Composites based on drawn strands of thermotropic liquid crystalline polymer reinforced polypropylene

This paper is concerned with the use of two thermotropic liquid crystalline polymers (TLCPs), HX1000 and Vectra B950, to reinforce a thermoplastic matrix of polypropylene (PP). The goal was to pregenerate the optimal TLCP reinforcement in PP and then process the material at a lower temperature than the melting point of the TLCP to form a composite structure. Specifically, strands of the blend were produced using a dual extrusion process, which resulted in the formation of axially continuous TLCP fibrils within the PP matrix. It was found that the mechanical properties of the strands were greatly improved by increased draw ratio and that optimal reinforcement, as predicted by the rule of mixtures, could be achieved. Initial studies indicated that injection molding and sheet extrusion of the pelletized strands caused the TLCP phase to agglomerate and deform, which resulted in a reduction of the mechanical property enhancement. However, the TLCP fibrillar morphology in the pregenerated strands was maintained during compression molding, which resulted in uniaxial composites with properties equal to or greater than properties of the strands. In addition, composites were made using compression molding in which strands were randomly oriented prior to consolidation to show the limits of properties possible in composites produced from the pregenerated strands. It was found that this process could be used to produce composites in which the mechanical properties were isotropic in the plane of the sample and approached the properly limits predicted by composite theory. Additionally, it was found that many of the mechanical properties of the VB/PP materials were greatly enhanced by the addition of a maleated PP throughout the composite forming process.     

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.-%.     

Stability of blends of thermotropic liquid crystalline polymers with thermoplastic polymers

Breakup of fibers of a thermotropic liquid crystalline polymer (TLCP) above the melting temperature in various ordinary polymers has been studied by capillary instability experiments on single TLCP fibers and by annealing experiments on extruded TLCP/thermoplast blends. The TLCP was an aromatic copolyester, Vectra A900, the matrix polymers were PP, PS, PC, PEL PES, and PEBT. Both types of experiments show that the fiber/matrix morphology is, in general, highly unstable in the molten state. The TLCP fibers break up into droplets by a combination of Rayleigh distortions, end-pinching and retraction, depending on the system and shape of the fiber. Fibers of a thickness of ～1 μm can break up in a few seconds. Breakup times of fibrous blends and individual fibers are in agreement provided size effects are accounted for. Rayleigh distortions develop exponentially in time up to relative distortions of 0.5 to 0.6. Breakup occurs within a range of wave numbers rather than at one distinct dominant wave number, which is shown to be the consequence of relatively large initial distortions. Apparent values for the interfacial tensions calculated with Tomotika's theory turned out to be of the correct order of magnitude, ranging from 7 mN/m for Vectra/PES to 24 mN/m for Vectra/PP and to yield correct values of the interfacial tensions of PP/PS, PP/PC, and PS/PC using Antonow's rule.     

Studies on compatibilization of blends of polypropylene and a thermotropic liquid crystalline polymer

Thermotropic liquid crystalline polymers, LCPs, are frequently blended with thermoplastics to achieve an in situ composite structure. Significant mechanical reinforcement is obtained for the matrix polymer in the direction of the LCP fibers, but the transversal properties are often inferior because of the incompatibility of the components. Blends of LCP with polypropylene, and with three related matrix polymers, and PP/LCP blends with added potential compatibilizers were prepared and studied for their mechanical properties and morphology. A notable improvement in impact strength was achieved when a small amount of ethylene-based terpolymer was added as compatibilizer. © 1993 John Wiley & Sons, Inc.     

Fibers from blends of PET and thermotropic liquid crystalline polymer

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. DSC melting and crystallization results show that the PET is compatible with LCP and the crystallization of PET decreases by the addition of LCP in the matrix. Upon heating above the crystal melting temperature of PET, the blend shows good dispersion of LCP in the PET matrix. Wide angle X-ray diffraction of drawn blended fibers show the possible formation of LCP oriented domains. The mechanical properties of drawn fiber up to 10 wt% LCP composition exhibit significant improvement in tensile modulus and tensile strength with values of 17.7 GPa and 1.0 GPa, respectively. Values of modulus are compared with prediction from composite theory, assuming the blend system as nematic domains of LCP. dispersed in PET matrix.     

