原位增强纤维的成形过程

介绍了液晶高分子(LCP)和聚丙烯共混纺丝过程中液晶相微纤维结构的形成过程。通过共混纺丝,LCP在聚丙烯纤维中形成了具有强化作用的微纤维,从而提高了聚丙烯纤维的综合性能。     

The effect of interface characteristics on the static and dynamic mechanical properties of three‐component polymer alloys

The effect of interfacial characteristics on the structure‐property relationships of ternary polymer alloys and blends comprising polypropylene (PP), ethylene‐vinyl alcohol copolymer (EVOH) and glass beads (GB) or fibers (GF) was investigated. The systems studied were based on a binary PP/EVOH immiscible blend, representing a blend of a semi‐crystalline apolar polymer with a semi‐crystalline highly polar copolymer. The ternary systems studied consisted of filler particles encapsulated by EVOH, with some of the minor EVOH component separately dispersed within the PP matrix. Modification of the interfacial properties was done using silane coupling agents for the EVOH/glass interface and compatibilization using a maleic anhydride grafted PP (MA‐g‐PP) for the PP/EVOH interface. Both glass fillers increased the dynamic modulus and decreased the damping of the neat polymers and of their binary blends, especially in the rubbery region. GF has a more profound effect on both the modulus and the damping. Glass surface treatments and compatibilization have only a marginal effect on the dynamic mechanical behavior of the ternary blends. Yet, compatibilization shifted the polymers' T_gS to higher temperatures. Both glass fillers increased the elastic modulus of the binary blends, where GF performed better than GB as a reinforcing agent. GF slightly increased the strength of the binary blends while, GB reduced it. Both fillers reduced the ductility of the binary blends. The blends' mechanical properties were related to the morphology and their components' crystallinity. The compatibilizer increases both stiffness and strength and reduces deformability.     

SELF REINFORCING COMPOSITE BASED ON EPR/LCP BLEND

Blends of ethylene propylene rubber (EPR) and thermotropic liquid crystalline polymer (TLCP) have been prepared by melt-mixing technique. Processing studies indicated the decrease in the viscosity of the blends with the addition of LCP. The mechanical properties like tensile strength and modulus increased up to 10% of LCP and then decreased. The crystallinity increased with an increase in the LCP content. At higher levels of LCP, crystal growth is favored. Thermal studies indicated the endothermic signals that were more prominent at all the peak temperatures. The surface degradation increases with an increase in elastomer (EPR) content in the blend. The relaxation phenomena, as observed from Dynamic Mechanical Thermal Analysis (DMTA) analysis, are changing depending on the blend ratio. The dynamic modulus and stiffness increased with the addition of LCP in the blend. Under dynamic application, at higher levels of LCP, it was observed from scanning electron microscope that there were no cracks at the interface between the EPR and the glass fibers suggesting the better wetting of the fibers by the EPR.     

Development of Micro-Debond Methods for Thermoplastics Including Applications to Liquid Crystalline Polymers

Micro-bead and related debond techniques were used to study adhesion of liquid crystalline copolyesters (LCPs) and other semi-crystalline thermoplastic polymers to glass fibers. For polymers with poor flow even at high temperatures, symmetric beads on fibers were difficult to prepare so an alternative sample preparation method was developed where glass fibers were inserted into thin sections of molten polymer. Glass fibers of widely-varying diameters were used in order to extend the dynamic range of the debond techniques in terms of debonding area, showing a significant improvement in precision over that demonstrated previously with micro debond techniques. The fibers were freshly prepared in our laboratory and silane coated when necessary, which allowed us to minimize fiber surface heterogeneity effects which are believed to influence strongly debond test results. It was found that chemical bonding of the LCPs was quite favorable as was indicated by fracture surface analysis and by comparison with the shear strength of the neat resins. The apparent poor interphase strength in fiber-reinforced LCP composites is proposed to be due to orientation of the LCP molecules near the fiber interface leading to a cohesively weak layer of LCP near the interface. Reactive silane coupling agents lead to no improvement in interface strength as compared with bare glass because chemical reaction occurs on both surfaces. This results in very strong interfaces leading to polymer cohesive failure near the interface of all thermoplastics studied here     

Effect of a filler on the rheological and mechanical properties of the liquid‐crystalline polyester–poly(methyl methacrylate) blends

