Viscoelastic properties of a 60 mol% para-hydroxybenzoic acid/40 mol% poly(ethylene terephthalate) liquid crystalline copolyester. I: Effect of temperature history

In this paper, the rheology of a 60 mol% para-hydroxybenzoic acid (PHB)/40 mol% poly(ethylene terephthalate) (PET) copolyester (herein referred to as PHB60/PET40) produced by Unitika Co., Japan, was investigated using viscoelastic property temperature sweeps. In addition to the large-scale hysteresis (super-cooling) of viscoelastic properties that has also been seen with other PHB-based materials, in which it is possible for several PHB linkages to occur side by side along the polymer backbone (most notably the PHB60/PET40 polymer produced by Tennessee Eastman), smaller-scale viscoelastic transitions, one present in heating, and believed to be associated with the partial isotropization of liquid crystalline material, and the other apparent on cooling, occurring at a lower temperature than the first and thought to be associated with the opposite process, were observed. When overall mol% PHB composition along individual chains is considered, the well-defined appearance of the additional smaller-scale rheological transitions seen here is believed to be due to a unimodal composition distribution, rather than a bimodal distribution of which there is increasing evidence in the Tennessee Eastman materials. This difference is believed to be caused by differences in the preparation technique used for the Unitika version of the polymer.     

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.     

Reactive blending of poly(ethylene terephthalate) with a liquid crystalline copolyester and polyhydroxyether

Poly(ethylene terephthalate) modified with a dianhydride (PET–anhydride) was melt‐blended with a liquid crystalline copolyester (Vectra A) in the presence of a small amount of a liquid crystalline polyhydroxyether. The mechanical properties of a blend consisting of PET–anhydride/Vectra A/polyhydroxyether were drastically improved compared to blends without polyhydroxyether or without anhydride. Melt‐spun fibers of PET–anhydride/Vectra A/polyhydroxyether in a 80/20/0.75 weight ratio displayed a much higher tensile modulus (17 GPa) and tensile strength (214 MPa) than did a 80/20 PET–anhydride/Vectra A blend (4 GPa and 60 MPa, respectively). A similar increase in modulus and strength was found for a 90/10/0.75 relative to a 90/10 blend. The tensile moduli of the blends can well be described by the Tsai–Halpin equation. A better fibril formation was observed, which was attributed to an improved viscosity ratio. Reactions between the various functional groups during melt processing were indicated by viscosity measurements. The polyhydroxyether may act as a reactive compatibilizer which improves the interfacial adhesion, chemically and/or physically. WAXD recordings of both blends showed a crystalline and highly oriented Vectra phase. The PET phase was unoriented and amorphous in a PET/Vectra blend and semicrystalline and weakly oriented in a PET/Vectra/polyhydroxyether blend. Postdrawing of the various blend fibers to λ = 4 increased the modulus by about 40% and the tensile strength by more than 100%, mainly through orientation of the PET phase. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1107–1123, 1999     

Rheology and thermal properties of liquid crystalline copolyester and poly(ethylene 2,6-naphthalate) blends

Blends of a poly(ethylene 2,6-naphthalate) (PEN) and a liquid crystalline copolyester (LCP), poly(benzoate-naphthoate) were prepared in a twin-screw extruder. Specimens for thermal properties were investigated by means of an instron capillary rheometer (ICR) and scanning electron microscopy (SEM). The blend viscosity showed a minimum at 10 wt% of LCP and increased with increasing LCP content above 10 wt% of LCP. Above 50% of LCP and at higher shear rate, phase inversion occured and the blend morphology was fibrous and similar to pure LCP. The ultimate fibrillar structure of LCP phase appeared to be closely related to the extrusion temperature. By employing a suitable deformation history, the LCP phase may be elongated and oriented such that a microfibrillar morphology can be retained in the solid state. Thermal properties of the LCP/PEN blends were studied using DSC and a Rheovibron viscoelastomer. These blends were shown to be incompatible in the entire range of the LCP content. For the blends, the T_g and Tm were unchanged. The half time of crystallization for the LCP/PEN blends decreased with increasing LCP content. Therefore, the LCP acted as a nucleating agent for the crystallization of PEN. The dimensional and thermal stability of the blends were increased with increasing LCP content. In studies of dynamic mechanical properties, the storage modulus (E′) was improved with increasing LCP content and synergistic effects were observed at 70 wt% of LCP content. The storage modulus for the LCP/PEN 70/30 blend is twice that of PEN matrix and exceeded pure LCP.     

