Poly(p-phenylene sulfide)/liquid crystalline polymer blends. II. Crystallization kinetics

The crystallization kinetics of blends made of poly(p-phenylene sulfide) (PPS) with a liquid crystalline polymer (LCP) was studied. The blends were found to be immiscible by dynamic mechanical thermal analysis (DMTA). Results of non-isothermal and isothermal crystallization experiments made by differential scanning calorimetry (DSC) showed that both components had their crystallization temperatures increased; also the LCP melting temperature was found to increase in the blends. It was concluded that the addition of LCP to the PPS increased the PPS overall crystallization rate due to heterogeneous nucleation. The fold interfacial free energy, σ_e of the PPS in the blends was observed not to vary with composition. © 1996 John Wiley & Sons, Inc.     

A preliminary investigation of flash formation during injection molding of polyphenylene sulfide and liquid crystalline polymer blends

Flashing in pure polyphenylene sulfide (PPS) and a blend containing PPS and liquid crystalline polymer (LCP) during injection molding was investigated by differential scanning calorimetry and scanning electron microscopy. The shape of the flash was observed by use of a projector. Flashing was detected in pure PPS and 90/10 PPS/LCP blend but was not found in other compositions, including pure LCP. The DSC thermograms of the flash revealed both exothermic and endothermic peaks at around 120° and 285°C. The first peak, known as crystallization temperature on heating, occurred as a result of early crystallization of PPS. The observed double peaks indicated that the degree of crystallinity was lower in the flash than in the molded part. The morphological studies revealed the presence of LCP fibrils in the skin region and droplets in the core region of 90/10 PPS blend. The absence of flash was attributed to the diameters of the fibrils and droplets, which were found to increase with increasing LCP component.     

Blends of polypropylene resins with a liquid crystalline polymer. I. Isothermal crystallization

The isothermal crystallization kinetics of blends of different polypropylene (PP) resins and a liquid crystalline polymer (LCP) after two different melting conditions (200 and 290°C) were studied by DSC and polarized light optical microscopy. The resins were a homopolymer (hPP), a random copolymer with ethylene (cPP), and a maleic anhydride grafted PP (gPP). The LCP was Vectra A950, a random copolymer made of 75 mol % of 4‐hydroxybenzoic acid and 25 mol % of 2‐hydroxy,6‐naphthoic acid. It was observed that the overall crystallization rates of all the blends after melting at 200°C were higher than those after melting at 290°C. The LCP acted as a nucleating agent for all the PP resins; however, its nucleating effect was stronger for the hPP than for the cPP and gPP resins. After both melting conditions, an increase was observed in the overall crystallization rate of the hPP and gPP resins with the increase in the amount of LCP, but not in the cPP crystallization rate. The fold surface free energy σ_e of hPP and cPP in the blends decreased, but increased in the gPP blends. Finally, all the PP resins formed transcrystallites on the LCP domain surfaces. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 916–930, 2003     

Post extrusion hot drawing of polycarbonate/liquid crystalline polymer blends

The post extrusion hot drawing of polycarbonate/liquid crystalline polymer (PC/LCP) blends, over the entire composition range, was studied. The extruded filament morphology and elastic modulus were followed as a function of blends composition, initial phase morphology, and draw ratio (DR). Hot drawing was found to cause further orientation to the already existing partially oriented LCP phase at the die exit, as reflected by the increased blends modulus. The additional orientation depends on the initial filaments structure, the blend composition, and the DR. Moreover, the orientability of the LCP phase is much higher, similar to that of neat LCP, for blends in which the LCP forms the continuous phase. In low LCP content blends, a critical DR was identified, beyond which the LCP fibrils undergo fragmentation and voids at the fibrils/matrix interface are formed, resulting in a decrease in the drawn filament modulus.     

Rheological behavior and thermal stability of poly(phenylene sulfide)/vectra-B950 blends

Blends of polyphenylene sulfide (PPS) with a commercial, wholly aromatic, liquid crystalline polymer (LCP), Vectra-B950, have been prepared by melt-blending. Their rheological behavior has been studied in order to determine if the LCP displays a processing aid ability, and under what conditions it gives rise to potentially reinforcing fibrils dispersed in the PPS matrix. The problem of the thermal stability of PPS/LCP blends, which has been considered by some authors as the main obstacle to the production of usable materials due to the evolution of gaseous substances during processing, has been discussed. © 1994 John Wiley & Sons, Inc.     

