Self-reinforced polypropylene/LCP prepregs and laminates

Polypropylenes (PPs) of various molecular weights were mixed with a thermotropic liquid crystal polymer (LCP) to prepare unidirectional sheets (prepregs), quasi-isotropic and unidirectional laminates. The mechanical properties and the morphology of the prepregs and the laminates at 0° and 90° with respect to the machine direction were investigated as a function of draw ratio, LCP concentration and molecular weight of the PP. The results for prepregs and laminates showed that both drawing and LCP concentration generally enhanced modulus and tensile strength in machine direction. The morphology of LCP changed from spherical or ellipsoidal droplets to elongated fibrils as the draw ratio increased. The diameter of LCP fibrils decreased with increasing molecular weight of the PP matrix, indicating more effective droplet breakup and better mixing in the case of high molecular weight PP.     

Self-reinforced thermoplastic-LCP prepregs and laminates

Self-reinforced sheets (prepregs) have been prepared by stretching extruded sheets made of thermoplastic (TP) and a thermotropic liquid crystalline polymer (LCP) blend. The sheets are formed by extrusion through a coathanger die, device. Processing at this stage is done at a temperature at which both components in the blend are melt processable. These prepregs are laid up in multi-layers in a direction parallel to the stretching direction or in the direction of 45° with respect to each previous layer. The lay-ups are compression molded into unidirectional or isotropic laminates at temperatures below the melt processing temperature of the LCP. Various pairs of TP and LCP have been studied. These include polypropylene and an LCP based on p-oxybenzoyl, terephthaloyl and hydroquinone moieties, polyphenylene oxide (PPO) and polystyrene/PPO alloy and a LCP based on 6-oxy-2-naphthoyl and p-oxybenzoyl moieties. Mechanical properties of the prepregs and laminates were measured and compared with those obtained from injection molded samples. Surprisingly, tensile strength and modulus of isotropic laminates are found to be higher than those of injection molded samples in the flow direction. Morphlogical studies of the prepregs and laminates indicate the presence of well-defined LCP fibers in various thermoplastic matrices.     

(±45°/90°/0°)_s准各向同性层合板的拉伸强度

根据经典层合板理论,层合板(±45°/90°/0°)s是准各向同性层合板,其拉伸刚度在板面内各个方向上都相同,而拉伸强度是随偏轴角θ改变而变化,即强度方面不具有各向同性的特点。本文首先研究(±45°/90°/0°)s这种准各向同性层合板拉伸强度在偏轴角θ从0°至45°之间的变化情况,然后通过分别改变单层板强度参数和弹性常数来研究该层合板的拉伸强度的变化情况,并分析其破坏形式。最后与NCF材料的试验结果进行了比较。     

The production and properties of oriented polypropylene laminates

The mechanical properties of isotactic polypropylene can be enhanced in one direction by a combination of rolling and drawing in a rolling mill. The longitudinal strength and modulus of the oriented polypropylene (OPP) increases with an increase in draw ratio; however, the transverse properties remain relatively unchanged. In this study, multidirectional OPP laminates [with (0)₂, (0/90)_s and (0/±45)_s lay-ups] were made to obtain sheet materials with improved properties in more than one direction in the plane. A hot-plate welding technique was used to produce these translucent and recyclable laminates. The in-plane properties of the laminates were successfully predicted with classical laminate theory (CLT), which is commonly used to predict the properties of fiber reinforced materials. These laminates can be quasi-isotropic and were found to have improved modulus [up to 6 GPa for (0/90)_s laminates] and strength [up to 150 MPa for (0/90)_s laminates] as well as exceptionally good impact toughness.     

Tensile behavior of unidirectional polyethylene fibers PMMA and glass fibers—PMMA composite laminates

Unidirectional (UD) composite laminates based on glass fibers (GF) and high‐performance polythylene fibers (PEF) were prepared with partially polymerized methyl methacrylate (MMA) at room temperature, followed by heating at 55°C (well below the softening point of PEF) for 2 h. The tensile strength, modulus of elasticity, fiber efficiency and strength efficiency of both the composite laminates, loaded parallel to the fibers, at the same volume fraction range, were investigated. All the properties were compared between the two composite laminates. It was observed that the measured tensile strength and modulus of elasticity deviated from the values calculated from the Rule of Mixture (ROM). The deviation was minimal at the lower volume fraction of fibers, and increased with the fiber volume. An interesting feature that was observed was that the efficiencies of PEF‐reinforced composite was higher than that of the GF‐reinforced composite at the same volume fraction of the fibers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1489–1493, 2000     

