliorate the performance of the binary blend and (2) find the best compatibilizer content. PEMA–Li did not modify the PET or LLDPE amorphous‐phase compositions or the crystalline content of PET. However, PEMA–Li did lead to a nucleation effect and to the presence of a second smaller and less perfect crystalline structure. PET induced a fractional crystallization in LLDPE that remained in the presence of PEMA–Li and reduced the crystallinity of LLDPE. The ternary blends showed two similar dispersed LLDPE and PEMA–Li phases with small subparticles, probably PET, inside. The compatibilizing effect of PEMA–Li was clearly shown by the impressive increase in the break strain, along with only small decreases in the modulus of elasticity and in the tensile strength. With respect to the recycling possibilities of LLDPE, a ternary blend with the addition of 22.5% PEMA–Li, which led to very slight modulus and yield stress decreases with respect to the binary blend and a break strain increase of 480%, appeared to be the most attractive. However, the highest property improvement appeared with the addition of 37.5% PEMA–Li, which led to elasticity modulus and tensile strength decreases of only 9%, along with a very high break strain increase (760%). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1322–1328, 2003     

Rheology of phase separated blends of two thermotropic liquid crystalline copolyesters

The melt rheology of phase separated blends of two thermotropic liquid crystalline polymers (LCPs) have been studied. The two components are a random copolyesters consisting of 73 mol% 4-hydrobenzoic acid (HBA) and 27 mol% 6-hydroxy-2-napthoic acid (Vectra A900 of Hoechst Celanese Corp.) and a poly(ethylene terephalate-co-4-oxybenzoate) containing 60 mol% HBA units (PET/60HBA of Eastman Kodak Corp.). Most striking is the effect of adding 10% PET/60HBA to Vectra A900: The viscosity at 290°C drops by a factor of 4 and the terminal zone of the relaxation time spectrum is shifted to much shorter times. This is an interesting effect that could be used for LCP processing even if its origin is not yet understood. Differential scanning calorimetry measurements support the hypothesis that the blend is phase separated and that no transestification reaction occurs during the experiments.     

Morphological and mechanical properties of PET-LCP blend fibers

Blends of poly(ethylene terephthalate-co-p-oxybenzoate) (PET–PHB) with poly(ethylene terephthalate) (PET) have been studied in the form of as-spun and drawn fibers. Mechanical properties of drawn blend fibers (DR-6.0) up to 10 wt % liquid crystalline polymer (LCP) component exhibit significant improvement in modulus and strength. With the addition of 10 wt % LCP content in PET matrix, the modulus increases from 11.78 to 17.72 GPa, and the strength increases from 0.76 to 1.0 GPa in comparison to the PET homopolymer. With further addition of LCP content, the properties drop down. Scanning electron microscopy studies of drawn blend fibers show that up to 10 wt % LCP content the blends contain the LCP domains in the size range of 0.07–0.2 μm and are well distributed in the PET matrix. © 1995 John Wiley & Sons, Inc.     

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.     

Properties of blends of starch and synthetic polymers containing anhydride groups. II. Effect of amylopectin to amylose ratio in starch

Corn starch with different amylopectin to amylose ratios was blended with styrene maleic anhydride copolymer (SMA) and ethylene–propylene-g-maleic anhydride copolymer (EPMA). The starch had an amylose content of approximately 0, 50, and 70%. The concentration of starch in the blend was kept constant at 60% by weight. The samples were melt blended in a corotating twin screw extruder. Scanning electron micrographs showed that the amount of starch granules remaining in the samples varied with the torque. Optical micrograph showed that starch/EPMA blends formed a cocontinuous phase in all blends irrespective of starch variety. For starch/SMA blends, the starch granules remained dispersed in the SMA phase. The torque during blending, tensile strength, water absorption, storage and loss modulus, and data on biodegradability of the blends are presented. Tensile strength and water absorption correlated well with the torque generated during blending: the higher the torque, the lower the tensile strength and the higher the water absorption. The tensile strength of blends containing SMA decreased when the humidity increased. Fractured surfaces of starch/SMA blends exhibited brittle failure; for the ductile starch/EPMA blends, shear tearing appeared to be the major failure mechanism. For blends containing EPMA, the percentage elongation increased with increased humidity. Dynamic mechanical analysis of the blends showed two sharp peaks for tan δ vs. temperature plot for starch/EPMA plots, but showed a single peak for starch/SMA blends. Starch/EPMA blends had a higher percentage of water aborption that became constant after 20 days. Using the ASTM test method D5902, the starch content in the samples was found to degrade. © 1995 John Wiley & Sons, Inc.     