The rheological and mechanical properties of the blends of liquid‐crystalline polyester (LCP) and poly(methyl methacrylate) (PMMA) filled with aluminum borate whiskers have been studied. It was established the combined action of reinforcing LCP and filler onto the property of PMMA matrix leads to marked reinforcing of PMMA. At 10% of filler and 30% of LCP, the tensile strength of PMMA increases by 30% and elasticity modulus by 110%, the processability being no worse. The viscosity of the blend PMMA + 30% LCP + 10% filler practically is the same as the PMMA melt viscosity at 220°C. With increasing concentration of LCP up to 30%, the filler effect in binary matrix becomes more essential. The possible reason is the preferential adsorption of LCP at the filler interface (surface segregation) and additional ordering of LCP near the surface, possible, due to additional stretching of nematic phase in the convergent flow zone. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 993–999, 2000     

Reactive extrusion of in-situ composite based on PET and LCP blends

The “in-situ” compatibilization for a PET/LCP blend via transesterification reactions in a twin-screw extruder having a very short residence time is investigated through thermal, rheological, and mechanical studies. Inclusion of a small amount of liquid crystalline polymer (LCP) enhanced the crystallization rate of the poly(ethylene terephthalate) (PET) matrix. It acted as a nucleating agent. LCP lowered the blend viscosity above T_cn (crystalline-nematic transition temperature), working as a processing aid. However, the addition of dibutyltindilaurate (DBTDL) as a reaction catalyst was found to increase the viscosity of the blends, diminish the size of the dispersed phase, enhance its adhesion with the matrix, and lead to an increase of mechanical properties of two immiscible phases. Hence DBTDL is helpful in producing a reactive compatibilizer by reactive extrusion at the interface of this polyester blend system. The optimum catalyst amount turned out to be about 500 ppm when the reaction proceeds in 90/10 PET/LCP polyester blend systems. Its effect on the mechanical properties is discussed in detail. The structural change of reactive blend was identified by H¹ NMR and wide angle X-ray diffraction patterns.     

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

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

Silica‐reinforced dynamically vulcanized ethylene–propylene–diene monomer/polypropylene thermoplastic elastomers: Morphology,rheology, and dynamic mechanical properties

Attempts were made to prepare dynamically crosslinked ethylene–propylene–diene monomer/polypropylene (EPDM/PP, 60/40 w/w) blends loaded with various amounts of silica as a particulate reinforcing agent. The dispersion of silica between the two phases under mixing conditions, and also extent of interaction, as the two main factors that influence the blend morphology were studied by scanning electron microscopy. Increasing the silica concentration led to the formation of large‐size EPDM aggregates shelled by a layer of PP. Dynamic mechanical thermal analysis performed on the dynamically cured silica‐loaded blend samples showed reduction in damping behavior with increasing silica content. Higher rubbery‐like characteristics under tensile load were exhibited by the silica‐filled EPDM/PP‐cured blends. However, increasing the silica level to 50 phr led to the enhancement of interface, evidenced by increases in the tensile modulus and extensibility of the blend compared with those of the unloaded sample. Addition of a silane coupling agent (Si69) into the mix improved the mechanical properties of the blend, attributed to the strengthening of interfacial adhesion between the PP matrix and silica‐filled EPDM phase. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2000–2007, 2004     

Development and evaluation of surface treatments to enhance the fiber-matrix adhesion in PAN-based carbon fiber/liquid crystal polymer composites. Part I: Coupling agent and amine surface treatments

Several surface treatments, using both commercially available coupling agents and reagents containing multiple amines, were applied to commingled continuous as-received AS4 carbon reinforcing fiber/liquid crystal polymer (LCP) matrix fibers. Unidirectional composites (normally 60 vol% carbon fiber) were prepared from as-received and treated commingled fibers and characterized. To estimate the effect the effect of the treatments on fiber-matrix adhesion, short beam shear (SBS) tests were conducted, the failure surfaces were examined, and spectroscopic studies wee performed. The mean SBS strength of the as-received unidirectional AS4 carbon fiber/LCP matrix composite system was 49 MPa. The best coupling agent and amine treatments yielded increases in composite shear strength of ∼ 10 to 20%, relative to the as-received AS4/LCP system. For the amine treatments, ESCA and FTIR analyses suggested of both the carbon and LCP fibers may have caused the increased adhesion. Moreover, SEM analysis of the failure surfaces of SBS specimens from composites prepared with the treated fibers may have caused the increased adhesion. Moreover, SEM analysis of the failure surfaces of SBS specimens from composites prepared with the treated fibers (both with coupling agents and amines) showed that strong fiber-matrix adhesion was present. That is, failure occurred in the LCP matrix material.     

