Dispersed Liquid Crystalline Polymer Phase Research Articles

Mechanical, morphological and thermal properties of in situ ternary composites based on poly(ether imide), silicone rubber and liquid crystalline polymer

A compatibilization method for improving the mechanical and thermal properties of thermoplastic/thermotropic liquid crystalline polymer (LCP) blends has been tested in blends of poly(ether imide), PEI, with a thermotropic copolyester (Vectra B-950). It is based on the addition of a third component, a functionalized elastomer (hydroxy terminated silicone rubber), to the blend that interacts with the matrix polymer and the thermotropic liquid crystalline polymer, facilitates the structural development of the thermotropic liquid crystalline polymers (TLCP) phase by acting as a compatibilizer at the interface. The main properties of blends required are flexibility of material in presence of compatibilizer. The viscosity of the compatibilized in situ composite was increased by the silicone rubber owing to the strong interaction. The coefficient of thermal expansion (CTE) of PEI/TLCP blend becomes lowered when the content of silicone rubber is increased. Morphological observation showed that the addition of compatibilizer significantly reduced the size of the dispersed LCP phase and improved their dispersion within the matrix. Measurement of the tensile properties shows increased strength as well as enhanced modulus and elongation when PEI/TLCP blend is properly compatibilized. This is attributed to fine fibril generation induced by the addition of compatibilizer.

A gradient structure formed in injection-molded polycarbonatein situ hybrid composites and its corresponding performances

Three polycarbonate (PC) composites that were reinforced, respectively, with liquid crystalline polymer (LCP), glass fibers, and both of them were prepared by a single injection-molding process. The role of LCP in improving the processibility of the composites was characterized by torque measurement test. The transitions of LCP morphology in two- and three-component composites were investigated by using polarizing optical microscopy and scanning electron microscopy. The micrographs showed a skin–core gradient structure in all three systems investigated, and the addition of glass fiber to the PC/LCP blend affected the morphological transition and content distribution of dispersed LCP phase through the thickness of the injection-molded samples. These results were correlated well with the measurements of tensile mechanical properties and dynamic mechanical analysis. How to fully use the dispersed LCP phase in PC in situ hybrid composites was discussed for the thickness change of core layer and the heterogeneous distribution of more LCP in the core. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 625–634, 2004

Mechanical performance of blends of thermotropic liquid crystalline polymer spheres-dispersed polycarbonate

Liquid crystalline polymer (LCP) blends with a thermotropic LCP dispersed in the form of microspheres is studied to show the role of LCP spheres. Polycarbonate (PC), p-hydroxybenzoic acid–poly(ethylene terephthalate) copolyester, and random styrene–maleic anhydride copolymer are used as the matrix, the dispersed phase, and the compatibilizer, respectively. A scanning electron microscopy observation shows the formation of LCP spheres with improved interfacial adhesion in the injection-molded samples via compatibilization. The mechanical tests show increased modulus, elongation at break, and fracture-absorbed energy of blends of LCP spheres-dispersed PC. This shows an optimistic potential for the dispersed LCP phase, in spite of its morphology in the form of fibrils for reinforcing the matrix or in the form of microspheres for toughening the matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1493–1499, 2003

Mechanical properties and morphology of LCP/ABS blends compatibilized with a styrene–maleic anhydride copolymer

AbstractA 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

Studies on morphology, mechanical, thermal, and rheological behavior of extrusion‐blended polypropylene and thermotropic liquid crystalline polymer

AbstractPolypropylene (PP) was melt‐blended in a single‐screw extruder with a thermotropic Vectra B‐950 liquid crystalline polymer (LCP) in different proportions. The mechanical properties of such blends were compared in respect of their Young's moduli, ultimate tensile strength (UTS), percent elongation at break, and toughness to those of pure PP. The thermal properties of these blends were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The morphology was studied by using a polarizing light microscope (PLM) and a scanning electron microscope (SEM) while the rheological aspects of the blends and the pure PP were studied by a Haake Rheowin equipment. Mechanical analysis (tensile properties) of the blends showed pronounced improvement in the moduli and the UTS of the PP matrix in the presence of 2–10% of LCP incorporation. TGA of all the blends showed an increase in the thermal stability for all the blends with respect to the matrix polymer PP, even at a temperature of 410°C, while PP itself undergoes drastic degradation at this temperature. DSC studies indicated an increase in the softening range of the blends over that of PP. Morphological studies showed limited mixing and elongated fibril formation by the dispersed LCP phase within the base matrix (PP) at the lower ranges of LCP incorporation while exhibiting a tendency to undergo gross phase separation at higher concentrations of LCP, which forms mostly agglomerated fibrils and large droplets. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 767–774, 2003

