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.     

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     

含TLCP的PET共混纤维结构和性能

以热致性液晶共聚酯——聚对苯二甲酸乙二酯／对羟基苯甲酸（ＰＥＴ／ＰＨＢ）作为添加剂与ＰＥＴ共混纺丝，研究该ＰＥＴ／ＴＬＣＰ（热致性液晶高聚物）共混物的可纺性，并用ＤＳＣ、Ｘ光衍射、声速和应力－应变等方法对纤维的热性能、结晶和取向结构以及力学性能进行了表征。结果表明，ＴＬＣＰ质量含量为５％左右的ＰＥＴ共混物可纺性良好。ＴＬＣＰ对ＰＥＴ从熔体结晶具有阻止作用，共混初生纤维的玻璃化转变和冷结晶温度均因ＴＬＣＰ的存在而升高。ＴＬＣＰ质量含量为５％的共混物纤维结晶结构与纯ＰＥＴ纤维相似，但晶粒尺寸较小，且晶粒尺寸大小与共混物组成、喷丝头拉伸比和后拉伸比有关。ＴＬＣＰ含量增加，共混纤维取向度和模量增大，而强度下降，但后拉伸可使纤维强度有较大的提高。     

Speculation on interfacial adhesion and mechanical properties of blends of PET and thermotropic polyester with flexible spacer groups

A thermotropic liquid crystalline polyester (LCP) with a long flexible spacer group in the main chain was prepared by melt polymerization and mixed with poly(ethylene terephthalate) (PET). Differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) studies revealed that the crystallization of PET was accelerated by the addition of LCP in the matrix. Interfacial adhesion between PET and LCP was much improved by introduction of a long flexible spacer in the main chain. Fibers of the blend with 30 wt percent of LCP had fine microfibrillar structure with a large aspect ratio formed in the matrix. Initial modulus and ultimate strength were highly elevated by the addition of LCP due to good interfacial adhesion and microfibrillar structure of LCP in the blend.     

液晶聚合物增强PC／PET共混物挤出片材的性能研究

介绍液晶聚合物对ＰＣ／ＰＥＴ共混体系的增强改性。选用了六种不同熔眯的ＬＣＰ引入到ＰＣ／ＰＥＴ共混体系中，用自制的有利于形成定向的口模，将共混物挤出成片材，并测定了拉伸强度，维卡软化点，结晶速率，结果表明：在ＰＣ／ＰＥＴ共混物中，加入少量ＬＣＰ后，拉伸强度可比原体系提高３０％左右，不同熔点的ＬＣＰ影响有差异，熔点太高的ＬＣＰ反而会使体系的拉伸强度下降，维卡软化点未见明显变化，当增大ＬＣＰ用量后，体系     

Morphological Characteristics and the Modulus of Liquid Crystalline Polymer Fibers Dispersed in a Thermoplastic Matrix

The morphology of a polycarbonate (PC)-based blend containing a thermotropic liquid crystalline polymer (LCP) component has been characterized in terms of the layer structure, layer thickness, aspect ratio, and number of the shear-induced fibers developed during injection molding. This dispersed LCP phase was still embedded as fibers and deformed droplets in the PC matrix, and their tensile modulus was usually unknown due to the testing problems. Based on the morphological characteristics, a calculation procedure has been developed to estimate the modulus of these fibers and droplets by using a set of micromechanical models. It has been found that the average tensile modulus of these shear-induced LCP fibers and deformed droplets seems to be a material constant, independent of the injection molding condition, i.e., the shear flow condition. For the LCP Vectra A950 studied, the calculated tensile modulus was 24.0 GPa. This value was in fair agreement with that reported in literature. It was larger than that of the injection-molded pure LCP samples and smaller than that of the drawn pure LCP strand.     

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 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.     

Mixtures of poly(ethylene terephthalate) and liquid-crystalline polyesters with Y-shaped mesogens

Some liquid-crystalline polyesters (LCP) with Y-shaped mesogens, differing only in the length of their spacers, were blended with poly(ethylene terephthalate) (PET). Calorimetric measurements show significant influence of the LCP on the crystallization of PET even at low concentrations. The mixtures are spun into fibres and their mechanical properties are compared with fibres made from pure LCPs. The formation of LCP-fibrils leads to improved values of Young's modulus and tensile strength.     

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.     