Effect of interface on the morphology and properties of composites comprising poly(propylene) and short organic fibers

The effect of the fiber surface modification with an azide derivative on the morphology and properties of composites based on poly(propylene) (PP) and short poly(ethylene terephthalate) (PET) and nylon 66 (PA) fibers, has been investigated. Both organic fibers act as reinforcement of the PP, and the reinforcing effect increases with the introduction of azide groups on the chemical structure of the fibers. This effect is more sensible in PP/short PET fiber composites although PA fibers gives rise to higher improvements in toughness. Scanning electron microscopy (SEM) has shown that the azide treatment of PET fibers gives rise to a better wettability and adhesion at the fiber/matrix interface. A good correlation between SEM and mechanical behavior of the composites has been observed.     

In-situ composites: Evaluation of the adhesion between the thermoplastic matrix and the fibers of liquid crystalline polymer

Mechanical properties of fiber reinforced composites depend on the formation of stable adhesive bonds between the constituents. In order to evaluate quantitatively the adhesion between liquid crystal polymer (LCP) fibers and a thermoplastic matrix of polycarbonate, the single fiber composite test (SFC), utilized for testing glass or carbon fiber composites, has been used. Neither chemical nor physical interaction has been found: the PC and LCP phases are completely incompatible. However, a mechanical friction between PC and LCP was observed during the drawing of the sample when the neck of the matrix started.     

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

A co‐polyester liquid crystalline polymer (LCP) was melt blended with an acrylonitrile–butadiene–styrene copolymer (ABS). LCP fibrils are formed and a distinct skin/core morphology is observed in the injection moulded samples. At higher LCP concentration (50 wt%), phase inversion occurs, where the dispersed LCP phase becomes a co‐continuous phase. While the tensile strength and Young's modulus remain unchanged with increasing LCP content up to 30 wt% LCP, a significant enhancement of the modulus at 50 wt% LCP is observed due to the formation of co‐continuous morphology. The blend modulus is lower than the values predicted by the rule of mixtures, suggesting a poor interface between the LCP droplets and ABS matrix. A copolymer of styrene and maleic anhydride (SMA) was added in the LCP/ABS blends during melt blending. It is observed that SMA has a compatibilizing effect on the blend system and an optimum SMA content exists for mechanical properties enhancement. SMA improves the interfacial adhesion, whereas excess of SMA reduces the LCP fibrillation. Copyright © 2003 Society of Chemical Industry     

In situ composites: Blends of isotropic polymers and thermotropic liquid crystalline polymers

Melt blending of a variety of conventional isotropic polymers (both crystalline and amorphous) has shown that considerable reinforcement is obtained from the inclusion of thermotropic liquid crystalline polymers (LCP). When the LCP is a minor component it forms highly elongated domains parallel to the flow direction. The intrinsically high strength and stiffness of the LCP improve the mechanical properties of the resulting blend. This approach is distinguished from the common practice of filling polymers with chopped glass and carbon fibers by the fact that the reinforcing component comes into existence during processing (molding or extrusion). Many of the problems associated with fibrous fillers are avoided. For example, viscosity of the “in situ composite” is actually lower than that of the base polymer and wear on the compounding and processing equipment is reduced.     

Carbamoyl ethylation of starch for enhancing the adhesion capacity to fibers

The influence of starch carbamoylethylation upon the adhesion capability of starch to pure cotton, all polyester, and polyester/cotton blend fiber substrates were investigated. The carbamoylethyl starch was prepared by the reaction of starch with acrylamide in an aqueous dispersion. The capability was evaluated in terms of the maximum strength and work‐to‐break of a roving impregnated with the starch pastes. The mechanical behaviors of the adhesive layers were estimated through a method by casting starch films and then by measuring their behaviors under controlled condition. It was found that the carbamoylethylation is an effective means for enhancing the adhesion of starch to fibers. No matter what type of the fibers is used, the adhesion capability obviously enhances compared with those of unmodified starch, even if the degree of substitution is at a very low level. The capacity increases steadily as the modification extent increases. Moreover, the experimental results are also discussed and analyzed especially through the failure type, internal stress, stress concentration, and mechanical behaviors of the adhesive layers among fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Reinforcing performance of recycled PET microfibrils in comparison with liquid crystalline polymer for polypropylene based composite fibers

Recycled polyethylene terephthalate (rPET) used as an alternative reinforcing additive for polypropylene (PP) based composite fibers, compared with liquid crystalline polymer (LCP), was investigated. Both PP-LCP and PP-rPET composites were prepared as fiber using hot drawing process. The effects of draw ratios and compatibilizer dosages on morphology in relation to tensile properties of both types of the composite systems were studied. The variation of draw ratios resulted in much change of stress–strain behavior in compatibilized rPET composite system owing to the obvious difference in morphological change of rPET dispersed phase upon drawing. Tensile strength and extensibility of both composites system were significantly improved with compatibilizer loading. The tensile strength of compatibilized rPET-composite fibers was higher than that of the compatibilized LCP system. The obtained results demonstrated the high potential of rPET as a well-defined reinforcing material for PP based composite fiber under the improved interfacial adhesion promoted by compatibilizer.     