Mechanical,morphological, and thermal properties of poly(ethylene 2,6-naphthalate) and copolyester LCP blends

Binary blends of a liquid crystalline polymer (LCP) and poly(ethylene 2,6-naphthalate) (PEN) were melt blended and injection molded. The mechanical properties were studied as a function of LCP content. Both the ultimate tensile strength and Young's modulus are higher than the theoretical values predicted by the rule of mixtures and they display a synergistic behavior at 70 wt % LCP content. However, the tensile strength decreases with LCP content and Young's modulus remained unchanged at lower LCP contents (10 to 30 wt %). The poor mechanical property is attributed to the immiscibility between PEN and LCP and the fibrillation behavior of LCP as revealed by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) results. However, LCP and PEN are found to be partially miscible at higher LCP content, ascertained by DSC and dynamic mechanical analysis (DMA). This is attributed to the transesterification reaction between PEN and PET moiety in the LCP molecules. SEM micrographs reveal a skin/core morphology in the tensile bars, that is, the LCP is better oriented in the skin than in the core region. At lower LCP content, the dispersed LCP phase is spherical in the core and ellipsoidal in the skin, with long axes oriented in the flow direction. DSC studies show that the crystallization rate is significantly enhanced by the presence of LCP up to 50 wt %, where the LCP acts as a nucleating agent for PEN crystallization. The melting temperature decreases with LCP content, probably as a result of imperfect crystals formed in the presence of LCP heterogeneous nucleating centers and the increasing miscibility between LCP and PEN. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 477–488, 2001     

碳玻混编单向复合材料的性能分析

采用碳纤维质量含量分别为7.4%、10.7%、13.8%的三种碳玻层间混编单向织物制备了纤维增强环氧树脂复合材料,分析了该类材料的力学性能与工艺性能。结果表明:碳玻层间混编复合材料的0°拉伸模量和0°压缩模量均随碳纤维含量的提高而升高,掺入碳纤维后碳玻混杂复合材料的0°拉伸强度比纯玻纤复合材料的有所降低,但随碳纤维含量的增加而升高,碳玻层间混编复合材料的0°压缩强度则没有明显的变化规律;掺入碳纤维后,碳玻层间混编复合材料的90°拉伸强度和模量均有所下降;低碳纤维含量的碳玻层间混编单向织物具有良好的Z向渗透性能。该类新材料未来有望在风电叶片结构减重和成本优化上发挥重要作用。     

Mechanical anisotropy in injection-molded polypropylene

By use of a mod with a film gate, two straight polypropylenes (PP) with different melt flow index (MFI) and a glass fiber-reinforced polypropylene (FRPP) were injection molded at various molded at various temperatures into square plates with orientational anisotropy. The anisotropies of tensile property, tensile impact strength, and flexural property were studied on the molded sample cut mainly in the machine direction (MD), 45°-direction (45°), and transverse direction (TD). Both the orders of the yield strength and tensile impact strength of the FRPP, and those of the necking stress and tensile impact strength of the straight PP, were MD >45° >TD, which are reasonable tendencies. The orders of the yield strength and flexural modulus of the straight PP were MD > TD > 45°, which suggests the presence of shear deformation between the lamellae in the skin layer. The variation of the flexural modulus with the angle to the MD fitted well to Hearmon's equation. Generally, for straight PP, the anisotropy of various properties increased as the MFI and cylinder temperature became lower, or as the skin layer became thicker. For the FRPP, the anisotropy increased as the cylinder temperature became higher, or as the degree of the orientation of glass fibers became higher.     