Strengthening of poly(butylene adipate-co-terephthalate) by melt blending with a liquid crystalline polymer

Poly(butylene adipate-co-terephthalate) (PBAT) is a soft biodegradable polymer with a low melting temperature. PBAT has been melt-blended with a liquid crystalline polymer (LCP) aiming at preparing a new biodegradable polymer blend with improved mechanical properties. The phase structure and crystalline morphologies of the PBAT/LCP blends were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). It was found that the LCP domains are precisely dispersed in the PBAT matrix and that these domains act as the nuclei for PBAT crystallization. The nonisothermal crystallization temperature from the melt was dramatically shifted from 50°C to about 95°C by the addition of 20% LCP. In addition, the tensile modulus of the prepared blends increases gradually with increasing LCP content, indicating the excellent strengthening effects of LCP on the PBAT matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

聚酯/液晶聚合物共混纤维的热处理

采用Ｘ射线衍射法、双折射法以及声速法研究了ＰＥＴ及其与液晶聚合物（ＬＣＰ）的共混初生纤维以及经过热处理后纤维的结晶结构和取向结构,并用应力－应变（Ｓ－Ｓ）法测定其断裂强度和初始模量。结果表明,ＬＣＰ的加入使初生纤维取向度和结晶度均下降,而喷头拉伸率增大则使共混初生纤维的结晶度和取向度均提高;由较大喷丝头拉伸率得到的共混纤维经热处理后取向度下降,而结晶度增大;当ＬＣＰ含量大于或等于１０％时,经热处理后共混纤维取向度下降;纤维２１０℃热处理后的晶粒尺寸明显大于１８０℃处理的,且前者的纤维各晶面的晶粒尺寸随着ＬＣＰ加入均有增大;纯ＰＥＴ纤维经热处理后力学性能提高,而ＰＥＴ／ＬＣＰ共混纤维热处理前后力学性能则呈较复杂的变化。     

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.     

Recycling of poly(ethylene terephthalate) as polymer‐polymer composites

Microfibrillar reinforced composites (MFC) comprising an isotropic matrix from a lower melting polymer reinforced by microfibrils of a higher melting polymer were manufactured under industrially relevant conditions and processed via injection molding. Low density polyethylene (LDPE) (matrix) and recycled poly(ethylene terephthalate) (PET) (reinforcing material) from bottles were melt blended (in 30/70 and 50/50 PET/LDPE wt ratio) and extruded, followed by continuous drawing, pelletizing and injection molding of dogbone samples. Samples of each stage of MFC manufacturing and processing were characterized by means of scanning electron microscopy (SEM), wide‐angle X‐ray scattering (WAXS), dynamic mechanical thermal analysis (DMTA), and mechanical testing. SEM and WAXS showed that the extruded blend is isotropic but becomes highly oriented after drawing, being converted into a polymer‐polymer composite upon injection molding at temperatures below the melting temperature of PET. This MFC is characterized by an isotropic LDPE matrix reinforced by randomly distributed PET microfibrils, as concluded from the WAXS patterns and SEM observations. The MFC dogbone samples show impressive mechanical properties—the elastic modulus is about 10 times higher than that of LDPE and about three times higher than reinforced LDPE with glass spheres, approaching the modulus of LDPE reinforced with 30 wt% short‐glass fibers (GF). The tensile strength is at least two times higher than that of LDPE or of reinforced LDPE with glass spheres, approaching that of reinforced LDPE with 30 wt% GF. The impact strength of LDPE increases by 50% after reinforcement with PET. It is concluded that: (i) the MFC approach can be applied in industrially relevant conditions using various blend partners, and (ii) the MFC concept represents an attractive alternative for recycling of PET as well as other polymers.     

Rheological and physical properties of in situ composite based on liquid crystalline polymer and poly(ethylene 2,6‐naphthalate) blends

The in situ composites based on poly(ethylene 2,6‐naphthalate) (PEN) and liquid crystalline polymer (LCP) were investigated in terms of thermal, rheological, and mechanical properties, and morphology. Inclusion of LCP enhanced the crystallization rate and tensile modulus of the PEN matrix, although it decreased the tensile strength in the PEN‐rich phase. The orientation effect of this blend system was composition and spin draw ratio dependent, which was examined by Instron tensile test. Further, the addition of dibutyltindilaurate (DBTDL) as a reaction catalyst was found to increase the viscosity of the blends, enhance its adhesion between the dispersed LCP phases and matrix, and led to an increase of mechanical properties of two immiscible blends. Hence DBTDL is helpful in producing a reactive compatibilizer by reactive extrusion at the interface of this LCP reinforced polyester blend system. The optimum catalyst amount turned out to be about 500 ppm, when the reaction proceeded in the 75/25 PEN/LCP blend system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2448–2456, 1999     

Effect of drawing on structure and properties of a liquid crystalline polymer and polycarbonate in-situ composite