Phase behavior of thermotropic liquid crystalline/conducting polymer blends

Summary Liquid crystalline/conducting polymer blends have been prepared. The conductingpolymer [poly(2,5-dimethoxyphenylene vinylene)] retards the liquid crystallinity of the liquid crystalline polymer (hydroxypropyl cellulose), while the liquid crystalline polymer reduces the conductivity of the conducting polymer. However, blends with 17% conducting polymer were both liquid crystalline and conductive. Dedicated to Prof. Dragutin Fleš on the occasion of his 70th birthday     

Properties of films from polypropylene and thermotropic liquid crystalline polymer blends

In this paper the effect of the inclusion of two different thermotropic liquid crystalline polymers, namely Rodrun 3000 and Vectra A950, in a PP matrix is analyzed with particular attention to the gas transport and mechanical properties of the extruded blend films. The experiments, conducted on PP/Rodrun 3000 and PP/Vectra A950 films, have shown that the presence of TLCPs, also at low percentages, modify the properties of the thermoplastic matrix in a manner depending on the degree of compability and interfacial adhesion between the two components of the blends. Moreover, the effect of a maleic anhydride grafted PP (MAP), used as compatibilizing agent, on the properties and morphology of the PP/Rodrun 3000 system was examined. It was found that the addition of the MAP determines an increase in the barrier properties and in toughness of the films compared to those without MAP.     

Rheology of blends of a thermotropic liquid crystalline polymer with polyphenylene sulfide

Blends of thermotropic liquid crystalline polymer (LCP) and polyphenylene sulfide (PPS) were studied over the entire composition range using Rheometrics Stress Rheometer, capillary rheometer, and differential scanning calorimeter. There is no molecular scale mixing or chemical reaction between the components, as evidenced by melting and crystallization points in the PPS phase. From the strain scaling transients test at low‐rate, LCP and the blends require approximately 60 strain units to obtain steady stale shearing results. The large recoveries in the strain recovery test, magnitude 3 to 3.3 strain unit, are likely the results of texture present in LCPs. With increasing PPS content in LCP/PPS blends, the total recovery declines. Scaling of the transient strain rate remains, but the magnitude of the transients is reduced. At low‐rate, when the LCP is added to the PPS, the pure melts have similar visosity: 500 Pa · s for LCP and 600 Pa · s for PPS, but the viscosity of the blends goes through a maximum with concentration that is nearly three times the viscosity of the individual melts. At high‐rate, a significant depression of the viscosity is observed in the PPS‐rich compositions and this may be due to the fibrous structure of the LCP at high shear rates.     

Processing and properties of polyimide melt blends containing a thermotropic liquid crystalline polymer

Several polymer blend compositions of LaRC-TPI 1500 and New TPI 450 (Mitsui Toatsu) with Xydar SRT 900 LCP (Amoco Performance Products) were extrusion processed. In addition to binary blends containing one TPI with an LCP, ternary blends consisting of an alloy containing both TPIs as the matrix were also processed. By varying the ratio of the polyimides in the matrix, the blends' thermal behavior could be tailored. This paper addresses both processing issues and film properties of these blends. Rheological and thermal studies were conducted on both blends made in a torque rheometer and on biaxially oriented film produced with a counter-rotating annular die. These biaxial blend films were further characterized by measuring tensile and electrical properties. For 70/30 New TPI/Xydar equal biaxial films of 50 μm thickness, a modulus of 3.8 GPa and a stress at break of 100 MPa were measured. For near uniaxial blend films (±3°) a modulus of 14.5 GPa and a strength of 220 MPa in the machine direction (MD) were measured. The transverse direction (TD) properties were still higher than the neat New TPI. The electrical properties of these blends were outstanding. The dissipation factor was typically less than 0.01 for most blend compositions. Similarly, the dielectric constant was typically less than 3 up to temperatures as high as 300°C.     