Effects of processing conditions on the mechanical performance of maleic anhydride compatibilized in-situ composites of polypropylene with liquid crystalline polymer

Maleic anhydride compatibilized blends of isotactic polypropylene (PP) and thermotropic liquid crystaline polymer (LCP) were prepared either by the direct injection molding (one-step process), or by twin-screw extrusion blending, after which specimens were injection molded (two-step process). The morphology and mechanical properties of these injection molded in situ LCP composites were studied by means of scanning electron microscopy (SEM), Izod impact testing, static tensile, and dynamic mechanical measurements. SEM observations showed that fine and elongated LCP fibrils are formed in the maleic anhydride compatibilized in situ composites fabricated by means of the one-step process. The tensile strength and modulus of these composites were considerably close to those predicted from the rule of mixtures. Furthermore, the impact behavior of LCP fibril reinforced composites was similar to that of the glass fiber reinforced polymer composites. On the other hand, the maleic anhydride compatibilized blends prepared from the two-step process showed lower mechanical performance, which was attributed to the poorer processing behavior leading to the degradation of PP. The effects of the processing steps, temperatures, and compatibilizer addition on the mechanical properties of the PP/LCP blends are discussed.     

Through-thickness distribution of LCP in PPS/LCP blends

Through-thickness distribution of liquid crystalline polymer (LCP) of blends containing polyphenylene sulfide (PPS) and LCP was investigated using differential scanning calorimetry and scanning electron microscopy. The effect of the LCP distribution on the mechanical test was checked through bending testing of the various compositions of the injection molded samples. These studies showed a nonuniform distribution of LCP in the PPS-rich region where the LCP content in the skin layer was higher than in the core layer or boundary between the two layers. The LCP component was uniformly distributed in the LCP-rich region. The increase of bending modulus with increasing LCP content was attributed to the reinforcing nature of the LCP fibrils in the skin layer. © 1994 John Wiley & Sons, Inc.     

Liquid crystalline polymer (LCP) reinforced polyethylene blend blown film: Effects of counter-rotating die on fiber orientation and film properties

Polyethylene blends (LLDPE:HDPE ≈ 2:1 by wt) used in NASA's balloon film applications can be effectively reinforced by addition of a small amount of liquid crystalline polymer (LCP). Cast and blown PE films containing ≈ 10% LCP show an appreciable enhancement in tensile modulus ≈400% over that of the neat PE matrix. Anisotropy in these in-situ composites was reduced by controlling LCP molecular orientation via a counter-rotating (C/R) annular die. LCP/PE blend blown films with nearly isotropic properties are obtained. Based on microscopy studies, LCP domains were generally present as fibrils with diameters of ≈ 1 to 3 µM and lengths of ≈ 100 to 300 µM. Films, produced using a C/R die, had fibrillated LCP phases and variable orientation through the film thickness. This paper describes the influence of some key process variables including temperature profile, number of extrusion cycles, degree of mixing, adapter geometry, and die counter-rotation on LCP/PE blend film morphology and mechanical properties. The structure of LCP/PE blend blown films was also evaluated using scanning electron microscope (SEM) and wide angle X-ray scattering (WAXS) techniques.     

Effects on the melt rheology of systems of Nd‐Fe‐B particles suspended in a poly(phenylene sulfide) and liquid crystalline polymer blend

