超高分子量聚乙烯膜轴向压缩变形结构的研究

继刚性聚合物经溶液液晶(如芳香族聚酰胺)或熔融液晶(如芳香族聚酯)纺丝制取高性能纤维获得成功后,利用冻胶纺丝等技术制取超高分子量聚乙烯(UHMW-PE)高性能纤维的研究已取得突破性进展。这类纤维具有伸直链结构,大分子沿材料拉伸方向高度取向和结晶,显示出优异的抗张性能,具有很大的拉伸强度和模量。     

冻胶纺丝法制备高强度高模量纤维

本文概述了冻胶纺丝技术发展简况,以聚乙烯为例,对冻胶超高拉伸制备高强度高模量纤维的原理以及制备过程和用途作了介绍。     

长碳链聚醚酰胺弹性纤维开发及其弹性机理

以长碳链聚酰胺弹性体为原料,通过熔融纺丝技术制备了高性能化新型长碳链聚醚酰胺(LPAE)弹性纤维.该弹性体是以基于生物来源单体的长碳链聚酰胺为硬段,以聚醚为软段,其弹性可通过调节软硬段比例有效调控.测试结果表明,与目前市场上应用广泛的氨纶莱卡(LYCRA)相比,软段含量较高的LPAE纤维具有高断裂伸长,低初始模量的特点;在200%伸长范围内,其弹性回复率与氨纶相当,耐热性优于氨纶.分析得知,LPAE纤维的高弹性源于硬段聚酰胺存在强氢键相互作用且结晶度高,同时硬段充当物理交联点;软段具有良好的柔性,可以发生大变形,这种软硬段交替的嵌段分子链结构形成三维网络.大应变下,LPAE纤维弹性回复率降低是由分子链滑移及软段拉伸诱导结晶共同造成的.     

稳定射流电纺丝法制备定向排列的壳聚糖超细纤维

采用电驱动纺丝,以壳聚糖(CTS)为研究对象材料,通过引入超高分子量聚氧化乙烯(PEO)调节纺丝液的黏弹性,实现抑制电纺丝固有的射流不稳定弯曲摆动来得到单一的稳定射流,从而可以像传统工业上的干、湿法纺丝一样制备定向的超细CTS纤维(称为稳定射流电纺丝,SJES).系统地研究了SJES的工艺参数(如CTS/PEO质量比、纺丝电压、接收距离、凝固浴成分、辊筒转速等)对制备定向的超细壳聚糖纤维的影响,并通过SEM、FTIR、WAXD、纳米力学拉伸仪等研究了所制备纤维的形貌、结构与性能.结果表明,SJES法制备的CTS纤维直径在10μm以下,优化参数(如电压和辊筒转速)可使纤维直径细化到3μm左右.纤维单丝具有较高的力学性能,断裂强度和纤维模量可以分别达到(762±93)MPa和(11±6)GPa.稳定射流电纺丝方法制备的超细纤维与常规电纺丝法制备的纤维相比,具有较高的微晶取向度.     

聚酰亚胺纤维

聚酰亚胺纤维具有高强度模、耐高温、耐辐射等优越的性能。在多种纺制聚酰亚胺纤维的方法中,湿纺容易制得高强高模的样品。本文主要介绍了聚酰亚胺纤维的一步法湿纺、二步法湿纺和熔融纺丝方法,并对纤维的性能进行了概述。     

盐浓度与海藻酸钠/磷虾蛋白复合体系性能的相关性

采用湿法纺丝技术制备了海藻酸钠/磷虾蛋白(SA/AKP)复合纤维, 通过傅里叶变换红外光谱(FTIR)分析了SA/AKP复合体系的氢键相互作用, 用X射线衍射仪、 流变仪及SEM研究了盐(NaCl)浓度对复合体系的结晶、 流动性和形态结构的影响. 结果表明, SA/AKP复合体系中存在分子内和分子间氢键, 分子间氢键的强度随复合材料中盐浓度的增加而增强. 盐浓度的增加导致SA/AKP复合材料的结晶度增加, 流动黏度先降低后增加, 力学性能先增加后降低. SA/AKP纤维的SEM照片显示结晶的盐与纤维分离, 并且复合纤维表面沟槽结构逐渐减少, 表面更加致密光滑. AKP在SA/AKP复合体系中呈完全取向状态.     

