Crystallization kinetics of compatibilized blends of a liquid crystalline polymer with polypropylene

Blends of a maleic anhydride-grafted polypropylene (m-PP) and a liquid crystalline polymer (LCP) based on a copolyester of hydroxynapthoic acid and hydroxybenzoic acid were fabricated. The morphology and isothermal and nonisothermal crystallization kinetics behavior of the m-PP copolymer and m-PP/LCP blends were investigated using polarizing optical microscopy, depolarized light intensity, and differential scanning calorimetry. A polarizing optical micrograph revealed that the m-PP is very effective to promote a finer dispersion of the LCP phase in the PP matrix. Consequently, the LCP domains or fibrils acted as potential sites for the spherulite nucleation. The isothermal kinetics measurements also indicated that the rate of crystallization is enhanced in the maleated PP/LCP blends which exhibit transcrystallinity. In general, the nonisothermal kinetics results were in good agreement with those obtained from the isothermal kinetics measurements. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 707–715, 1997     

聚丙烯/热致性液晶聚合物原位复合材料的研究进展

聚丙烯是一个通用塑料,为了提高聚丙烯的性能,拓宽其应用领域,人们对聚丙烯进行了改性研究.笔者简述了热致液晶聚合物原位复合改性聚丙烯的研究进展,并讨论热致液晶聚合物对聚丙烯结晶与熔融行为、微观结构、流变性及力学性能的影响,介绍了改进TLCP与PP之间相容性的常用方法.最后对TLCP/PP原位复合材料的发展提出一些看法.     

Engineering properties of compatibilized polypropylene/liquid crystalline polymer blends

Polypropylene (PP) and Vectra A950, a thermotropic liquid crystalline polymer (LCP), blends were prepared in a single‐screw extruder with the variation in Vectra A950 content in presence of fixed amount (2%, with respect to PP and LCP mixture as a whole) of ethylene‐acrylic acid (EAA) copolymer as a compatibilizer. Mechanical analysis of the compatibilized blends within the range of LCP incorporations under study (2–10%) indicated pronounced improvement in the moduli, ultimate tensile strength (UTS), and hardness. Fourier transform infrared (FTIR) spectroscopy studies revealed the presence of strong interaction through H‐bonding between the segments of Vectra A950 and the compatibilizer EAA. Morphological studies performed by scanning electron microscopy (SEM) manifested the development of fine fibrillar morphology in the compatibilized PP/Vectra A950 blends, which had large influence on the mechanical properties. Differential scanning calorimetry studies showed an initial drop of the melting point of PP in the presence of EAA followed by enhancement of the same in presence of Vectra A950. TGA showed an increase in the thermal stability for all blends with respect to matrix polymer PP. Rheological studies showed that a very small quantity of Vectra A 950 was capable of reducing the melt viscosity of PP particularly in the lower shear rate region and hence facilitated processibility of the blends. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of nano‐silica filler on the rheological and morphological properties of polypropylene/liquid‐crystalline polymer blends

A fumed hydrophilic nano‐silica‐filled polypropylene (PP) composite was blended with a liquid‐crystalline polymer (LCP; Rodrun LC5000). The preblended polymer blend was extruded through a capillary die; this was followed by a series of rheological and morphological characterizations. The viscosity of the PP matrix increased with the addition of the hydrophilic nano‐silica. At shear rates between 50 and 200 s^?1, the composite displays marked shear‐thinning characteristics. However, the incorporation of LC5000 in the PP composite eliminated the shear‐thinning characteristic, which suggests that LC5000 destroyed the agglomerated nano‐silica network in the PP matrix. Although the viscosity ratio of LCP/PP was reduced after the addition of nano‐silica fillers, the LCP phases existed as droplets and ellipsoids. The nano‐silicas were concentrated in the LC5000 phase, which hindered the formation of LCP fibers when processed at high shear deformation. We carried out surface modification of the hydrophilic nano‐silica to investigate the effect of modified nano‐silica (M‐silica) on the morphology of the PP/LC5000 blend system. Ethanol was successfully grafted onto the nano‐silica surface with a controlled grafting ratio. The viscosity was reduced for PP filled with ethanol‐M‐silica when compared to the system filled with untreated hydrophilic nano‐silica. The LC5000 in the (PP/M‐silica)/LC5000 blend existed mainly in the form of fibrils. At high shear rates (e.g., 3000 s^?1), the LC5000 fibril network was formed at the skin region of the extrudates. The exclusion of nano‐silica in the LC5000 phase and the increased viscosity of the matrix were responsible for the morphological changes of the LCP phase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1484–1492, 2003     

