Atomic force microscopy (AFM) studies of liquid crystalline polymer (LCP) surfaces

An atomic force microscope (AFM) operating in tapping or contact mode was used to study the surface topography and the molecular organization of Vectra‐A and Vectra‐B films. Large‐scale (15 × 15 μm) AFM images revealed that ribbonlike fibrils with a width/height ≫ 1.0 are the dominant surface features of these liquid crystalline polymers (LCPs). The region of local disorder, surface debris, and interfibrillar debris as well as possible amorphous regions were observed in both LCP samples. Large fibrils, 5.0–10.0 μm in width, can be thought of as formed by smaller microfibrils capable of forming ordered structures. Microfibrils can bend upward, forming raised surface features; bend inward, originating cracks 1–2 μm wide on the film surface; or divide and subdivide into smaller units. Longitudinal and lateral stresses are believed responsible for the variation in fibril size, shape, and orientation. AFM images containing molecular‐scale details showed that microfibrils consists of chains of molecules coiled around a central axis and that they can be only about 2.0 nm wide. These submicron surfaces consist of white spots (representing molecules) that can form ordered structures or that can cluster to form agglomerates distributed in a random manner. Submicron fibrils are believed to represent the LCP basic structural unit. AFM results indicate that the surface topography of Vecta‐B is more ordered and uniform than is the one observed for Vectra‐A. Seemingly, amorphous particles form debris on Vectra‐A surfaces. Short rods oriented crosswise on the fibril surface are instead what increases the Vectra‐B roughness. These LCPs can have a surface topography similar to the one observed in AFM images of a spiderweb. However, the spiderweb fibrils are formed by more uniform microfibrils that are oriented parallel to each other. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2243–2254, 1999     

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.     

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     

Partial crystallisation in liquid polymer electrolytes based on co-polymers of ethylene oxide/propylene oxide

Solutions of lithium perchlorate in a low molecular weight ethylene oxide/propylene oxide (EO/PO) co-polymer were studied by differential scanning calorimetry. The pure co-polymer was found to crystallise partially, while addition of the salt impaired crystallisation first by slowing crystal growth then by slowing nucleation. At high salt concentrations (～1·0 molal) no crystallisation occurred. The solvation of Li⁺-ions and the introduction of ‘transient crosslinking’ between cations and anions effectively suppresses the separation of the polymer into microregions of EO and PO. The crystallisation phenomena are relevant to the use of these copolymers as ‘model’ polymer electrolyte systems.     

Crystallization kinetics of poly(ethylene terephthalate) with thermotropic liquid crystalline polymer blends

The isothermal and dynamic crystallization behaviors of polyethylene terephthalate (PET) blended with three types of liquid crystal polymers, i.e., PHB60–PET40, HBA73–HNA27, [(PHB60–PET40)–(HBA73–HNA27) 50 : 50], have been studied using differential scanning calorimetry (DSC). The kinetics were calculated using the slope of the crystallization versus time plot, the time for 50% reduced crystallinity, the time to attain maximum rate of crystallization, and the Avrami equation. All the liquid crystalline polymer reinforcements with 10 wt % added accelerated the rate of crystallization of PET; however, the order of the acceleration effect among the liquid crystalline polymers could not be defined from the isothermal crystallization kinetics. The order of the effect for liquid crystalline polymer on the crystallization of PET is as follows: (PHB60–PET40)–(HBA73–HNA27) (50 : 50); HBA73–HNA27; PHB60–PET40: This order forms the dynamic scan of the DSC measurements. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1383–1392, 1998     

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     

Structure and properties of blend fibers from poly(ethylene terephthalate) and liquid crystalline polymer

The structure and properties of the as-spun fibers of poly(ethylene terephthalate) (PET) blends with a thermotropic liquid crystalline polymer (LCP), Vectra A900, were studied in detail. The DSC results indicate that the LCP component may act as a nucleating agent promoting the crystallization of the PET matrix from the glassy state but which inhibits its crystallization from the melt due to the existence of an LCP supercooled mesophase. The effect of the drawdown ratio on the orientation of the as-spun blend fibers is highly composition-dependent, which is mainly associated with the formation of LCP fibrils during melt spinning. The modulus of the as-spun blend fibers has a significant increase as the content of LCP reaches 10%, while the tensile strength has a slightly decreasing tendency. The mechanical properties of the as-spun blend fibers could be well improved by heat treatment because of a striking increase in the crystallinity of the PET matrix. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 217–224, 1997     

Injection molding of poly(ethylene terephthalate) reinforced with pregenerated thermotropic liquid crystalline polymer microfibrils

This work was concerned with the injection molding of poly(ethylene terephthalate) (PET) reinforced with pregenerated thermotropic liquid crystalline polymer (TLCP) fibrils, where the TLCP had a higher melt processing temperature than PET. These composites, referred to as pregenerated microcomposites, were produced using a two step processing scheme. First, a novel dual extrusion process was used to spin strands of PET reinforced with nearly continuous TLCP fibrils. Second, these strands were subsequently chopped into pellets and injection molded below the melt processing temperature of the TLCP but above that of PET. This allowed the high modulus TLCP fibrils generated in the spinning step to be retained in the injection molded samples. TLCP concentration and strand draw ratio were varied in the composite strands to determine how they affected mechanical properties. It was shown that the best properties were obtained using strands containing 50 weight percent TLCP with draw ratios greater than 50, which were diluted to the desired loading level with a low viscosity injection molding grade of PET. Specifically, these composites had tensile moduli as high as 5.7 GPa when reinforced with 30 weight percent HX1000. Also, it was determined that pregenerated microcomposites had smoother surfaces than glass-filled PET.     