In situ composites based on blends of a polyetherimide and thermotropic liquid crystalline polymers subjected to shearfree deformations

The effects of shearfree elongational flows on the morphology and mechanical properties of blends of a polyetherimide (PEI) with thermotropic liquid crystalline polymers (TLCP) have been investigated. Extruded sheets and injection molded plaques of PEI/Vectra A and PEI/HX1000 blends, with a TLCP concentration of ≤30 wt%, were subjected to uniaxial elongation, planar and biaxial deformations at 240°C, above the glass transition temperature of the PEI, and at 265°C, which is below the melting point of the TLCPs. Experimental results revealed that each particular mode of shearfree deformation had a distinct effect on the morphology and properties of the blends. For instance, TLCP droplets were deformed into elongated fibrils by application of uniaxial elongation, deformed into elongated ribbon-like structures after planar deformation, and deformed into a disc-like shape by application of equibiaxial flow. Regarding mechanical properties, it was observed that the tensile modulus and strength of molded plaques of PEI/HX1000 80/20 wt% increased to about twice their initial values (from 5.13 to 10.40 GPa and from 105 to 198 MPa, respectively) after a strain of 0.75 was applied in a direction parallel to the initial direction of the TLCP fibers. In addition, samples exhibiting equal values of flow and transverse direction tensile modulus of ∼5.0 GPa were obtained when molded plaques of PEI/HX1000 80/20 wt% were subjected to planar stretching in a direction transverse to the initial direction of the fibers. Thus, by subjecting injection molded plaques to planar stretching, it was possible to obtain a sample exhibiting balanced flow and transverse direction mechanical properties and, consequently, reduced anisotropy.     

Thermal decomposition behavior of carbon nanotube reinforced thermotropic liquid crystalline polymers

Thermotropic liquid crystalline polymers (TLCP), 4‐hydroxybenzoic acid (HBA)/6‐hydroxyl‐2‐naphthoic acid (HNA) copolyester, and HNA/hydroxylbenzoic acid (HAA)/terephthalic acid (TA) copolyester reinforced by carbon nanotube (CNT) were prepared by melt compounding using Hakke internal mixer. The thermal behavior and degradation of CNT reinforced HBA/HNA copolyester and HNA/HAA/TA copolyester have been investigated by dynamic thermogravimetric analysis under nitrogen atmosphere in the temperature range 30 to 800°C to study the effect of CNT on the thermal decomposition behavior of the TLCP/CNT nanocomposites. The thermal decomposition temperature at the maximum rate, residual yield, integral procedural decomposition temperature, and activation energy for thermal decomposition was studied to investigate thermal stability of TLCP/CNT nanocomposites. The thermal stability of CNT reinforced HBA/HNA copolyester was increased by addition of a very small quantity of CNT and the residual weight was 42.4% and increased until 50.8% as increasing CNT contents. However, the thermal stability of CNT reinforced HNA/HAA/TA copolyester was decreased initially when a very small quantity of CNT added. The residual weight was decreased from 50.4% to 45.1%. After addition of CNTs in the TLCP matrix, the thermal stability of CNT reinforced HNA/HAA/TA copolyester increased as increasing content of CNT and the residual weight was increased until 53% as increasing CNT contents. The activation energy was calculated by multiple heating rate equations such as Friedman, Flynn‐Wall‐Ozawa, Kissinger, and Kim‐Park methods to confirm the effect of CNT in two different TLCP matrices. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel thermotropic liquid crystalline polyphosphonates

Main chain liquid crystalline polyphosphonates containing semi-flexible phenylester mesogen with even number of methylene spacers (2-10) have been synthesized. The monomers and polymers were characterized by IR, ¹H, ¹³C and ³¹P NMR spectroscopy. The spectral details are in accordance with the structures. All the polymers were exhibited liquid crystalline property in the Hot stage optical polarized microscope (HOPM). DSC thermal analysis confirms the mesophase formation for all the polymers. The grain size of the liquid crystalline mesophase is increasing with increasing methylene chain. T_g, T_m and T_i of the polymers decreased with increase in spacer length. The T_g of these phosphorus-containing polymers is much lower than that of non-phosphorus polymers containing triad ester mesogens. Energy minimized structures for the molecules which mimic the polymer chain suggests that the reduction in T_g may be due to entanglement raised by incorporation of phosphorus heterogeneity.     