Effect of a compatibilizer on the structural development of a thermotropic liquid crystalline polymer/polystyrene blend

AbstractA fine fibril structure of a thermotropic liquid crystalline polymer (TLCP, a poly(ester amide)) can be developed in a shear flow field of a thermoplastic matrix (polystyrene, PS). Addition of a third component, a poly(styrene‐co‐maleic anhydride) (SMA), that interacts with the thermotropic liquid crystalline polymer facilitates the structural development of the TLCP phase by acting at the interface. Moreover, it brings about good adhesion at the interface and enables the dispersed liquid crystalline polymer phase to be deformed in shear flow without strong elongation even though the viscosity of the matrix is much lower than that of the liquid crystalline polymer. The mechanical properties were substantially improved because of both the good adhesion at the interface and fibril generation, which were ascribed to the SMA interaction. These results have important implications in that they provide a means to produce strong and tough in‐situ composites when the viscosity of the matrix polymer is lower than that of the dispersed liquid crystalline polymer which is immiscible with the matrix polymer. Morphological observations determined the significance of the third component (SMA) in immiscible polymer blends, and an optimum amount of SMA exists for best mechanical performance.

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

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

Morphologies and mechanical properties of polyarylate/liquid crystalline polymer blends compatibilized by a multifunctional epoxy resin

The tetrafunctional epoxy resin, tetraglycidyl-4′,4′-diaminodiphenyl methane (TGDDM), has been investigated as an efficient reactive compatibilizer for the blends of polyarylate (PAr) with a liquid crystalline polymer (LCP). TGDDM can react with PAr and LCP at the interface simultaneously to produce the PAr-co-TGDDM-co-LCP mixed copolymers during melt blending. These copolymers tend to anchor along the interface as the result of the interfacial reaction and thus serve as effective compatibilizers to reduce the interfacial tension and to enhance the interfacial adhesion in the solid state. The morphologies of the PAr/LCP blends were inspected by means of scanning electron microscopy (SEM). It is observed that the dispersed LCP phase domains reduce obviously after compatibilization. Furthermore, it is also found that the reduced interfacial tension caused by the addition of TGDDM plays a vital role in affecting the deformation of the LCP phase domains in the compatibilized PAr/LCP blends. The LCP phase tends to deform into greater numbers and finer fibrils with high aspect ratio after the addition of TGDDM in those blends containing adequate LCP content (> 10 %). In the blend containing low amount of LCP (Par / LCP = 95/5) with high TGDDM content (0.3 phr or higher), however, the LCP phase can only exist as fine but short fibrils or even ellipsoids. The overall mechanical properties of the PAr/LCP blends are substantially improved after compatibilization by this coupling-type reactive compatibilizer. The generation of LCP fibrils with high aspect ratio and improved interfacial adhesion are the two hinges to enhance the performance of the compatibilized PAr/LCP blends.

Crystallization and morphology of fibers prepared from compatibilized blends of polyethylene with a liquid crystalline polymer

Fibers prepared by melt spinning of compatibilized blends of high-density polyethylene (HDPE) with a semiflexible liquid crystalline polymer (LCP) SBH 1 : 1 : 2 of Eniricerche, Italy, have been investigated by differential scanning calorimetry (DSC) and optical microscopy. Two grades of HDPE with different molar mass have been used to prepare the blends. The compatibilizers are an acrylic acid functionalized polyethylene (Escor 5 000 by Exxon) and an ad hoc synthesized graft copolymer of the liquid crystalline polymer grafted to Escor 5 000 (PE-g-SBH). The studies cover the non-isothermal and isothermal crystallization, and the morphology of the fibers. The influence of the matrix molar mass and the maximal draw ratio of the fibers upon PE crystallization rate have been established. It has been shown that the overall PE crystallization rate under non-isothermal and isothermal conditions increases for fibers prepared from blends of lower molar mass HDPE, compatibilized by PE-g-SBH copolymer. The dispersed LCP phase in the latter fibers due to the enhanced interfacial adhesion in the presence of the copolymer compatibilizer appears as fibrils with high aspect ratio. The results have been interpreted by an increase in interfacial area between the SBH fibrils and the matrix phase, which enlarges the number of heterogeneous nuclei and increases the PE nucleation rate. These effects are less pronounced for the fibers compatibilized with Escor, due to the lower draw ratio of the fibers and to the lower aspect ratio of the SBH fibrils.