Impact-modified blends of compatibilized polyamide-6 with liquid crystalline copolyester

Compatibilized blends of polyamide-6 (PA6) and thermotropic liquid crystalline polymer (LCP) modified with various high-impact polypropylene (HIPP) contents were injection-molded. These blends were compatibilized with maleic anhydride-grafted polypropylene (MAP). The effects of impact modification on the morphology, impact, static, and dynamic mechanical properties were investigated. The results showed that the HIPP addition leads to an improvement of the Izod impact strength of the blends significantly while it reduced the tensile strength and stiffness properties. An attempt was made to correlate the structure of the PA6(MAP)/HIPP/LCP blends from the scanning electron microscopic observations with the measured mechanical properties. This work provides a way to produce a tough in situ composite. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1611–1619, 1998     

Morphology and rheology of composites based on anisotropic polymer matrix and different clays

Structure and rheological properties of hybrids with polymer matrix and layered silicates as filler were studied. Solution containing 60% wt of hydroxypropylcellulose (HPC) in oligomeric polyethyleneglycol (PEG) was used as a matrix. The peculiarity of this study is that the matrix depending on temperature can form different phase states including liquid‐crystalline (LC). So, a possibility of coexistence and superposition of different ordered structures can be realized at different temperatures. Three different fillers were used: natural Na‐montmorillonite (MMT) and organoclays obtained by treating MMT with surfactants varying in polarity of their molecules. Depending on the type of clay, materials with different morphology can be obtained. X‐ray data showed that PEG intercalates all types of clay used whereas penetration of HPC macromolecules into clay galleries during mixing does not occur. Clay modified with more polar surfactant should be treated as the most convenient material to be intercalated by PEG. Rheological studies (included steady‐state and dynamic shear properties in a wide temperature range) demonstrate that composites are viscoplastic materials and the yield stress is observed already at 5% fillers loading. The level of the yield stress depends on the phase state of the matrix being induced by the superposition of structures formed by clay particles as well as by the LC phase (if it exists). The same conclusion can be made on the base of linear oscillatory measurements because the existence of the LC phase and/or the presence of filler lead to a pseudo solid‐like behavior of a system as whole. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Mechanical and morphological study of polyphenylene sulfide/liquid crystalline polymer blends compatibilized with a maleic anhydride grafted copolymer

Blends of thermotropic liquid crystalline polymer (LCPA‐950), based on a copolyester of hydroxynapthoic acid and hydroxybenzoic acid with an engineering thermoplastic, poly(phenylene sulfide) (PPS), were prepared using a corotating twin‐screw extruder. Addition of a third component, a functionalized polypropylene (maleic anhydride grafted polypropylene, MA‐PP), that interact with the thermotropic liquid crystalline polymer (TLCP) facilitates the structural development of the TLCP phase by acting as a compatibilizer at the interface. Differential scanning calorimetry and dynamic mechanical thermal analysis results, however, show that there is an interaction between the polymers in the presence of compatibilizer. This means that MA‐PP can be used as a compatibilizer for the PPS/LCP in situ composite system. The viscosity of the compatibilized in situ composite was decreased by the compatibilizer, and this is mainly due to the fibrous structure of the LCP at the high shear rate. The mechanical properties of the ternary blends were increased when a proper amount of MA‐PP was added. This is attributed to fine fibril generation induced by the addition of MA‐PP. Morphological observations determined the significance of the third component in immiscible polymer blends, and an optimum amount of MA‐PP exists for the best mechanical performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Study on compatibilization of polypropylene-liquid crystalline polymer blends