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

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

Structure–tensile property relationship of knitted fabric composites

This paper reports some further studies on the tensile properties of plain weft knitted DuPont Kevlar fiber fabric reinforced epoxy matrix composites. One aim of this work is to investigate systematically the anisotropy of knitted fabric composites. Tensile tests were conducted at different off‐axial angles (0°, 30°, 45°, 60° and 90°) with respect to the wale direction. Fracture modes corresponding to this off‐axial variation were clearly identified. The elastic modulus and tensile strength were found to be the highest in the wale direction (0°), but decreased gradually towards the course direction (90°). This anisotropic study was carried out on both single layered and multilayered (four layered) knitted fabric composites. Another aim is to study the effect of specimen width (or number of loops per specimen width) on the tensile properties. This study indicated an optimum number of loops per sample width required to obtain meaningful tensile test results. Further, edge effect on the tensile properties of the knitted fabric composites was also investigated in the paper. This was achieved through comparative studies on cut and uncut four layered specimens. In the cut specimens the continuity of the yarns is lost at the cut edges, which show a marginal variation in the properties compared with the uncut specimens where the yarns are continuous throughout the specimen. Finally, a study was also carried out to investigate the effect of loop size (or stitch density) on the tensile strength and stiffness of the single layered composites.     

Blends containing liquid crystalline polymers: Preparation and properties of melt-drawn fibers,unidirectional prepregs,and composite laminates

This paper discusses the effect of melt drawing on the mechanical properties and morphology of liquid crystalline polymer (LCP) and thermoplastic polymer blends. Extruded fibers and films of LCP/polymer blends were melt drawn to develop uniaxial orientation of the dispersed LCP phase. The longitudinal modulus increased with increasing draw. The increase in modulus was due to higher aspect ratio of the LCP fibrils and improved molecular orientation of the LCP chains within the fibrils. Laminated composites were prepared using the extruded sheets as prepregs. The mechanical properties and the coefficient of thermal expansion (CTE) of the prepreg and the laminates agreed well with predictions from conventional composite lamination theories.     

Blends of a liquid crystalline polymer with polyether ether ketone

Blends of Polyether ether ketone (PEEK) and a thermotropic liquid crystalline Polymer (LCP) based on paraoxy-benzoyl and oxy-biphenylene terepthaloyl units were prepared using a static mixer attached to a single screw extruder at 420°C. Rheological studies indicated an increase in the viscosity of the blends upon the addition of LCP. Thermal studies on these blends demonstrated their poor thermal stability compared to the parent materials. The mechanical properties indicated improvement in Young's tensile and flexural modulus but no improvement in the break strength with the addition of the LCP. Morphological studies indicated the formation of ellipsoids of LCP at low LCP concentration in the matrix of PEEK, with extended ellipsoids being observable at 25 percent LCP composition. Phase inversion was noticeable at higher LCP content blends with the formation of PEEK fibrils in the matrix of the LCP. Dynamic studies on these blends showed an increase in the storage modulus with the addition of LCP.     

连续玻璃纤维增强聚氨酯复合材料的力学性能

为了代替传统的钢制鱼尾板与绝缘部件组成的"机械绝缘接头",通过拉挤成型制备了连续玻璃纤维(GF)质量分数高达70.5%的聚氨酯/玻璃纤维(PUR/GF)复合材料。分别对复合材料在0°和90°方向进行了拉伸、弯曲和压缩性能测试;同时,结合扫描电子显微镜(SEM)观察了拉伸断口,分析了GF在PUR基体中的分布情况及复合材料在拉伸试验中的断裂机理。研究结果表明,0°方向的拉伸强度、弯曲强度以及压缩强度都有很明显的提高,且均符合钢轨鱼尾板的强度标准。     

Mechanical performance of ternary in situ polycarbonate/poly(acrylonitrile‐butadiene‐styrene)/liquid crystalline polymer composites

Ternary in situ polycarbonate (PC)/poly(acrylonitrile‐butadiene‐styrene) (ABS)/liquid crystalline polymer(LCP) composites were prepared by injection molding. The LCP used was a versatile Vectra A950, and the matrix of composite specimens was PC/ABS 60/40 by weight. Maleic anhydride (MA) copolymer and solid epoxy resin (bisphenol type‐A) were used as compatibilizers for these composites. The tensile, dynamic mechanical, impact, morphology, and thermal properties of the composites were studied. Tensile tests showed that the tensile strength of the PC/ABS/LCP composite in the longitudinal direction increased markedly with increasing LCP content. However, it decreased slowly with increasing LCP content in the transverse direction. The modulus of this composite in the longitudinal direction appeared to increase considerably with increasing LCP content, whereas the incorporation of LCP into PC/ABS blends had little effect on the modulus in the transverse direction. The impact tests revealed that the Izod impact strength of the composites in both longitudinal and transverse direction decreased with increasing LCP content up to 15 wt %; thereafter it increased slowly with increasing LCP. Dynamic mechanical analyses (DMA) and thermogravimetric measurements showed that the heat resistance and heat stability of the composites tended to increase with increasing LCP content. Scanning electron microscopy observation and DMA measurement indicated that the additions of epoxy and MA copolymer to PC/ABS matrix appeared to enhance the compatibility between the PC and ABS, and between the matrix and LCP. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2274–2282, 1999     

