Crystallization kinetics of poly(ethylene terephthalate) with thermotropic liquid crystalline polymer blends

The isothermal and dynamic crystallization behaviors of polyethylene terephthalate (PET) blended with three types of liquid crystal polymers, i.e., PHB60–PET40, HBA73–HNA27, [(PHB60–PET40)–(HBA73–HNA27) 50 : 50], have been studied using differential scanning calorimetry (DSC). The kinetics were calculated using the slope of the crystallization versus time plot, the time for 50% reduced crystallinity, the time to attain maximum rate of crystallization, and the Avrami equation. All the liquid crystalline polymer reinforcements with 10 wt % added accelerated the rate of crystallization of PET; however, the order of the acceleration effect among the liquid crystalline polymers could not be defined from the isothermal crystallization kinetics. The order of the effect for liquid crystalline polymer on the crystallization of PET is as follows: (PHB60–PET40)–(HBA73–HNA27) (50 : 50); HBA73–HNA27; PHB60–PET40: This order forms the dynamic scan of the DSC measurements. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1383–1392, 1998     

Injection molding of poly(ethylene terephthalate) reinforced with pregenerated thermotropic liquid crystalline polymer microfibrils

This work was concerned with the injection molding of poly(ethylene terephthalate) (PET) reinforced with pregenerated thermotropic liquid crystalline polymer (TLCP) fibrils, where the TLCP had a higher melt processing temperature than PET. These composites, referred to as pregenerated microcomposites, were produced using a two step processing scheme. First, a novel dual extrusion process was used to spin strands of PET reinforced with nearly continuous TLCP fibrils. Second, these strands were subsequently chopped into pellets and injection molded below the melt processing temperature of the TLCP but above that of PET. This allowed the high modulus TLCP fibrils generated in the spinning step to be retained in the injection molded samples. TLCP concentration and strand draw ratio were varied in the composite strands to determine how they affected mechanical properties. It was shown that the best properties were obtained using strands containing 50 weight percent TLCP with draw ratios greater than 50, which were diluted to the desired loading level with a low viscosity injection molding grade of PET. Specifically, these composites had tensile moduli as high as 5.7 GPa when reinforced with 30 weight percent HX1000. Also, it was determined that pregenerated microcomposites had smoother surfaces than glass-filled PET.     

Thermal properties of blends of poly(ethylene terephthalate) and a liquid crystalline copolyester

Summary A thermotropic liquid crystal copolyester (CHQ/BP/TA/IA; 40/10/40/10) (LCP), and melt blends of poly (ethylene terephthalate) (PET) with LCP have been studied for thermal transition and crystallization behaviour. The LCP has a mesophase transition (KM) in the temperature range of 295–315°C. The endothermic peak showing mesophase to Isotropic (MI) transition is observed around 420°C. These transitions are supported by hot stage polarizing microscopy. In blends of PET/LCP, the mesomorphic transition is observed at temperature around 314°C, along with the melting transition of PET around 274°C. The dynamic calorimetric measurements reveal that the two polymers are at least partially miscible.     

Novel blends made of ionic naphthalene thermotropic polymer and poly(ethylene terephthalate)

Novel blends made of ionic naphthalene thermotropic polymer (NTP) and poly(ethylene terephthalate) (PET) have been prepared by melt mixing. Homogeneous blends were formed when a small amount (5 wt%) of ionic NTP was blended with PET; but, phase separation occurred at a higher composition of the ionic NTP (10 wt%). Both the stiffness and the strength are enhanced in all the blends studied as compared with PET. A remarkable increase in ductility and toughness is noted during necking in these blends. Enhancement in tensile properties and good homogeneity of the blends at low composition (5 wt%) are attributed to ion-dipole interactions between the ionic groups of the ionic NTP and the dipolar units of the PET. It is suggested that ionic NTP chains not only act as reinforcer in the homogeneous blends, but also serve as a nucleating agent to increase crystallinity and as a good stress transfer agent to ease an inhomogeneous deformation process during necking of the PET matrix under tensile stress.     

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.-%.     

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.     