Effect of blend composition on crystallization behavior of polyoxymethylene/poly(ethylene oxide) crystalline/crystalline blends

The influence of blend composition on crystallization behavior of a typical crystalline/crystalline blend, polyoxymethylene (POM)/poly(ethylene oxide) (PEO), during slow non-isothermal crystallization was investigated by polarized light microscope (PLM) connected with a THMS600 hot-stage, scanning electron microscope (SEM), differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The experimental results indicated that with increasing PEO content in the blend, the crystallization temperature of POM of the blends reduced and the multiple crystalline morphologies or structures including two kinds of interfibrillar or interlamellar structures were produced. The melting point of each component decreased with raising the content of the other constituent due to the inclusion and entanglement between POM and PEO molecules. The shoulder melting peak of POM appeared in DSC heating traces of the PEO-rich blend because the stronger inclusion and entanglement induced the imperfect crystallization of POM.     

Miscible crystalline/crystalline polymer blends of polyoxymethylene copolymer/poly(ethylene oxide) with interpenetrated spherulites and enhanced properties

Miscibility and crystallization behavior of a polymer blend consisting of two crystalline components, polyoxymethylene copolymer (Co‐POM) and poly(ethylene oxide) (PEO), have been investigated. Experimental results indicate that Co‐POM is thermodynamically miscible with PEO, as shown by the existence of single‐composition dependent glass transition temperature over the entire composition range. The crystal structures and spherulitic morphologies of (Co‐POM)/PEO blends were studied by X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, and polarizing light microscopy. It was found that the PEO spherulites crystallized within the matrix of the crystals of the pre‐existing Co‐POM phase and resulted in a high extent of interfibrillar segregation. The unique interpenetrated crystalline structure was beneficial for the sufficient contact between the two components and significantly improved both the toughing and the lubricating effect of PEO on the POM matrix. On incorporation of 30 wt% PEO, the notched impact strength of POM was enhanced from 6.7 to 10.3 MPa, by about 53.7%, while the elongation at break increased from 28.5% to 121.0%, by about 3.2 times. Furthermore, the friction coefficient drastically decreased from 0.35 to 0.17, demonstrating the enhanced tribological performance of the miscible blends. J. VINYL ADDIT. TECHNOL., 22:479–486, 2016. © 2015 Society of Plastics Engineers     

Fast crystallization of liquid crystalline copolyesters based on poly(ethylene terephthalate)

Crystallization of a series of liquid crystalline copolyesters prepared from p‐hydroxybenzoic acid (HBA), hydroquinone (HQ), terephthalic acid (TA), and poly(ethylene terephthalate) (PET) was investigated by using differential scanning calorimetry (DSC). It was found that these copolyesters are more crystalline than copolyesters prepared from PET and HBA. Insertion of HQ–TA disrupts longer rigid‐rod sequences formed by HBA and thus enhances molecular motion and increases the crystallization rate. The effects of additives on the crystallization of the copolyesters were also studied. Sodium benzoate (SB) and sodium acetate (SA) increase the crystallization rate of the copolyesters at low temperature, but not at high temperature. It is most likely that liquid crystalline copolyesters do not need nucleating agents, and small aggregates of local‐oriented rodlike segments in nematic phase could act as primary nuclei. Chain scission of the copolyesters caused by the reaction with the nucleating agents was proved by the determination of intrinsic viscosity and by the IR spectra. Diphenylketone (DPK) was shown to effectively promote molecular motion of chains, leading to an increase in the crystallization rate at low temperature, but it decreased the crystallization rate at high temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 497–503, 2001     

Isothermal decomposition behavior and dynamic mechanical properties of in situ‐reinforcing elastomer composites based on thermoplastic elastomers and thermotropic liquid crystalline polymer