Morphology and mechanical properties of liquid crystalline copolyester and poly(ethylene 2,6-naphthalate) blends

Blends of poly(ethylene 2,6-naphthalate) (PEN) 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 and mechanical properties were investigated by scanning electron microscopy (SEM) and an Instron tensile tester. SEM studies revealed that finely dispersed spherical domains of the liquid crystalline polymer (LCP) were formed in the PEN matrix, and the inclusions were deformed into fibrils from the spherical droplets with increasing LCP content. The morphology of the blends was found to be affected by their composition and a distinct skin-core morphology was found to develop in the injection molded samples of these blends. Mechanical properties were improved with increasing LCP content, and synergistic effects have been observed at 70 wt% LCP content whereas the elongation at break was found to be reduced drastically above 10 wt% of LCP content. This is a characteristic typical of chopped-fiber-filled composites. The improvement in mechanical properties is likely due to the reinforcement of the PEN matrix by the fibrous LCP phase as observed by scanning electron microscopy. The tensile and modulus mechanical behavior of the LCP/PEN blends was very similar to those of the polymeric composite, and the tensile strength and flexural modulus of the LCP/PEN 70/30 blend were two times the value of PEN homopolymer and exceeded those of pure LCP, suggesting LCP acts as a reinforcing agent in the blends.     

Enhancement of fiber structure formation of a liquid crystalline copolyester via ultra-high speed bicomponent spinning with poly(ethylene terephthalate)

A thermotropic liquid crystalline copolyester, poly(hydroxybenzoic acid-co-ethylene terephthalate) (LCP), and poly(ethylene terephthalate) (PET) were coextruded using two different extrusion systems to form sheath-core type biocomponent fibers. The bicomponent fibers could be spun up to a take-up velocity of 8 Km/min. The structural characterization of the individual components in the as-spun fibers showed that the orientation development in the PET component was significantly suppressed compared with the corresponding single component fibers. A significant increase in the tensile modulus of the LCP core component, which was estimated by the simple rule of mixtures, was observed above a take-up velocity of 4 km/min. The increase in tensile modulus was attributed to the increase in the overall orientation of the LCP core resulting from the combination of the high levels of stress generated during spinning at very high speeds and the altered thermal and stress generated during spinning at very high speeds and the altered thermal and stress histories provided by the bicomponent spinning process. On-line study of the thinning behavior of single component and bicomponent spinning was carried out in order to gain an understanding of the spinline dynamics, which improved the processability and structure development of LCP.     

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     

Crystallization kinetics of poly(ethylene terephthalate): Cmemory effect of shear history

The memory effect of shear history was studied with poly(ethylene terephthalate) (PET) prepared under different shear conditions of 11.7 to 1168 s^?1 in a capillary rheometer. The shear history of PET resin led to a memory effect, which in turn affected the crystallization kinetics. The crystallization rate increased with increasing shear rate. Double peaks of heating crystallization exotherms and a low value of Avrami exponent appeared at low shear rates, which was attributed to the existence of crystallization processes with different rates; one was the fast process involving the disentangled molecules that persisted during melting, and the other was the slow process involving the highly entangled molecules. The change of instantanenous Avrami exponent and overall crystallization rate constant was in good agreement with the expected trends assuming coexistence of the two crystallization processes. The crystallization kinetics of PET with shear history could be regarded as a growth rate decrease problem to be interpreted by the modified Avrami equation, 1 ? V_c = exp[? K·f(t)ⁿ], when the fast process dominated the overall crystallization. The effect of shear history was reduced because of the relaxation process as the holding time in melt state before crystallization was increased.     

Segmented liquid crystalline copolyesters and blending with poly(ethylene terephthalate)

Summary A series of segmented copolyesters with semi-regular structure was synthesized. In these copolymers, fully aromatic triad hard segments-HB-T-HB-, acting as mesogenic units, are linked each other by poly(ethylene terephthalate) (PET) segments with different average chain lengths as flexible spacers. The liquid crystallinity of the copolymers, i.e. the meso-phase forming ability, was studied against length of the spacer. In subsequent blending of these copolymers with PET matrix, results were compared with those from a commercial TLCP of PHB/PET random copolyester. Better mechanical properties were gained as expected since the compatibility of the segmented liquid crystalline copolyesters with the matrix is believed to be improved.     

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     

Fast crystallization of liquid crystalline copolyesters based on poly(ethylene terephthalate)

Crystallization of a series of liquid crystalline copolyesters prepared from p‐hydroxybenzoic acid (HBA), hydroquinone (HQ), terephthalic acid (TA), and poly(ethylene terephthalate) (PET) was investigated by using differential scanning calorimetry (DSC). It was found that these copolyesters are more crystalline than copolyesters prepared from PET and HBA. Insertion of HQ–TA disrupts longer rigid‐rod sequences formed by HBA and thus enhances molecular motion and increases the crystallization rate. The effects of additives on the crystallization of the copolyesters were also studied. Sodium benzoate (SB) and sodium acetate (SA) increase the crystallization rate of the copolyesters at low temperature, but not at high temperature. It is most likely that liquid crystalline copolyesters do not need nucleating agents, and small aggregates of local‐oriented rodlike segments in nematic phase could act as primary nuclei. Chain scission of the copolyesters caused by the reaction with the nucleating agents was proved by the determination of intrinsic viscosity and by the IR spectra. Diphenylketone (DPK) was shown to effectively promote molecular motion of chains, leading to an increase in the crystallization rate at low temperature, but it decreased the crystallization rate at high temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 497–503, 2001     