Comparison of mechanical properties of epoxy composites reinforced with stitched glass and carbon fabrics: Characterization of mechanical anisotropy in composites and investigation on the interaction between fiber and epoxy matrix

The primary purpose of the study is to evaluate and compare the mechanical properties of epoxy‐based composites having different fiber reinforcements. Glass and carbon fiber composite laminates were manufactured by vacuum infusion of epoxy resin into two commonly used noncrimp stitched fabric (NCF) types: unidirectional and biaxial fabrics. The effects of geometric variables on composite structural integrity and strength were illustrated. Hence, tensile and three‐point bending flexural tests were conducted up to failure on specimens strengthened with different layouts of fibrous plies in NCF. In this article, an important practical problem in fibrous composites, interlaminar shear strength as measured in short beam shear test, is discussed. The fabric composites were tested in three directions: at 0°, 45°, and 90°. In addition to the extensive efforts in elucidating the variation in the mechanical properties of noncrimp glass and carbon fabric reinforced laminates, the work presented here focuses, also, on the type of interactions that are established between fiber and epoxy matrix. The experiments, in conjunction with scanning electron photomicrographs of fractured surfaces of composites, were interpreted in an attempt to explain the failure mechanisms in the composite laminates broken in tension. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Evaluation of mechanical properties of a dense SiC/SiCN composite produced via PIP process

The material behavior of Polymer Infiltration and Pyrolysis based SiC/SiCN composites is studied and the characteristic thermal and mechanical properties in on- (0/90 °) and off-axis (±45 °) direction are summarized. The tensile properties are determined at room temperature and 1300 °C. Based on the ratio of Young’s modulus and strength between on- and off-axis loading, a new approach for the classification of Weak Matrix Composites (WMC) and Weak Interface Composites (WIC) is proposed, which seems to be reasonable for various CMCs. Even without fibre coating mechanical behavior of SiC/SiCN is similar to that of WIC. In order to explain this, a microstructure model is developed and confirmed by analysis of fracture surface. The effect of temperature on the tensile properties is investigated through analysis of residual thermal stresses. Even though at 1300 °C the strength is slightly lower, the fracture strain increased significantly from RT to 1300 °C.     

In situ composites from blends of polycarbonate and a thermotropic liquid‐crystalline polymer: The influence of the processing temperature on the rheology,morphology, and mechanical properties of injection‐molded microcomposites

This work was aimed at understanding how the injection‐molding temperature affected the final mechanical properties of in situ composite materials based on polycarbonate (PC) reinforced with a liquid‐crystalline polymer (LCP). To that end, the LCP was a copolyester, called Vectra A950 (VA), made of 73 mol % 4‐hydroxybenzoic acid and 27 mol % 6‐hydroxy‐2 naphthoic acid. The injection‐molded PC/VA composites were produced with loadings of 5, 10, and 20 wt % VA at three different processing barrel temperatures (280, 290, and 300°C). When the composite was processed at barrel temperatures of 280 and 290°C, VA provided reinforcement to PC. The resulting injection‐molded structure had a distinct skin–core morphology with unoriented VA in the core. At these barrel temperatures, the viscosity of VA was lower than that of PC. However, when they were processed at 300°C, the VA domains were dispersed mainly in spherical droplets in the PC/VA composites and thus were unable to reinforce the material. The rheological measurements showed that now the viscosity of VA was higher than that of PC at 300°C. This structure development during the injection molding of these composites was manifested in the mechanical properties. The tensile modulus and tensile strength of the PC/VA composites were dependent on the processing temperature and on the VA concentrations. The modulus was maximum in the PC/VA blend with 20 wt % VA processed at 290°C. The Izod impact strength of the composites tended to markedly decrease with increasing VA content. The magnitude of the loss modulus decreased with increasing VA content at a given processing temperature. This was attributed to the anisotropic reinforcement of VA. Similarly, as the VA content increased, the modulus and thus the reinforcing effect were improved comparatively with the processing temperature increasing from 280 to 290°C; this, however, dropped in the case of composites processed at 300°C, at which the modulus anisotropy was reduced. Dynamic oscillatory shear measurements revealed that the viscoelastic properties, that is, the shear storage modulus and shear loss modulus, improved with decreasing processing temperatures and increasing VA contents in the composites. Also, the viscoelastic melt behavior (shear storage modulus and shear loss modulus) indicated that the addition of VA changed the distribution of the longer relaxation times of PC in the PC/VA composites. Thus, the injection‐molding processing temperature played a vital role in optimizing the morphology‐dependent mechanical properties of the polymer/LCP composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