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     

Blends of thermotropic liquid crystalline polyesters and poly(butylene terephthalate): Thermal,mechanical, and morphological properties

Blends of poly(butylene terephthalate) (PBT) with three different thermotropic liquid crystalline polyesters (TLCPs) were prepared. The first TLCP (HBH-6) consists of diad aromaticester type mesogenic units and the hexamethylene spacers along the main chain, and the second (TB-S6) is a wholly aromatic polyester TLCP having alkoxy side groups on the terephthaloyl moiety. The last (TR-4,6) is an LC copolymer comsisting of triad aromatic ester type mesogenic units and two differents spacers; tetramethylene and hexamethylene units. Blends of TLCP with PBT were melt spum at different LCP contents and differnt draw ratios to produce monofilaments. For the HBH-6/PBT and TB-S6/PBT blends, the ultimate tensile strength showed a maximum value at the 5 wt% level of LCP in the blends, and then it decreased when the LCP content was increased up to 20%. On the other hand, the initial modulus monotonically increased with increasing LCP content in all cases. The blends with TB-S6 showed the highest tensile properties of the three blends systems. This can be ascribed to the highest rigidity of the polymer chain, which still carries relatively long alkoxy substituents that promote sufficient adhesion between the LCP and PBT matrix. When compared with the PBT fiber itself, the fibers obtained from the 5% TB-S6/PBT blends exhibited an improvement in tensile strength by > 25% and in tensile modulus by ～ 200%.     

Fracture toughness and morphology of phenolphthalein poly(ether sulfone)–thermotropic liquid crystalline polymer blends

Blends of a new phenolphthalein poly(ether sulfone) (PES-C) and a thermotropic liquid crystalline polymer (LCP) were prepared by melt-blending in a twin-screw extruder. Rheological properties, fracture toughness, K_IC, and morphology of the blends were studied. It was found that the addition of LCP could reduce the melting viscosity and improve the fracture toughness of the PES-C matrix. The morphology of the LCP phase for the fractured section changed with increasing LCP content in the blend from dropletlike to fibrillar and layered structure. Strong interfacial adhesion could be observed at a lower content of LCP. The toughening mechanisms by blending LCP were also discussed. © 1994 John Wiley & Sons, Inc.     

Morphological studies of blends containing liquid crystalline polymers with poly(ethylene terephthalate)

The investigation involved the structure–property behavior of extruded cast films prepared from blends of thermotropic liquid crystalline copolyesters with poly(ethylene terephthalate) (PET). Data were obtained which showed not only the temperature dependence of the moduli and stress–strain behavior but also the orientation effects that must be prevalent in order to explain the differences between the moduli measured parallel and perpendicular to the extrusion direction. Only at high liquid crystal polymer (LCP) composition is the modulus particularly increased. The modulus enhancement with lower LCP content and utilization of process variables are discussed with respect to the induced morphological textures and nature of the process equipment. Specifically, the process variable extruder gear pump speed did not enhance Young's modulus at the same LCP content as extensively as did the process variable of extruder screw speed.     

Thermal properties of blends of a thermotropic liquid crystalline copolyester of poly(hydroxy benzoic acid-co-ethylene terephthalate) and polyarylate

Summary Thermal properties and transesterification reaction of blends of polyarylate (PAr) and a thermotropic liquid crystalline polymer (LCP) were investigated by differential scanning calorimetry (DSC) and Fourier Transform infrared (FT-IR) spectroscopy. In the thermogram of PAr-LCP blends, two glass transition temperatures (T_gs) were observed. Phase behavior of the blends revealed that the LCP dissolved more in the PAr-rich phase than did the PAr in the LCP-rich phase, indicating partial miscibility between two polymers. The polymer-polymer interaction parameter (χ₁₂) was calculated, and ranged from 0.069 to 0.076. In the calculation of the χ₁₂, the anisotropy of the LCP was considered. After annealing, the two T_gs of the blends were shifted toward the center. In the FT-IR spectroscopy study of the annealed PAr-LCP blends, three new characteristic peaks of the ester group were detected. The DSC and FT-IR results suggested that transesterification reaction between PAr and LCP occurred under the annealed condition. Received: 12 May 2000/Revised version: 11 July 2000/Accepted: 24 July 2000     

增容PP/回收PET共混物的力学性能

采用熔融挤出法制备了聚丙烯(PP)/增容剂/回收聚对苯二甲酸乙二酯(r-PET)共混物,研究了r-PET、不同增容剂和混合增容剂对PP/r-PET共混物力学性能的影响.r-PET提高了PP的拉伸强度、弯曲强度及其模量,但降低了冲击强度;采用马来酸酐接枝聚丙烯(PP-g-MAH)增容,可提高PP/r-PET共混物的拉伸强度、弯曲强度及其模量,但使冲击强度稍有降低;马来酸酐接枝乙烯-辛烯共聚物(POE-g-MAH)增容或PP-g-MAH/POE-g-MAH混合增容可提高PP/r-PET共混物的冲击强度,且对共混物的拉伸和弯曲强度影响不大.     