Morphology and mechanical properties of fibers from blends of a liquid crystalline polymer and poly(ethylene terephthalate)

The domain morphology and mechanical properties of fibers spun from blends of a thermotropic liquid crystalline polymer, Vectra A-900, and poly(ethylene terephthalate) (PET) have been studied across the entire composition range. The PET phase was removed by etching to reveal fibrillar LCP domains in the blends of all compositions. The 0.5μm fibril appeared to be the basic structural entity of the LCP domains. A primary effect of composition was the change from discontinuous fibrils when the composition was 35 and 60% by weight LCP to continuous fibrils when the composition was 85 and 96% LCP. This transition had major ramifications on the mechanical properties: the modulus increased abruptly between 60 and 85% LCP, and a change in the fracture mode from brittle fracture to a splitting mode was accompanied by an increase in fracture strength. Different models were required to describe the mechanical properties of the discontinuous and continuous fibril morphologies. Analytic models for short aligned fibers of Nielsen, and Kelly and Tyson were applicable when the LCP fibrils were discontinuous, while modulus and strength of blend fibers with continuous LCP fibrils were discribed by the rule of mixtures.     

Structural considerations in case II swelling of crystalline poly(ethylene terephthalate)

The Case II swelling in chloroform was discussed with regard to the fine structure for the crystalline PET. The case II swelling was associated with the character of the crystallites. It was inferred that the fine structure related to the Case II behavior was effectively plasticized during the swelling process.     

Characterizations for blends of phosphorus-containing copolyester with poly(ethylene terephthalate)

High molecular weight phosphorus-containing copolyesters, poly(ethylene terephthalate)-co-poly(ethylene DDP) (PET-co-PEDDP)s, were prepared and characterized with the objective of producing a non-halogen flame retardant system for practical applications. The phosphorus-containing copolyester with 30 wt% phosphorus (P30 copolyester) was blended with PET to evaluate their characteristics and flame retardancy. Higher phosphorus content results in lower crystallinity and higher char formation after thermal degradation. The rheological behavior remains similar to that of PET. The P30/PET blend possesses higher crystallization rate than the corresponding phosphorus-containing copolyester containing equal phosphorus content. Thermal and rheological behaviors of P30/PET blends are similar to PET or the phosphorus-containing copolyesters. The P30/PET blends are miscible or compatible base on single T_gs detected by DSC or DMA. The SEM/EDX phosphorus mapping image of the P30/PET blend shows uniform distribution of the phosphorus moieties within the P30/PET matrix, another indication of a compatible or miscible blend between the phosphorus-containing copolyester P30 and PET. Flame retardancy of the P30/PET blend is identical to that of the phosphorus-containing copolyester with identical phosphorus content. Blending of high phosphorus content copolyester with virgin PET provides a feasible method to obtain a flame resistant PET with LOI greater than 28.     

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     

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.     

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.     

Microstructure of amorphous and crystalline poly(ethylene terephthalate)

The microstructures of amorphous and crystalline poly(ethylene terephthalate) (PET) homopolymers have been determined in terms of their trans and gauche conformational isomer contents by using a combination of infrared and density characterization techniques. The effects of isothermal crystallization (from the glassy state between 105–150°C), as well as the effects of different monomer units in the polymerization process, have been investigated. Results indicate that samples, polymerized from different monomer and catalyst systems, show different microstructures in terms of trans and gauche isomers.These variations result in significant differences in PET optical properties. Further investigations find that these dissimilar behaviors accompany conformational isomer variations in the amorphous phase, suggesting different transformation mechanisms of trans and gauche isomers at early stages of crystallization. These unlike microstructural transformation processes give rise to further changes, which are evident in terms of the intensity of Vv light scattering, haze values, thermal properties, and FTIR spectral results. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1965–1976, 1998     

Polyester nanocomposite fibers: comparison of their properties with poly(ethylene terephthalate) and poly(trimethylene terephthalate) (II)

Summary Two polyester nanocomposites were synthesized, one with poly(ethylene terephthalate) (PET) and the other with poly(trimethylene terephthalate) (PTT), by using organoclay. The in-situ interlayer polymerization method was used to disperse the organoclay in polyesters at different organoclay contents and at different draw ratios to produce monofilaments. The thermal stability and tensile mechanical properties increased with increasing organoclay content at a DR=1 . However, the values of the tensile mechanical properties of the hybrid fibers decreased with increasing DR. The reinforcing effects of the organoclay of the PET hybrid fibers were higher than those of the PTT hybrid fibers.