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

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

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

A 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.     

Sheet extrusion of microcomposites based on thermotropic liquid crystalline polymers and polypropylene

This work is concerned with the extrusion of sheets from pellets of polypropylene (PP) containing pregenerated microfibrils of thermotropic liquid crystal polymers (TLCPs), referred to as microcomposites. The TLCPs used were HX6000 and Vectra A950. The microcomposites are produced by drawing strands of PP and TLCPs generated by means of a novel mixing technique and pelletizing the strands. The work was undertaken in an effort to improve on the properties for in situ composites in which the TLCP fibrils are generated in contractions in the die and the subsequent drawing step. In situ composites usually exhibit highly anisotropic mechanical properties and the properties do not reflect the full reinforcing potential of the TLCP fibers. Factors affecting the mechanical properties of the composite sheets considered include the effect of in situ composite strand properties and TLCP concentration. In addition, the properties of the extruded sheets are compared to those of microcomposites processed by means of injection molding. It is shown that the sheets produced using microcomposites have a good balance between the machine and transverse direction properties (ratios of these properties ranging from 0.8 to 1.2) and those properties compare well to those obtained by processing microcomposites in injection molding. The tensile modulus of the composite sheets increases with increasing in situ composite strand modulus. The moduli of the 20 wt% Vectra A950 and HX6000 composites are about equal to the modulus of 20 wt% glass reinforced PP (about 2.1 GPa), while the tensile strength of the TLCP reinforced composites is 28% lower than that of the glass reinforced PP. Furthermore, it is shown that the tensile modulus of the 10 wt% TLCP composites approach the predictions of composite theory, while at 20 and 30 wt% TLCP negative deviations from the predictions of composite theory are seen. Finally, it is concluded that the properties of the sheets produced through the extrusion of microcomposites may be further improved by improving the modulus of in situ composite strands and reducing the TLCP fiber diameter.     

Compatibilizers for thermotropic liquid crystalline polymer/polyethylene blends prepared by reactive mixing

This paper describes the effects of composition and processing conditions on the efficiency of the compatibilizer prepared from a thermotropic liquid crystalline polymer (TLCP) and the sodium salt of a poly(ethylene‐co‐r‐acrylic acid) ionomer (EAA‐Na) in TLCP/low‐density polyethylene (LDPE) blends and TLCP/high‐density polyethylene (HDPE) blends. The TLCP‐ionomer graft copolymer formed by a melt acidolysis reaction effectively reduced the interfacial tension between TLCP and polyethylene, which improved impact strength and toughness of the compatibilized blends. Higher processing temperatures for the reactive extrusion produced a more efficient compatibilizer, presumably due to increased graft‐copolymer formation, but the reaction temperature had little effect on the impact strength of compatibilized blends for temperatures above 300°C. The addition of the compatibilizer to TLCP/LDPE blends significantly increased the melt viscosity due to increased interfacial adhesion. The TLCP/EAA‐Na ratio used to prepare the compatibilizer had little effect on the performance of the compatibilizer. Although the compatibilizer can be prepared in situ by blending and extruding a ternary blend of TLCP/EAA‐Na/polyethylene, pre‐reacting the compatibilizer resulted in blends with improved toughness and elongation.     