Mechanical properties of the rubber-toughened polymer blends of polycarbonate (PC) and poly(ethylene terephthalate) (PET)

The intrinsically impact-brittle PC/PET blends can be effectively toughened, in terms of lower ductile brittle transition temperature (DBTT) and reduced notch sensitivity, by incorporating butylacrylate core-shell rubber. The rubber particles are distributed exclusively in the PC phase. Varying the PC melt flow rate (MFR) is more important than varying the PET I.V. to vary the low temperature toughness of the blends. PC with MFR = 3 is essential to produce the toughest PC/PET/rubber blend. The presence of rubber slightly relieves the strain rate sensitivity on yield stress increase. Lower MFR PC in the blend results in smaller activation volume and, therefore, higher strain rate sensitivity, because a greater number of chain segments are involved in the cooperative movement during yielding. Two separate modes, localized and mass shear yielding, work simultaneously in the rubber toughening mechanism. The plane-strain localized shear yielding dominates the toughening mechanism at lower temperatures and brittle failure, while the plane-stress mass shear yielding dominates at higher temperatures and ductile failure. The critical precrack plastic zone volume has been used to interpret the observed phenomenon. © 1994 John Wiley & Sons, Inc.     

Thermal and mechanical properties of injection molded blends of a liquid crystalline polymer and poly(butylene terephthalate)

The microstructure and the thermal and mechanical properties of injection molded samples of different blends of Vectra (LCP) and poly(butylene terephthalate) (PBT) have been studied. Differential scanning calorimetry and hot-stage polarized light microscopy showed that the crystallization of PBT was unaffected by the presence of LCP. X-ray diffraction showed that the PBT component was always unoriented in the injection molded samples. Blends with less than 28 vol% LCP exhibited the same stiffness and the same coefficient of linear thermal expansion as PBT. Blends containing more than 38 vol% LCP contained an oriented LCP phase and had a stiffness in accordance with the upper-bound composite equation. The coefficients of linear thermal expansion for these blends were close to that of pure LCP.     

Thermal behavior,morphology, and mechanical properties of blend strands consisting of poly(ethylene terephthalate) and semiaromatic liquid crystalline polymer

Polymer blends of poly(ethylene terephthalate) (PET) and a liquid crystalline polymer (LCP) [random copolymers of the poly(ethylene telephthalate) and poly (hydroxybenzoic acid)] were prepared by using a twin-screw extruder. Strands were extruded from a capillary die. Extruded stands were stretched in an oven at 80°C. DSC and SEM were employed to investigate the structural properties of the strands. Mechanical properties of the strands were evaluated by a sonic propagation method. DSC investigation suggested that LCP phases may act as a nucleating agent of PET and the orientation-induced crystallization of PET was accelerated by the presence of LCP. An SEM micrograph shows that the LCP phases formed finely spherical domains with a diameter of 0.1–1.0 μm in the PET matrix and large parts of LCP spherical droplets were deformed to fibrils. In the case of unstretched strands, sonic moduli increased linearly with increasing LCP content, because PET was reinforced by LCP fibrils as in the case of glass fiber-reinforced PET. The degree of crys-tallization of PET also increased with increasing LCP contents. In the case of stretched strands, sonic moduli increased with an increasing stretching ratio due to the orientation-induced crystallization of PET. A larger increasing of the sonic modulus was shown in LCP-containing strands in the regions of a low stretching ratio (1–5), since the orientation-induced crystallization of PET was accelerated by the presence of LCP phases. © 1996 John Wiley & Sons. Inc.     