In situ‐reinforcing composites based on two elastomer matrices very different in melt viscosity, styrene–(ethylene butylene)–styrene triblock copolymer (Kraton G1650), and styrene–(ethylene propylene) diblock copolymer (Kraton G1701), and a thermotropic liquid crystalline polymer (TLCP), Rodrun LC3000, were prepared using a twin‐screw extruder. The isothermal decomposition behavior and dynamic mechanical properties of the extruded strands were investigated by means of thermogravimetry (TG) and dynamic mechanical analysis (DMA), respectively. No significant change in the shape of TG curves for the neat matrices and their LC3000‐containing blends was observed under isothermal heating in nitrogen. In air, G1650 and G1701 showed a single weight‐loss stage and rapid decomposition whereas their blends with 30 wt % LC3000 showed different profiles of weight loss depending on isothermal temperatures. The calculated kinetic parameters indicated that the thermal stability of the polymers is much higher in nitrogen than in air and suggested an enhancement of thermal resistance of the elastomer matrices by addition of TLCP. DMA results showed a great enhancement in dynamic moduli for the blend with 10 wt % LC3000 when compared with the neat matrix. The tan δ peaks corresponding to the elastic and hard phases in both matrices mostly shifted to the lower temperature with LC3000 loading. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 917–927, 2007     

Characterization of drawn monofilaments of liquid crystalline polymer/carbon nanoparticle composites correlated to nematic order

In this study a nanocomposite monofilament composed of a nematic thermotropic liquid crystalline polymer (TLCP) mixed with 1.5 wt.% of carbon nanoparticles (CNP) was prepared by melt extrusion. The nanoparticles had either a fibrous (VGCF) or layered (GNP) geometry. The tensile strength and modulus of the fibers increased with the draw down ratio of the filament; a positive effect on the tensile modulus is displayed by fibrous CNP, achieving values higher than those of high property organic fibers utilized as reinforcement for composite materials. Thermotropic transitions were characterized by DSC and in situ synchrotron WAXD. In particular, it was shown that the breadth of the temperature span of the crystalline-nematic transition correlated inversely with the draw down ratio. At high draw down ratio, addition of CNP also increased the relative amount of oriented polymer chains and contributed to sharpening of the mesomorphic transition.     

Dye sorption characters of gamma irradiated foamed ethylene propylene diene monomer (EPDM) rubber/clay composites

Composites based on gamma irradiated ethylene propylene diene monomer rubber in foam structure, loaded with different types of clays were used as adsorbents for different classes of dyestuffs (basic, acid, reactive and disperse) from aqueous solutions. The clays under investigation were Aswan clay (ASC) and sodium montmorillonite (Na-MMT). The effect of adsorbent composition, irradiation dose, pH and contact time on dye sorption was studied. It was found that the rubber composites loaded by Na-MMT gave maximum adsorption of the basic dye (～42%) in aqueous solution, while the rubber composites loaded by AS clay gave maximum adsorption (～28%) of the acidic dye. On the other hand, both type of clays did not show no affinity toward reactive and disperse dyes. The efficiency of dye removal was found to increase with increasing the pH and contact time. It was also observed that the irradiation dose (50 kGy) was the optimum dose for the removal of dyes for all rubber composites.     

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。     

A study on synergistic reinforcing effect of halloysite nanotubes/diatomite mixture-filled polymer (PP and PA6) composites

In this paper, the nanotubular halloysite nanotubes (HNTs)/disc-shaped diatomite mixture (HD) was used to study the synergistic reinforcing effect of the filler in polymer matrix (PP and PA6). The structure of the HNTs/diatomite mixture filler-filled polymer composites with different proportions of HNTs/diatomite was determined by XRD and SEM. The mechanical performance of the composites was extensively investigated. The results indicated that the HNTs/diatomite mixture filler with different shapes could significantly reinforce the mechanical performance of polymer regardless of whatever it was filled in — PP or PA6. The synergistic reinforcing effect of HNTs/diatomite mixture filler in polymer matrix was verified.     

Supramolecular selectivity of poly(ethylene oxide) in semi‐crystalline polymer nanocomposites

Semi‐crystalline polymer nanocomposites were prepared using successive meltings and recrystallizations techniques by intercalation of small guest molecules such as 4‐chlorotoluene (PCT), 4‐bromotoluene (PBT) and 1,4‐dibromobenzene (PDBB) into poly(ethylene oxide) (PEO) crystals. Differential scanning calorimetry, Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction experimental results show that supramolecular selectivity exists for the PEO–PDBB/PBT ternary system, while there is no supramolecular selectivity for PEO–PCT/PBT ternary nanocomposites. The interactions between PEO chains and small guest molecules have an important influence on the polymer conformation, which results in the dramatic difference in intercalation behavior. Copyright © 2007 Society of Chemical Industry     

Thermodynamics of micellization of poly-styrene-block-poly(ethylene/propylene) copolymers in decane

Light scattering was used to establish the dependence of the critical micelle temperature, CMT, on concentration for solutions of three polystyrene-block-poly(ethylene/propylene) copolymers in decane. Electron microscopy studies of particles isolated from the solutions showed that the micelles had narrow size distributions and micellization could be treated thermodynamically as a closed association. The light scattering results were used to calculate the standard Gibbs energies of micellization, ΔG^φ, and the standard enthalpy, ΔH^φ, and entropy contributions, —TΔS^φ. The values of ΔH^φ were large and negative, and markedly dependent on the molecular weight of the polystyrene block. The values of ΔG^φ for the three samples were on the other hand very similar to each other. The standard entropy contributions were unfavourable to micelle formation.     

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

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