Fibers (strands) with various draw ratios were spun from the liquid crystalline state of a pure aromatic liquid crystalline copoly(ester amide) and the melts of its blend with polycarbonate. Scanning electron microscopy (SEM), wide angle X-ray scattering (WAXS), and differential scanning calorimetry (DSC) were employed to investigate the structure and properties of the resulting fibers. Mechanical properties of the fibers were also evaluated. It was found that both the crystallite size and heat of fusion of the liquid crystalline polymer (LCP) increase steadily with draw ratio. However, the crystal-nematic transition temperature of the LCP is virtually unaffected by drawing. Moreover, heat of fusion of LCP is much smaller than that of isotropic condensation polymers despite the presence of very sharp diffraction peaks in WAXS measurements. These results are ascribed to the (semi)rigid rod nature of the LCP chains and the persistence of an ordered structure in the LCP melt, i.e., entropy effect. It was further observed that tensile modulus and tensile strength along fiber axis rise with draw ratio for the composite fibers. The elastic modulus of the composite fibers were found to be as high as 19 GPa and tensile strength reached 146 MPa with draw ratios below 40 and an LCP content of 30 wt%. Compared with the thermoplastic matrix, the elastic modulus and tensile strength of the in-situ composite have increased by 7.3 times and 1.4 times, respectively, with the addition of only 30 wt% LCP. This improvement in mechanical properties is attributed to fibrillation of the LCP phase in the blend and the increasing orientation of the LCP chains along the fiber axis during drawing.     

Mechanical,morphological, and thermal properties of poly(ethylene 2,6-naphthalate) and copolyester LCP blends

Binary blends of a liquid crystalline polymer (LCP) and poly(ethylene 2,6-naphthalate) (PEN) were melt blended and injection molded. The mechanical properties were studied as a function of LCP content. Both the ultimate tensile strength and Young's modulus are higher than the theoretical values predicted by the rule of mixtures and they display a synergistic behavior at 70 wt % LCP content. However, the tensile strength decreases with LCP content and Young's modulus remained unchanged at lower LCP contents (10 to 30 wt %). The poor mechanical property is attributed to the immiscibility between PEN and LCP and the fibrillation behavior of LCP as revealed by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) results. However, LCP and PEN are found to be partially miscible at higher LCP content, ascertained by DSC and dynamic mechanical analysis (DMA). This is attributed to the transesterification reaction between PEN and PET moiety in the LCP molecules. SEM micrographs reveal a skin/core morphology in the tensile bars, that is, the LCP is better oriented in the skin than in the core region. At lower LCP content, the dispersed LCP phase is spherical in the core and ellipsoidal in the skin, with long axes oriented in the flow direction. DSC studies show that the crystallization rate is significantly enhanced by the presence of LCP up to 50 wt %, where the LCP acts as a nucleating agent for PEN crystallization. The melting temperature decreases with LCP content, probably as a result of imperfect crystals formed in the presence of LCP heterogeneous nucleating centers and the increasing miscibility between LCP and PEN. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 477–488, 2001     

In situ fibrillar reinforced PET/PA‐6/PA‐66 blend

Ternary fibrillar reinforced blends are obtained by melt‐blending of poly(ethylene terephthalate) (PET), polyamide 6 (PA‐6) and polyamide 66 (PA‐66) (20/60/20 by weight) in the presence of a catalyst, followed by cold drawing of the extruded bristles to a draw ratio of about 3.4 and additional annealing of the drawn blend at 220 or 240°C for 4 or 8 h. The blend samples are studied by DSC, X‐ray diffraction, SEM, and static and dynamic mechanical testing (DMA). SEM and DMA show that PA‐6 and PA‐66 form a homogeneous, continuous matrix in which PET regions are dispersed. X‐ray and DSC measurements of the drawn and annealed at 220°C samples suggest mixed crystallization (solid solubility) of PA‐6 and PA‐66, and cooperative crystallization of PET with the two polyamides. After annealing at 240°C (above the melting point of PA‐6 and below that of PET), the polyamide matrix becomes partially disoriented, while the oriented, fibrillar PET is preserved and plays the role of a reinforcing element. The DSC results for the same samples suggest in situ generation of an additional amount of copolymer. This additional copolymerization, together with that generated during blend mixing in the extruder, improves the compatibility of the blend components (mostly at the PET‐polyamide interface) and alters the chemical composition of the blend.     

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.     

Spinning and properties of poly(ethylene terephthalate)/organomontmorillonite nanocomposite fibers

By in situ polycondensation, a intercalated poly(ethylene terephthalate)/organomontmorillonite nanocomposite was prepared after montmorillonite (MMT) had been treated with a water‐soluble polymer. This nanocomposite was produced to fibers through melt spinning. The resulting nanocomposite fibers were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and transmission electron microscopy (TEM). The interlayer distance of MMT dispersed in the nanocomposite fibers was further enlarged because of strong shear stress during processing of melt spinning. This was confirmed by XRD test and TEM images. DSC test results showed that incorporation of MMT accelerated the crystallization of poly(ethylene terephthalate) (PET), but the crystallinity of the drawn fibers just had a little increasing compared with that of neat PET drawn fibers. Also compared with pure PET drawn fibers, tensile strength at 5% elongation and thermal stability of the nanocomposite fibers were improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1443–1447, 2005