The mechanical properties, melt rheology, and morphology of binary blends comprised of two polypropylene (PP) grades and two liquid crystalline polymers (LCP) have been studied. Compatibilization with polypropylene grafted with maleic anhydride (PP-g-MAH) has been attempted. A moderate increase in the tensile moduli and no enhancements in tensile strength have been revealed. Those findings have been attributed to the morphology of the blends, which is predominantly of the disperse mode. LCP fibers responsible for mechanical reinforcement were only exceptionally evidenced. Discussion of PP-LCP interfacial characteristics with respect to mechanical properties-morphology interrelations allowed evaluation of the compatibilizing efficiency of PP-g-MAH. Factors important for successful reinforcement of PP with LCP have been specified. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 969–980, 1997     

Properties of ternary in situ polycarbonate/polybutylene terephthalate/liquid crystalline polymer composites

Ternary in situ polycarbonate (PC)/polybutylene terephthalate (PBT)/liquid crystalline polymer (LCP) composites were prepared by injection molding. The liquid crystalline polymer used was a versatile Vectra A950. The matrix of composite was composed of PC/PBT 60/40 by weight. A solid epoxy resin (bisphenol type‐A) was used as a compatibilizer for the composites. Dynamic mechanical analysis (DMA) showed that epoxy resin was effective to improve the compatibility between PC and PBT, and between PC/PBT and LCP, respectively. Tensile tests revealed that the stiffness of composites shows little change with the LCP content up to 10 wt %. Above this concentration, the stiffness tended to increase with increasing LCP content. Furthermore, the tensile strengths appeared to increase with increasing LCP content, and their values were close to those predicted from the rule of mixtures. Scanning electron microscopic examination showed that LCP ribbons and short fibrils were developed in the composites containing LCP content ≤10 wt %. However, fine and elongated fibrils were formed in the skin and core sections of the composites when the LCP content reached 25 wt % and above. Thermogravimetric analysis indicated that the thermooxidative stability of the PC/PBT 60/40 blend tended to improve with increasing LCP content. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1827–1835, 1999     

Effects of shear rate,viscosity ratio and liquid crystalline polymer content on morphological and mechanical properties of polycarbonate and LCP blends

Studies were conducted on the effects of shear rate, viscosity ratio and liquid crystalline polymer (LCP) content on the morphological and mechanical properties of polycarbonate (PC) and LCP blends. The LCP (LC5000) used was a thermotropic liquid crystalline polymer consisting of 80/20 of parahydroxybenzoic acid and poly(ethylene terephthalate) (PHB/PET). The viscosity ratio (viscosity of LCP: viscosity of matrix) was varied by using two processing temperatures. Due to the different sensitivity of materials to temperature, variation in the processing temperature will lead to varying viscosity of the components in the blends. Based on this principle, the processing temperature could be manipulated to provide a favourable viscosity ratio of below unity for fibre formation. To study the effect of shear rate, the flow rate of the blend and the mould thickness were varied. The shear rate has a significant effect on the fibrillation of the LCP phase. The effect was more prominent when the viscosity ratio was low and the matrix viscosity was high. At 5 wt% LCP, fibrillation did not occur even at low viscosity ratios and high shear rates. It was also observed that the LCP content must be sufficiently high to allow coalescence of the dispersed phase for subsequent fibrillation to occur. © 2002 Society of Chemical Industry     

Rheology and relaxation processes in a melting thermotropic liquid–crystalline polymer

The relaxation behavior of a thermotropic liquid–crystalline polymer (TLCP), LC‐5000 from Unichika, Japan, was investigated by rheology and optical microscopy. The solid‐nematic transition was shown by DSC and dynamic temperature ramp. The transitions of dynamic modulus with temperature correspond to the end of the melting process. The TLCP is composed of unmelted solid crystals and nematic liquid crystal during the melting process. Macroscopically, it changes from a viscoelastic solid to a viscoelastic liquid in this process, as verified by creep test and dynamic frequency sweep under different temperature. The relaxation spectra of the TLCP under different temperature were calculated from the dynamic modulus. The characteristic relaxation processes determined from the relaxation spectrum are consistent with the observation from polarized optical microscopy. During melting, in particular, the relaxation of deformed polydomains and chain orientation slows down due to the constraining effects of unmelted solid crystals. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3780–3787, 2007     