Morphology and properties of blends of polyethylene with a semiflexible liquid crystalline polymer

Blends of three polyethylene (PE) samples (two HDPE grades and LLDPE) with an experimental sample of a semiflexible liquid crystalline polymer (SBH 1:1:2 by Eniricerche) have been prepared in a Brabender compounder. The processing-aid effect of the LCP has been demonstrated by the decreased energy required for extruding the blends, as compared to that needed for neat PE. The thermal properties, as studied by differential scanning calorimetry (DSC), have shown that the two components of the blends are immiscible. However, the dispersed SBH phase has been found to act as a nucleating agent for the crystallization of LLDPE, whereas no such effect was observed for HDPE. This has been taken as an indication that the phase interactions of SBH with LLDPE are more pronounced than with HDPE. The morphological study of the blends, done by scanning electron microscopy (SEM), has confirmed this conclusion. In fact, the SBH particles show a much better dispersion and a narrower size distribution in the LLDPE/SBH blends. The mechanical properties of the blends have been studied on compression-molded specimens. The results indicate that the reinforcing effect of SBH is practically none for both HDPE grades. In fact, the elongation at break decreases to very low values, and the tensile strength is also reduced, when the LCP concentration increases beyond 5–10%, whereas the tensile modulus does not vary appreciably, over the whole (0–20%) LCP range investigated. On the contrary, the tensile modulus of the LLDPE/SBH blends increases up to ca. 50%, and the elongation at break decreases more smoothly, on increasing the SBH content up to 20%. © 1995 John Wiley & Sons, Inc.     

Fibers from poly(ethylene terephthalate) and poly(butylene terephthalate) blends I. Mechanical behavior

Fibers prepared from poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) blends show a sharp decrease in tensile strength and modulus when blends are on the verge of phase segregation. The modulus values differ for homopolymers for their differences in chain configuration and methylene groups and that of the blends are in proportion. The experimental strength values are higher than the predicted values according to Paul's model for incompatible polymers. At 90/10 PET/PBT blend, the modulus is high, which may be a relative factor to the smaller crystal size of the components.     

The thermal and mechanical behavior of poly(ethylene terephthalate) fibers incorporating novel thermotropic liquid crystalline copolymers

This investigation explores the potential of improving the performance of poly(ethylene terephthalate) fibers by incorporating novel thermotropic liquid crystalline copolymers. Fibers were obtained by melt extrusion and the effect of processing conditions, i.e., spinning temperature, stretch ratio, and post treatment evaluated. The fibers were tested for mechanical performance, dimensional instability (shrinkage), and the development of shrinkage stresses. A segmented block copolymer consisting of rigid-rod, diad, and flexible coil segments was found to improve the performance of poly(ethylene terephthalate) (PET) fibers. At a concentration of 20 wt %, the alternating block copolymer increased the tensile modulus of the fibers by 40% and decreased free shrinkage by 20% compared to neat PET. © 1994 John Wiley & Sons, Inc.     

In situ composite fibers: Blends of liquid crystalline polymer and poly (ethylene terephthalate)

To augment the concept of in situ composites as alternatives to fiber-reinforced composites, polyblends of a thermotropic liquid crystalline polymer (LCP) and poly(ethylene terephthalate) (PET) were prepared. Fiber-spinning of the blends was performed on a piston-driven plastorneter. Blends of LCP and a low-intrinsic-viscosity PET resin showed poor mechanical performance, which was attributed to their processing behavior. Blends of LCP and a high intrinsicviscosity PET manifested an almost additive behavior with regard to tensile modulus and strength. Elongation of the blends, however, displayed a radical decline, which is reminiscent of fiber-reinforced composites. Heat treatment of the blend fibers modestly increased the tensile properties of the LCP-rich compositions. Blend fibers from PET-rich compositions exhibit a moderate decline in tensile properties owing to thermal relaxation of PET. The data demonstrate that in situ composites or blends of thermotropic LCPs and isotropic polymers present challenging alternatives to fiber-reinforced composite systems because of their ease of processing.     

High-impact poly(ethylene terephthalate) blends

Rubbers of different kind were tested as toughening agents of poly(ethylene terephthalate) (PET), noting significant morphological and mechanical differences. In particular, good results were obtained by using an ethylene–ethyl acrylate–glycidyl methacrylate copolymer. The resulting blend evidenced good particle distribution, and the latter was related to chemical interactions between the rubber epoxy groups and PET terminal groups, including the effect of low molecular weight and polymeric amine catalysts, and to extrusion conditions. © 1995 John Wiley & Sons, Inc.