The melt rheology of blends of a liquid crystalline polymer (LCP) and poly(phenylene sulfide) (PPS) and their composites with ferromagnetic Nd‐Fe‐B particles (MQP) was studied. We investigated the effects of LCP concentration, Nd‐Fe‐B particle volume fraction and size, distribution, and shear rate on the rheological properties of these composites. Enthalpy of fusion changes that were observed resulted from the addition of the LCP and Nd‐Fe‐B particles to the polymer blends/composites. The shear rate and frequency dependencies of the materials revealed a viscosity reduction at low (1–3 wt%) and moderate (10–15 wt%) LCP concentrations, and strong effects on the shear‐thinning characteristics of the melt. The suspensions of polydispersed Nd‐Fe‐B particle configurations in PPS that were of lower size ratios gave better processability, which is contradictory to previously reported behavior of suspensions containing spherical particles. Specifically, the compositions with unimodal and a bimodal distribution of Nd‐Fe‐B particles gave the lowest viscosities. The experimental data were correlated with semi‐empirical viscosity model equations of Maron‐Pierce, Krieger‐Dougherty, Eilers, and Thomas and were found to be consistent with the data. The maximum packing fraction, ϕ_m, of the MQP particles was estimated to be within the range of 0.78 ϕ ≤_m ≤ 1.0 through graphical and parametric evaluation methods.     

A method of forming composite structures using in situ-formed liquid crystal polymer fibers in a thermoplastic matrix

A new high speed and potentially economical method of creating a composite material and structures therefrom is tested. The method consists of spinning composite fibers from a melt blend of a thermoplastic with a liquid crystal polymer (LCP). Discontinuous fibrils of the LCP are formed in situ during the spinning process. These composite fibers are aligned and placed in a mold and heated to melt the thermoplastic matrix, but not the fibrils. A finished composite structure reinforced by the LCP fibrils is obtained when the thermoplastic phase is consequently consolidated. Our experiments show the proposed process is reasonable for an easily processed polystyrene matrix. High modulus fibrils with essentially infinite L/D ratios are readily produced in the extrusion process using 40 wt% of a wholly aromatic poly(ester-co-amide) LCP from Celanese. The integrity and alignment of the LCP fibrils is retained in the molding step. Mechanical tests show that the fibers produced by high shear rate processing have a stiffness approaching 23 GPa and match an axial rule-of-mixtures theory. The use of polystyrene resulted in brittleness. Molded composite plates exhibit slightly lower stiffness and significantly lower strength than individual fibers.     

Mechanical,dynamic mechanical properties and thermal stability of fluorocarbon elastomer–liquid crystalline polymer blends

Blends of fluorocarbon elastomer (FKM) and liquid crystalline polymer (LCP) have been prepared by the melt mixing technique. Processing studies indicated the increase in viscosity with the addition of LCP. The tensile strength, tear strength, and modulus of the elastomer are greatly improved by the addition of the LCP. Dynamic mechanical analysis (DMA) results showed that the shift in the glass transition temperature (T_g) of the elastomer with the addition of LCP and the storage modulus of the blends increased above the T_g of FKM, whereas decreases below the T_g of the elastomer were seen with up to 20 wt% LCP; this suggests that the LCP acts as an effective reinforcing agent above the T_g of FKM. From the thermogravimetric analysis (TGA) and differential thermogravimetry (DTG), we found that the thermal stability of the elastomer enhances by blending with the LCP. The weight loss and the weight loss rate of the FKM decrease enormously with the addition of LCP. From the X‐ray diffraction (XRD) study, it has been observed that the LCP acts as a nucleating agent by increasing the crystallinity of the blend. The failure mechanism of the blends was studied using a scanning electron microscope (SEM). It suggested that the failure occurred in the blends; mainly due to the pull out of the fibrils from the matrix phase and due to lower interfacial adhesion between the LCP phase and the elastomer. POLYM. COMPOS. 26:306–315, 2005. © 2005 Society of Plastics Engineers     

In situ compatibilized SAN/LCP blends through reactive copolymers

Styrene–acrylonitrile–glycidyl methacrylate (SAG) copolymers with various contents of glycidyl methacrylate (GMA) were used to compatibilize the incompatible blends of styrene–acrylonitrile (SAN) and a liquid crystalline polymer (LCP). These SAG copolymers contain reactive glycidyl groups that are able to react with the carboxylic acid and/or hydroxyl end groups of the LCP to form the SAG‐g‐LCP copolymers during melt processing. The in situ–formed graft copolymers tend to reside along the interface to reduce the interfacial tension and to increase the interface adhesion. The morphologies of the SAN/LCP blends were examined by using scanning electron microscopy (SEM), where the compatibilized SAN/LCP blends were observed with greater numbers and finer fibrils than those of the corresponding uncompatibilized blends. The mechanical properties of the blends increased after compatibilization. The presence of a small amount (200 ppm) of ethyl triphenylphosphonium bromide (ETPB) catalyst further promotes the graft reaction and improves the compatibilization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3321–3332, 2001     