Effect of PP-g-LCP compatibilizer on the structure and crystallization of blends of isotactic polypropylene (PP) with a semiflexible liquid crystalline polymer (LCP)

Blends of i-polypropylene and a semiflexible liquid crystalline polymer (iPP/LCP 90/10 and 80/20 w/w) were compatibilized with 2.5, 5 or 10 wt.-% PP-g-LCP copolymers. The crystal structure, crystallization behaviour and morphology of the compatibilized blends have been investigated by differential scanning calorimetry (DSC), wide angle X-ray scattering (WAXS) and optical microscopy. It is shown that the nucleation rate and crystallization rate of iPP strongly increased in the compatibilized blends in comparison to the uncompatibilized ones. In compatibilized blends, while iPP spherulites get smaller and crystallinity degree increases, the crystal growth mechanism of iPP remains unchanged. An assumption has been made about the mechanism of the compatibilization, using graft copolymers constructed of segments identical to the blended polymers: the PP segments of PP-g-LCP copolymers, if long enough, cocrystallize with bulk iPP, compatibilizing partially the two components; the LCP grafts of the copolymers cocrystallize with the bulk LCP or enter the amorphous phase of the blends. The miscibility of each part of the copolymer compatibilizers with the corresponding bulk component of the blend leads to a reduction of the interfacial tension and to a strong reduction of the dimensions of dispersed LCP phase. The compatibilized iPP/LCP blends display improved crystallization kinetics, enhanced degree of crystallinity and improved interphase adhesion. Consequently, an improvement of the mechanical properties and rheological characteristics should be expected for these blends.

Effect of PP-g-LCP compatibilizer on the structure and crystallization of blends of isotactic polypropylene (PP) with a semiflexible liquid crystalline polymer (LCP)

Blends of i-polypropylene and a semiflexible liquid crystalline polymer (iPP/LCP 90/10 and 80/20 w/w) were compatibilized with 2.5, 5 or 10 wt.-% PP-g-LCP copolymers. The crystal structure, crystallization behaviour and morphology of the compatibilized blends have been investigated by differential scanning calorimetry (DSC), wide angle X-ray scattering (WAXS) and optical microscopy. It is shown that the nucleation rate and crystallization rate of iPP strongly increased in the compatibilized blends in comparison to the uncompatibilized ones. In compatibilized blends, while iPP spherulites get smaller and crystallinity degree increases, the crystal growth mechanism of iPP remains unchanged. An assumption has been made about the mechanism of the compatibilization, using graft copolymers constructed of segments identical to the blended polymers: the PP segments of PP-g-LCP copolymers, if long enough, cocrystallize with bulk iPP, compatibilizing partially the two components; the LCP grafts of the copolymers cocrystallize with the bulk LCP or enter the amorphous phase of the blends. The miscibility of each part of the copolymer compatibilizers with the corresponding bulk component of the blend leads to a reduction of the interfacial tension and to a strong reduction of the dimensions of dispersed LCP phase. The compatibilized iPP/LCP blends display improved crystallization kinetics, enhanced degree of crystallinity and improved interphase adhesion. Consequently, an improvement of the mechanical properties and rheological characteristics should be expected for these blends.

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.

Structure and properties of injection molded blends of liquid crystal polymer (40 PET/60 PHB) with poly(butylene terephthalate)

Blends of a poly(butylene terephthalate) (PBT) and a liquid crystalline polymer (LCP) were prepared in a single screw extruder. The LCP used was a liquid crystalline copolyester of 40% polyethylene terephthalate with 60% p-hydroxybenzoic acid (40 PET/60 PHB). Specimens for mechanical testing were prepared by injection molding. Rheological, morphological, microstructural, and mechanical properties were investigated by capillary rheometry, polarized light microscopy, x-ray diffractometry, and a tensile tester, respectively. For the LCP content higher than 5 wt. % a significant decrease of the viscosity was noted. The morphology of the dispersed LCP phase varies between droplets and oriented fibrils. The degree of cystallinity of PBT and the crystal sizes were found to be affected by LCP addition. The tensile mechanical behavior of the PBT + LCP blends was also found to be affected by their compositions. The elasticity modulus and the parameter of elasticity anisotropy monotonically increase with the LCP content. The strain at break shows a drastic decrease for the blends containing more than 10 wt. % LCP. The long-term creep test shows that the creep compliance decreases noticeably when the LCP content increases.