Formation,stability, and properties of in-situ composites based on blends of a thermotropic liquid crystalline polymer and a thermoplastic elastomer

This paper describes the preparation and properties of in-situ composites based on polymers with no overlap in processing temperatures. The polymers used were Vectra A900, a thermotropic liquid crystalline copolyester (TLCP), and Arnitel em630, a thermoplastic elastomer. Blends were generated by feeding the two components from separate extruders into a Ross static mixer. Different morphologies were obtained by varying the number of mixing elements of the static mixer. Using 8 mixing elements led to a stratified morphology of Vectra layers in Arnitel, using 11 mixing elements resulted in the desired continuous fiber/matrix morphology whereas a pronounced skin-core morphology was obtained with 14 mixing elements. It is argued that in-situ composites can be generated by a distributive mixing process without the formation of an intermediate droplet/matrix morphology as occurs in common dispersive blending equipment. Tensile modulus and strength of all blends increased with extrudate draw ratio as a result of increased molecular orientation of the TLCP phase. The level of reinforcement, however, was lower than expected, probably due to the low temperature of drawing. Annealing and capillary instability experiments showed that above the melting point of the TLCP the fiber/matrix morphology rapidly breaks up into a droplet/matrix morphology. This process takes just a few seconds for fibers of thickness ∼ 1 μm. It is shown to be the probable cause of the skin-core morphology obtained in case of 14 mixing elements.     

The effects of reclamation on a thermotropic liquid crystalline polymer

In previous work, a process was developed to reclaim a thermotropic liquid crystalline polymer (DuPont HX8000) from composites comprised of polypropylene (PP) reinforced with HX8000. The reclamation was accomplished by chemically degrading the PP and then dissolving the PP away in heated mineral oil. From this work, it was found that there were significant drops in dynamic and steady shear viscosity for the reclaimed HX8000, but that there were no losses in mechanical properties when the recovered HX8000 was used to generate PP–HX8000 injection-molded composites. In the present work, the reclaimed HX8000 was analyzed to understand the contradiction between rheological and mechanical properties. The effects of the reclamation process on the recovered HX8000 were investigated by using pycnometry (density), thermogravimetric analysis (TGA), parallel plate rheometry, mechanical testing, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2517–2524, 1999     

Thermal properties,structure and morphology of PEEK/thermotropic liquid crystalline polymer blends

The dynamic crystallization and subsequent melting behaviour of poly(aryl ether ether ketone), PEEK, and its blends with a thermotropic liquid crystalline polymer, Vectra^®, have been studied using differential scanning calorimetry, optical microscopy and wide‐angle and small‐angle X‐ray diffraction (WAXS and SAXS) techniques in a wide compositional range. Differences in crystallization rates and crystallinities were related to the structural and morphological characteristics of the blends measured by simultaneous real‐time WAXS and SAXS experiments using synchrotron radiation and optical microscopy. The crystallization process of PEEK in the blends takes place in the presence of the nematic phase of Vectra and leads to the formation of two different crystalline families. The addition of Vectra reduces the crystallization rate of PEEK, depending on composition, and more perfect crystals are formed. An increase in the long period of PEEK during heating was generally observed in the blends at all cooling rates. Copyright © 2003 Society of Chemical Industry     

In situ composite: Phenolphthalein polyethersulfone—thermotropic liquid crystalline polymer blends

Phase behavior, thermal, rheological and mechanical properties plus morphology have been studied for a binary polymer blend. The blend is phenolphthalein polyethersulfone (PES-C) with a thermotropic liquid crystalline polymer (LCP), a condensation copolymer of p-hydroxybenzoic acid with ethylene terephthalate (PHB-PET). It was found that these two polymers from optically isotropic and homogeneous blends by means of a solvent casting method. The homogeneous blends undergo phase separation during heat treatment. However, melt mixed PES-C/PHB-PET blends were heterogeneous based upon DSC and DMA analysis and SEM examination. Addition of LCP in PES-C resulted in a marked reduction of melt viscosity and thus improved processability. Compared to pure PES-C, the charpy impact strength of the blend containing 2.5% LCP increased 2.5 times. Synergistic effects were also observed for the mechanical properties of blends containing < 10% LCP. Particulates, ribbons, and fibrils were found to be the typical morphological units of PHB-PET in the PES-C matrix, which depended upon the concentration of LCP and the processing conditions.