Effect of alkali‐resistant glass fiber on polypropylene/polystyrene blends: Modeling and characterization

Alkali‐resistant glass fiber (GF) reinforced polypropylene (PP)/polystyrene (PS) blends were prepared by melt mixing in a Thermo Haake Rheochord mixer. Variation in thermal and mechanical properties with the addition of glass fibers into the polypropylene/polystyrene blends was investigated. The characterization of PP/PS/GF composites was done by dynamic mechanical analysis (DMA), thermogravimetric analysis, scanning electron microscope, and transmission electron microscope. The experimentally observed tensile properties of glass fiber reinforced PP/PS blends were compared with various published models. It was found that the experimental results agree well with Hui‐ Shia and series models. DMA tests revealed an increase in storage modulus with fiber loading confirms the greater degree of stress transfer from the matrix to the fiber. TEM micrographs reveal that the glass fibers are located at the interface between the blend components. POLYM. COMPOS., 37:398–406, 2016. © 2014 Society of Plastics Engineers     

Prospect of nanoscale interphase evaluation to predict composite properties

For meeting the requirements of lightweight and improved mechanical properties, composites could be tailor-made for specific applications if the adhesion strength which plays a key role for improved properties can be predicted. The relationship between wettability and adhesion strength has been discussed. The microstructure of interphases and adhesion strength can be significantly altered by different surface modifications of the reinforcing fibers, since the specific properties of the interphase result from nucleation, thermal and/or intrinsic stresses, sizing used, interdiffusion, and roughness. The experimental results could not confirm a simple and direct correlation between wettability and adhesion strength for different model systems. The main objective of the work was to identify the interphases for different fiber/polymer matrix systems. By using phase imaging and nanoindentation tests based on atomic force microscopy (AFM), a comparative study of the local mechanical property variation in the interphase of glass fiber reinforced epoxy resin (EP) and glass fiber reinforced polypropylene matrix (PP) composites was conducted. As model sizings for PP composites, γ-aminopropyltriethoxysilane (APS) and either polyurethane (PU) or polypropylene (PP) film former on glass fibers were investigated. The EP-matrix was combined with either unsized glass fibers or glass fibers treated with APS/PU sizing. It was found that phase imaging AFM was a highly useful tool for probing the interphase with much detailed information. Nanoindentation with sufficiently small indentation force was found to be sufficient for measuring actual interphase properties within a 100-nm region close to the fiber surface. Subsequently, it also indicated a different gradient in the modulus across the interphase region due to different sizings. The possibilities of controlling bond strength between fiber surface and polymer matrix are discussed in terms of elastic moduli of the interphases compared with surface stiffness of sized glass fibers, micromechanical results, and the mechanical properties of real composites.     

Mechanical properties of in-situ composites based on partially miscible blends of glass-filled polyetherimide and liquid crystalline polymers

The use of inorganic (glass) fiber reinforcement to enhance the mechanical properties and reduce the anisotropy of in situ composites based on blends of liquid crystalline polymers (LCPs) with polyetherimide (PEI) is discussed. It was found that the tensile and flexural moduli are increased and the anisotropy is reduced with increasing grass content (when compared at equivalent LCP weight fractions). The creep compliance of the PEI/LCP composites is reduced upon the addition of glass fibers. However, the disadvantage is that the processability worsens upon addition of glass fibers to the PEI/LCP in situ composites. The effect of adding glass reinforcement on the ultimate tensile strength is less clear, because the data do not show any consistent trend. Similarly, the elongation at break and toughness do not show any consistent improvement upon addition of glass reinforcement. Morphological studies show that there is considerable difference between the size and texture of the reinforcing glass fibers and LCP microfibrils.     

低摩尔质量PC/PP共混体系的增韧机理研究

以熔融共混法制备了低摩尔质量PC／PP合金材料，借助于力学性能测试、SEM观察等手段对这一共混体系的增韧机理进行了研究。结果表明，剪切屈服和界面脱粘是该共混体系能量耗散的主要形式．界面张力对体系形态结构和韧性的影响较大，增强界面粘结有利于材料韧性的提高。提出的增韧机制模型可以较好地对该体系的增韧机理作出解释。PP可以作为PC的增韧剂使用，并且可在不降低其流动性的前提下较大幅度地提高低摩尔质量PC的韧性。     

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