环氧液晶对木质素/聚丙烯复合材料结构和性能影响

以4,4'-二(β-羟乙氧基)联苯(BP2)、环氧氯丙烷及对苯二甲酰氯等为原料,通过取代反应合成一种小分子的环氧液晶(LCEP),将该LCEP与木质素(lignin)/聚丙烯(PP)进行共混改性,采用FT-IR、DSC、POM及TGA等对LCEP结构和液晶相转变行为进行了表征,并研究了LCEP含量对Lignin/PP复合材料物理力学性能和热性能的影响。利用SEM观察了复合材料断裂形貌,探讨其增韧增强机理。结果表明:加入4%的LCEP聚丙烯/木质素复合材料的综合性能最好,其冲击强度、弯曲强度和弯曲模量较未改性前分别提高了38.6%、30.5%和20%,热稳定性、结晶性和结晶速率也有明显提高。     

Self‐reinforcing elastomer composites based on polyolefinic thermoplastic elastomer and thermotropic liquid crystalline polymer

In situ reinforcing elastomer composites based on Santoprene thermoplastic elastomer, a polymerized polyolefin compound of ethylene–propylene–diene monomer/polypropylene, and a thermotropic liquid crystalline polymer (TLCP), Rodrun LC3000, were prepared using a single‐screw extruder. The rheological behavior, morphology, mechanical, and thermal properties of the blends containing various LC3000 contents were investigated. All neat components and their blends exhibited shear thinning behavior. With increasing TLCP content, processability became easier because of the decrease in melt viscosity of the blends. Despite the viscosity ratio of dispersed phase to the matrix phase for the blend system is lower than 0.14, most of TLCP domains in the blends containing 5–10 wt % LC3000 appeared as droplets. At 20 wt % LC3000 or more, the domain size of TLCP became larger because of the coalescence of liquid TLCP threads that occurred during extrusion. The addition of LC3000 into the elastomer matrix enhanced the initial tensile modulus considerably whereas the extensibility of the blends remarkably decreased with addition of high TLCP level (>.20 wt %). The incorporation of LC3000 into Santoprene slightly improved the thermal resistance both in nitrogen and in air. Dynamic mechanical analysis results clearly showed an enhancement in dynamic moduli for the blends with 20–30 wt % LC3000. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Crystallization and compatibilization of polypropylene–liquid crystalline polyester blends

A liquid crystalline polyester, LC3000, has been blended with polypropylene. These polymers form an incompatible and immiscible blend. Polypropylene grafted with epoxy via glycidyl methacrylate forms an effective compatibilizer. The dispersed liquid crystalline polyester particle size was decreased when the compatibilizer was used. The polyester influenced the morphology of the polypropylene continuous phase by increasing the nucleation, and the effect was enhanced when the compatibilizer was present. This was demonstrated using continuous cooling DSC where the crystallization temperatures were increased. Isothermal crystallization showed decreased crystallization half‐times with the polyester present, and these were further reduced with compatibilizer. Avrami analysis showed that the exponent values increased by an average of 0.1–0.2, so nucleation was assisted by the LC3000, and the rate coefficients were increased. The continuous cooling and isothermal DSC measurements provided complementary results. Optical microscopy showed that the spherulite size of the polypropylene was reduced. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2229–2236, 2000     

Effect of compatibilization in injection‐molded polycarbonate and liquid crystalline polymer blend

The effect of compatibilizing polycarbonate (PC) and LC5000, a thermotropic liquid crystalline polymer consisting of 80/20% of hydroxybenzoic acid and poly(terephthalate) with a laboratory synthesized compatibilizer was studied. The compatibilizer was synthesized by transesterification of PC and LC5000 with the aid of a catalyst. The effect of compatibilization was investigated by studying the mechanical and morphological properties of injection‐molded plaques with different thicknesses. Substantial improvement was observed in the mechanical properties after compatibilization. Significant enhancement in the fibrillation was also observed in the samples after addition of compatibilizer. The surface finish of the compatibilized samples was smooth and homogenous as compared to the uncompatibilized samples. The skin‐core phenomenon in the tensile fractured surfaces was less obvious in the former samples, indicating better adhesion and homogeneity. These morphological studies showed that the mechanical properties enhancement lay in improved fibrillation and interfacial adhesion between the dispersed and major phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 568–575, 2002; DOI 10.1002/app.10308     