国产CCF300碳纤维4轴向无屈曲织物层合板力学性能对比研究

设计制备了两种4轴向碳纤维无屈曲织物(NCF):第一种织物全部采用东丽公司T700 12k碳纤维,第二种织物中66.7%碳纤维采用国产CCF300 3k碳纤维(与东丽T300 3k碳纤维相当)。对该两种织物层合板0°、90°和±45°4个方向的抗拉伸、抗弯曲和抗层间剪切性能进行了测试与对比研究。结果表明:在现有生产条件下,国产CCF300 3k碳纤维最多可以代替4轴向NCF中66.7%的进口T700 12k碳纤维;国产碳纤维NCF层合板各方向归一化后的抗拉伸强度比进口碳纤维NCF层合板低18.7%～26.1%,而其他性能没有显著差别;两种NCF层合板的抗拉伸和抗层间剪切破坏模式相似。     

In‐situ reinforcement of PBT/ABS blends with liquid crystalline polymer

Ternary in‐situ poly(butylene terephthalate) (PBT)/poly(acrylonitrile‐butadienestyrene) (ABS)/liquid crystalline polymer(LCP) blends were prepared by injection molding. The LCP used was a versatile Vectra A950, and the matrix material was PBT/ABS 60/40 by weight. Maleic anhydride (MA) copolymer and solid epoxy resin (bisphenol type‐A) were used as compatibilizers for these blends. The tensile, dynamic mechanical, impact, morphology and thermal properties of the blends were studied. Tensile tests showed that the tensile stregth of PBT/ABS/LCP blend in the longitudinal direction increased markedly with increasing LCP content. However, it decreased sharply with increasing LCP content up to 5 wt%; thereafter it decreased slowly with increasing LCP content in the transverse direction. The modulus of this blend in the longitudinal direction appeared to increase considerably with increasing LCP content, whereas the incorporation of LCP into PBT/ABS blends had little effect on the modulus in the transverse direction. The impact tests revealed that the Izod impact strength of the blends in longitudinal direction decreased with increasing LCP content up to 10 wt%; thereafter it increased slowly with increasing LCP. Dynamic mechanical analyses (DMA) and thermogravimetric measurements showed that the heat resistance and heat stability of the blends tended to increase with increasing LCP content. SEM observation, DMA, and tensile measurement indicated that the additions of epoxy and MA copolymer to PBT/ABS matrix appeared to enhance the compatibility between PBT/ABS and LCP.     

Blends of PBT with rigid thermotropic LCP having flexible side groups: Comparison of their tensile properties with semirigid main-chain TLCP blends

Two new thermotropic liquid crystalline polymers (LCPs) were synthesized. One is a di-mesogenic LCP having a flexible hexamethylene spacer in the main chain, the other is a rigid-type main-chain LCP having alkoxy side groups on the terephthaloyl moiety of the polymer. Blends of LCP with poly(butylene) terephthalate were melt-spun at different LCP contents and different draw ratios to produce a monofilament. Maximum enhancement in the ultimate tensile strength was observed for the blends containing 5% LCP at any draw ratio, and decreased with further increase in LCP content. The initial modulus monotonically increased with increasing LCP content. The tensile properties of the rigid-type LCP blends were higher than those of the flexible main-chain LCP blends. © 1996 John Wiley & Sons, Inc.