Polymer bonded magnets. II. Effect of liquid crystal polymer and surface modification on magneto‐mechanical properties

We studied the effect of liquid crystal polymer (LCP) and surface modification of neodymium‐iron‐boron (Nd‐Fe‐B) magnetic alloy on the magneto‐mechanical behavior of poly (phenylene sulfide) (PPS) bonded Nd‐Fe‐B magnets to accelerate efforts to develop useful thermoplastic magnets with optimal performance. The results indicate that blending the LCP with PPS provides the required balance of properties for the targeted applications. These properties include superior magneto‐mechanical performance at elevated temperatures, minimal melt viscosity at optimal LCP volume fraction, high stiffness, and improved dimensional stability, making the thermoplastic magnets suitable for use at elevated temperatures and in chemically corrosive environments where commercial rare earth alloy magnets are not useable. Enhanced wetting of the magnetic Nd‐Fe‐B powders by the polymers, formation of reinforcing LCP domains, and interactions between the polymers and the magnetic powders are thought to be responsible for the beneficial function of the LCP and Nd‐Fe‐B surface modifier in the PPS bonded Nd‐Fe‐B magnets.     

Novel approach to fibrillation of LCP in an LCP/PP blend

A novel concept of improving shear‐induced fibrillation of liquid crystalline polymer (LCP) in LCP/thermoplastic blend systems was introduced. Silica fillers (SiO₂) were added to an LCP/polypropylene (PP) system to serve as a viscosity thickening agent and to improve the fibrillation of the LCP phase. The formation of LCP fibrils was found to enhance with the incorporation of 5–15 wt % of fillers. The presence of LCP fibrils improved the flow properties of the LCP/PP/SiO₂ composites. It was evident from the rheological and morphological studies that the addition of silica led to an increase of the aspect ratio of the LCP fibrils, which, in turn, should improve their effectiveness as reinforcements and/or toughening agents. Substantial improvement in LCP aspect ratio was achieved by the introduction of hydrophobic SiO₂ fillers in the PP/LCP blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2070–2078, 2002     

Molecular orientation and mechanical properties of polymer blends of PBT and a liquid crystalline polyester

A thermotropic liquid crystalline polyester (LCP) based on 4-hydroxyacetophenone azine and sebacoyl dichloride was synthesized via a low-temperature solution route. The liquid crystalline polymer was characterized by ¹H-NMR, DSC, GPC, and polarizing microscopy experiments. The LCP was melt-blended with poly(butylene terephthalate) (PBT), followed by the melt-spinning process at take-up speeds ranging from 14 to 50 m/min. We analyzed the molecular orientational order of LCP and PBT in as-spun fibers of the LCP/PBT blends by the attenuated total reflection (ATR) FTIR dichroism technique and WAXS. The order parameter (S), representing the molecular orientational order, of LCP in the polyblend fibers increased as the employed LCP amounts and the draw ratio increased. Moreover, the order parameter of PBT in the blends increased dramatically when sufficiently large amounts of LCP (over 50 wt %) were employed, especially for highly drawn fibers, which suggested a considerable miscibility between LCP and PBT. The thermal behavior of the blends investigated by DSC also indicated that the synthesized LCP was miscible, at least partially, with PBT. All these results correlated with the enhancement of mechanical properties observed for higher concentrations of LCP in the blends and for highly drawn samples. © 1996 John Wiley & Sons, Inc.     