Wear and mechanical properties of reactive thermotropic liquid crystalline polymer/unsaturated polyester/glass fiber hybrid composites

To improve the performance of unsaturated polyester (UP) under cold‐heat alternate temperature, self‐synthesized reactive thermotropic liquid crystalline polymer (TLCP)‐methacryloyl copolymer (LCMC), UP, and glass fiber (GF) hybrid composites was prepared by molding technology. The apparent activation energy and crystal behavior analysis of LCMC/UP blends were investigated by Differential scanning calorimetry and X‐ray diffraction (XRD), respectively, the results showed that the addition of LCMC can reduce apparent activation energy and accelerate the curing reaction of UP, the XRD analysis indicated that the crystal phase of LCMC still exist in the blends after blending with UP. The effect of LCMC content on the properties of LCMC/UP/GF hybrid composites such as impact strength, bending strength, and ring‐on‐block wear were also investigated through static mechanical tests and wear tests. The mechanical properties of hybrid composites increased significantly because of the addition of LCMC. The wear tests showed that LCMC can improve the wear resistance of the UP/GF/LCMC hybrid composites even though the content of LCMC was at a relatively low level (5–7.5 wt %). This makes it possible to develop novel kind of UP‐based materials with good wear resistance for various applications. The Worn surface was observed by scanning electron microscopy (SEM) and the mechanism for the improvement is discussed in this paper. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3899–3906, 2007     

Microstructure of carbon nanofiber/thermotropic liquid crystalline polymer composites

The properties and microstructure of a thermotropic liquid crystalline polymer (TLCP, Vectran V400P) were investigated in the presence of carbon nanofibers (CNF). The electrical conductivity of TLCP increased with an addition of CNFs. The thermal analysis of pure TLCP and its composites revealed that a glass transition at ～ 110°C did not change significantly. However, a decrease of tensile modulus and strength was observed with the addition of CNFs. WAXD studies showed a decrease of Herman's orientation parameter, indicating reduction of anisotropy of TLCP. Further, the disruption of molecular orientation of TLCPs was inferred by SEM and TEM analysis. SEM micrographs revealed a fibrillar structure for pure TLCPs at a macro‐scale (2–5 μm). However, this structure was not observed in composites at the same scale even though micro‐size fibrils (0.05 μm) were found with the addition of CNFs. TEM micrographs displayed banded structures of pure TLCPs, but these structures were not significant in the vicinity of CNFs. These observations confirmed that a decrease of molecular alignment and disruption of fibrillar structure of TLCP, in the presence of nanofibers, are attributed to a significant decrease in tensile modulus and strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Carboxylated multiwall carbon nanotube-reinforced thermotropic liquid crystalline polymer nanocomposites

Thermotropic liquid crystalline polymer (TLCP) nanocomposites reinforced with carboxylated multiwall carbon nanotube (c-MWCNT) were prepared through melt compounding in a twin screw extruder. The thermal stability of TLCP/c-MWCNT nanocomposites increased with even a small amount of c-MWCNT added. The rheological properties of the TLCP/c-MWCNT nanocomposites were depended on the c-MWCNT contents. The contents of c-MWCNT have a slight effect on the complex viscosity of TLCP/c-MWCNT nanocomposites due to the high-shear thinning of TLCP. The storage modulus of TLCP/c-MWCNT nanocomposites was increased with increasing c-MWCNT content. This result can be deduced that the nanotube–nanotube interactions were more dominant, and some interconnected or network-like structures were formed in the TLCP/c-MWCNT nanocomposites. Incorporation of very small amount of c-MWCNT improved the mechanical properties of TLCP/c-MWCNT nanocomposites, and this was attributed to the reinforcement effect of c-MWCNT with high aspect ratio and their uniform dispersion through acid treatment in the TLCP matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008