Factors influencing microstructure formation in polyblends containing liquid crystalline polymers

AbstractFour isotropic polymers, poly(butylene terephthalate) (PBT), polycarbonate (PC), polyethersulfone (PES) and polysulfone (PSU), were blended by extrusion with a thermotropic liquid crystalline polymer (LCP) at different temperatures. The morphology of extrudates was observed by means of scanning electron microscopy and the intrinsic aspect ratio of LCP fibrils and particles separated from matrix resin was measured with an image analysis. Special attention was paid to the LCP fibrillation in these four matrices in a wide temperature range from 270 to 360°C and the internal relations among the effects of processing parameters, such as viscosity ratio, extrusion temperature, and LCP concentration. The results show that the viscosity ratio of the dispersed LCP phase to the continuous phase is a decisive factor determining the formation of LCP fibrils, but its effect closely relates with the LCP content. In the range of viscosity ratios investigated, 0.004 to 6.9, and lower LCP content of 10%, significant fibrillation took place only at viscosity ratios below 0.01. It is predicted that the upper limit of the viscosity ratio for LCP fibrillation will increase with increasing LCP content. A comparison of the morphologies of LCP/PES blends with different LCP concentrations reveals that the LCP phase becomes continuous at a concentration of less than 50%, and high LCP content does not always favor the formation of long and uniform LCP fibrils. The extrusion temperature has a marked effect on the size of the minor LCP domains. For fibril forming systems, the percentage of LCP fibrils with larger aspect ratios increases with increasing extrusion temperatures. All these results are explained by the combined role of deformation and coalescence of the LCP disperesed phase in the blend.

Influence of processing history on the properties of a thermotropic copolyester/polycarbonate blend

AbstractRelationships between the rheological, morphological, and tensile properties of an immiscible blend of 25 wt% of a thermotropic liquid crystalline polymer (LCP) with polycarbonate are presented. The shear viscosity of the blend is intermediate between the two constituent materials, and indicates immiscibility in the melt. Extrudate swell behavior is examined and found to be closely related to that of polycarbonate. The morphology of the dispersed LCP phase varies between droplets and oriented fibrils, and is highly correlated with changes in tensile properties. Fibrils are associated with increased tensile modulus, and their development is favored in the elongation flow fields present in the spinline and in the die convergence section. In all cases, blend stiffness is less than that predicted for a continuous fiber‐reinforced composite. Enhanced tensile modulus is associated with both extrusion from shorter length dies and increases in spinline draw ratio, with the latter proving the most important in fibril formation.

Liquid crystalline polymer/fluoropolymer blends: Preparation and properties of unidirectional “prepregs” and composite laminates

AbstractExtruded films of liquid crystalline polymer (LCP)/fluoropolymer blends were melt drawn to develop uniaxial orientation of a microfibrillar dispersed LCP phase. The anisotropy of the films increased with increasing draw and LCP content in the blend. Laminated composite plates were prepared using the extruded sheets as prepreg. The mechanical properties and coefficient of thermal expansion (CTE) of the prepreg and laminates agreed well with predictions from composite lamination theories. The potential for replacing glass fiber reinforced fluoropolymers with LCP/fluoropolymer blends in applications such as microwave circuit boards is discussed.

Blends containing liquid crystalline polymers: Preparation and properties of melt‐drawn fibers, unidirectional prepregs, and composite laminates

AbstractThis paper discusses the effect of melt drawing on the mechanical properties and morphology of liquid crystalline polymer (LCP) and thermoplastic polymer blends. Extruded fibers and films of LCP/polymer blends were melt drawn to develop uniaxial orientation of the dispersed LCP phase. The longitudinal modulus increased with increasing draw. The increase in modulus was due to higher aspect ratio of the LCP fibrils and improved molecular orientation of the LCP chains within the fibrils. Laminated composites were prepared using the extruded sheets as prepregs. The mechanical properties and the coefficient of thermal expansion (CTE) of the prepreg and the laminates agreed well with predictions from conventional composite lamination theories.

Novel reinforced polymers based on blends of polystyrene and a thermotropic liquid crystalline polymer

AbstractA thermotropic liquid crystalline polymer (LCP), when added to polystyrene (PS), can function as both a processing aid and a reinforcing filler. Thermal, rheological, and mechanical properties of the pure components and blends containing up to 10 percent LCP are reported. The LCP used is immiscible with PS, and when an extensional component of flow is present during processing, the LCP forms an elongated fibrous phase oriented in the flow direction. This oriented phase lubricates the melt, substantially lowering the viscosity. When the processed blend is cooled, the dispersed fibrous LCP phase is preserved in the solidified material. The LCP microfibers behave like short reinforcing fibers to improve the mechanical properties of the blend; for example, at an LCP concentration of 4.5 percent, the modulus is increased about 40 percent vs. pure PS.