Rheology and impact characteristics of compatibilized polypropylene-liquid crystalline polymer composites

Polypropylene-liquid crystalline polymer (PP/LCP) and maleic anhydride compatibilized PP/LCP blends were prepared using the extrusion technique followed by injection molding. The LCP employed was Vectra A950 which consists of 25 mol % of 2,6-hydroxynaphthoic acid and 75 mol % of p-hydroxybenzoic acid. The rheology, morphology, and impact behavior of compatibilized PP/LCP blends were investigated. The rheological measurements showed that the viscosity of LCP is significantly higher than that of the PP at 280°C. This implied that the viscosity ratio of the LCP to the polymer matrix is much larger than unity. Scanning electron microscopy (SEM) observations revealed that the LCP domains are dispersed mainly into elongated ellipsoids in the PP/LCP blends. However, fine fibrils with large aspect ratios were formed in the compatibilized PP/LCP blends containing LCP content ≥ 10 wt %. The development of fine fibrillar morphology in the compatibilized PP/LCP blends had a large influence on the mechanical properties. The Izod impact strength of the PP/LCP blends showed little dependence on the LCP concentrations. On the other hand, the impact strength of the compatibilized PP/LCP blends was dependent on the LCP concentrations. The correlation between the LCP fibrillar morphology and spherulitic structure with the impact properties of the compatibilized PP/LCP blends is discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 521–530, 1998     

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.     

Manufacturing and characterisation of microfibrillar reinforced composites from liquid crystalline polymers and poly(phenylene ether)

Abstract

The purpose of the present study was to investigate the fibrillisation process of liquid crystalline polymers (LCPs) in an amorphous poly(phenylene ether) (PPE) matrix during melt blending and a subsequent drawing operation, as well as to analyse the relationship between morphology and mechanical properties of the fibrillar reinforced LCP/PPE blends. In order to understand the effect of the compatibility between the blend partners, an additional set of LCP/PEE blends, containing different amounts of a compatibiliser, was studied too. The processing steps included: (i) melt extrusion and continuous hot stretching for fibrillisation of the LCP component in the different LCP/PPE blends, and (ii) compression (CM) or injection moulding (IM) of the drawn blends at temperatures below the melting temperature (T_m) of the LCPs. Samples from each processing stage were characterised by means of scanning electron microscopy (SEM), wide and small angle X-ray scattering (WAXS and SAXS), and mechanical testing. SEM and WAXS showed that the as extruded blends were isotropic, but after hot stretching the LCP components became highly oriented, with a high aspect ratio and a diameter of the fibrils between 0·4 and 3 μm. The fibrillated structure of the LCPs in the blends could be preserved after the compression and injection moulding only at temperatures below T_m of the LCPs. Addition of a compatibiliser to the LCP/PPE blend did not remarkably improve the adhesion between the components, as a result of the large difference between the coefficients of thermal expansion of the blend partners, which leads to different shrinkage conditions of the LCP fibrils and the PPE matrix. The flexural modulus (E) of all IM blends increased stepwise with an increase in the weight (wt) fraction of the LCP. At the same time, the highest values for the flexural strength (σ) were obtained for the LCP/PPE blends containing 5 wt-% LCP.     

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.     

Thermal conductivity and thermal expansivity of in situ composites of a liquid crystalline polymer and polycarbonate

The thermal conductivity and thermal expansivity of extruded blends of a liquid crystalline polymer (LCP) and polycarbonate (PC) with volume fraction (V_f) of LCP between 0.09 and 0.8 have been measured as functions of draw ratios λ ranging from 1.3 to 15. At V_f < 0.3, the LCP domains are dispersed in a PC matrix and the aspect ratio of the domains increases with increasing λ. At V_f > 0.55, phase inversion has occurred and the LCP becomes the continuous phase. The axial thermal conductivity K_∥ increases while the axial expansivity α_∥ decreases sharply with increasing λ, as a result of the higher aspect ratio of the LCP fibrils and the improved molecular orientation within the fibrils. Since the transverse thermal conductivity and expansivity are little affected by drawing, the blends exhibit strong anisotropy in the thermal conduction and expansion behavior at high λ. At V_f < 0.3, the behavior of K_∥ is reasonably modeled by the Halpin-Tsai equation for short fiber composites. At high draw ratio (λ = 15), all the blends behave like unidirectional continuous fiber composites, so K_∥ and α_∥ follow the rule of mixtures and the Schapery equation, respectively.