High modulus/tenacity filaments from blends of different molecular weights of polypropylene

Polypropylene (PP) filaments are prepared by blending two different molecular weight components of PP. A melt‐spinning process to produce filaments includes mixing of components, extrusion, and two‐stage drawing, followed by a unique Gradient Drawing? process. Blending results in highly deformable as‐spun filaments with high draw ratios. For 90:10 blends of PP samples with melt flow indexes of 35 and 3, a high level of crystallinity and crystalline and amorphous orientations are obtained. A sonic modulus of 28 GPa, dynamic modulus of 20 GPa, tensile modulus of 16 GPa, and tenacity of 667 MPa are achieved. These samples are dimensionally stable up to ～100°C. All steps in the production of the filaments are continuous. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1021–1028, 2005     

Morphology and mechanical performance of pregenerated and “in-situ” PP/vectra B composites

Polypropylene/Vectra B blends were obtained at different LCP contents and barrel temperatures by an extrusion-injection process. The wide barrel injection temperature range chosen, from 200 to 300°C, gave rise to blends in which the pregenerated extruded morphology was preserved, partially preserved, or lost. The blends processed at 260 and 300°C showed the usual morphology and properties of “in-situ” composites. The blends injected at 240°C showed the worst properties because of their partially melted and agglomerated morphology. A barrel temperature of 200°C (80°C below the melt temperature of Vectra B) was needed to maintain the pregenerated fibers. These pregenerated composites, without post-extrusion drawing, showed smaller modulus of elasticity and tensile strength than those of the “in-situ” composites, but an increased notched impact strength as a consequence of their less perfectly oriented but more homogeneous morphology.     

Interface modification of compatibilized polyethylene terephthalate/polypropylene blends: Effect of compatibilization on thermomechanical properties and thermal stability

Polyethylene terephthalate (PET) and polypropylene (PP) are incompatible thermoplastics because of differences in chemical structure and polarity, hence their blends possess inferior mechanical and thermal properties. Compatibilization with a suitable block/graft copolymer is one way to improve the mechanical and thermal properties of the PET/PP blend. In this study, the toughness, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA) of PET/PP blends were investigated as a function of different content of styrene‐ethylene‐butylene‐styrene‐g‐maleic anhydride (SEBS‐g‐MAH) compatibilizer. PET, PP, and SEBS‐g‐MAH were melt‐blended in a single step using the counter rotating twin screw extruder with compatibilizer concentrations of 0, 5, 10, and 15 phr, respectively. The impact strength of compatibilized blend with 10 phr SEBS‐g‐MAH increased by 300% compared to the uncompatibilized blend. Scanning electron microscope (SEM) micrographs show that the addition of 10 phr SEBS‐g‐MAH compatibilizer into the PET/PP blends decreased the particle size of the dispersed PP phase to the minimum level. The improvement of the storage modulus and the decrease in the glass transition temperature of the PET phase indicated an interaction among the blend components. Thermal stability of the PET/PP blends was significantly improved because of the addition of SEBS‐g‐MAH. J. VINYL ADDIT. TECHNOL., 23:45–54, 2017. © 2015 Society of Plastics Engineers