纤维的纺丝与拉伸

某些高聚物经过纺丝加工可以变成纤维状,但其时强度低、断裂伸长大,必须经过拉伸使分子取向,并固定下来,所谓定型:其时强度大增,断裂伸长也降低,这样才成为有用的纤维。纤维的形状有显著的几何不对称性,它的直径一般在10—20微米,作特殊用途的纤维也有0.1—100微米的,长度比直径大20—500倍以至无限大。截面形状有各种各样,随纺丝条件而不同;如聚酰胺类是圆的,而聚丙烯腈是哑铃式,纤维素衍生物纤维是无规的,用特制纺孔还可以制成空心纤维,它的强度不降低而同时有保温作用。作为纤维材料应具下列性质:分子量在10~4数量级,具有一定高的     

丙烯腈的悬浮聚合

<正> 适用于普通溶液纺丝加工成形的聚丙烯腈(PAN)的分子量一般在5—8万范围内,近年来发展起来的冻胶纺丝方法使得(?)>4.0×10~5的超高分子量PAN也可以纺丝成形,成为制备高强高模PAN纤缎的有效方法之一。随着PAN材料应用领域的开拓,合成超高分子量的PAN是一个首要解决的问题。     

PHBV电纺纤维结构与形态的研究

利用电纺丝法制备了超细聚 β 羟基丁酸戊酸酯 (PHBV)纤维 ,通过扫描显微镜 (SEM)、差热分析(DSC)、宽角X射线衍射和偏振红外吸收光谱对产品进行了结构与形态的表征 .研究了纺丝过程中溶液浓度、电压和接收距离 3个参数对纤维形态的影响 .结果表明 ,溶液浓度是决定性的 ,只有高于一个定值才能获得单一的纤维产品 .与流延成型的PHBV相比 ,电纺丝具有较高的取向度和结晶度 .原因可能是 ,电场力下喷丝震荡过程中带来的拉伸作用从而引起分子链的规整排列     

定形相变复合材料的研究进展——静电纺丝法

静电纺丝是制备定形相变复合材料的重要方法之一,本文综述了静电纺丝法制备定形相变复合材料的研究进展,主要包括溶液静电纺丝、溶液-溶液同轴静电纺丝、熔融-溶液同轴静电纺丝和静电纺纳米纤维膜物理吸附等,总结了静电纺丝常用的固-液相变材料(如脂肪族长链烷烃、大豆蜡、脂肪酸及其二元低共熔物、脂肪酸酯和聚乙二醇等)和支撑材料(如醋酸纤维素、聚对苯二甲酸乙二醇酯、聚乙烯吡咯烷酮、聚偏氟乙烯、聚乳酸、聚氨酯、聚酰胺6、聚丙烯腈及其碳纳米纤维等)。     

表面复合纳米SiO_2和碳纳米管玻璃纤维增强尼龙6的结构与性能

利用静电相互作用在玻璃纤维(GF)表面分别复合纳米二氧化硅(SiO2)和多壁碳纳米管(MWNTs),制备了GF-SiO2、GF-MWNTs复合增强体,并通过转矩流变仪制备了尼龙6(PA6)/GF-SiO2和尼龙6(PA6)/GF-MWNTs复合材料.利用扫描电子显微镜(SEM),示差扫描量热仪(DSC),热机械分析仪(DMA)等手段研究了复合材料的微观结构、热学及力学性能.结果表明,静电复合的方法可以使纳米二氧化硅(nano-SiO2)、多壁碳纳米管(MWNTs)在GF表面达到均匀吸附,复合增强体能加快尼龙6的结晶速度,并使材料的玻璃化温度、动态模量、拉伸强度、结晶温度等明显提高,其中GF-MWNTs对复合材料性能的提高最明显,拉伸强度提升了21%,模量提高了28%.     

Structure and Properties of β-Polypropylene Reinforced by Polypropylene Fiber and Polyamide Fiber

Matrix/fiber composites of β-form isotactic polypropylene(iPP) matrix and α-iPP or PA6 fibers were prepared by laminating technique under different preparation temperatures. The mechanical properties and interfacial morphologies of these composites were studied by tensile test, optical microscopy and scanning electron microscopy, respectively. The experimental results show that the tensile yield load and tensile modulus of β-iPP/PA6 matrix/fiber systems increased significantly at the expense of elongation at break. These mechanical properties show essentially no dependence on the sample preparation temperature. On the other hand, the mechanical properties of iPP matrix/fiber single polymer composites depend strongly on the sample preparation temperature. At low sample preparation temperature, e.g., 172 ℃, the solid α-iPP fiber induces α-iPP crystallization, leading to the formation of α-iPP transcrystalline layer around the fiber. This results in a remarkable increment of the tensile yield load and tensile modulus. The elongation at break is also much better than that of the iPP/PA6 matrix/fiber system. It reflects a better interfacial adhesion of the single polymer composite compared with the iPP/PA6 composite. At higher sample preparation temperature, e.g., 174 ℃ or 176 ℃, the partial surface melting of the oriented fiber allows interdiffusion of iPP molecular chains in the molten fiber and matrix melt. The penetration of matrix chains into the molten iPP fiber results in some iPP molecular chains being included partially in the recrystallized fiber and the induced β-transcrystalline layers. This kind of configuration leads to an improvement of interfacial adhesion between the fiber and matrix, which causes a simultaneous increase of the tensile yield load, tensile modulus and elongation at break of β-iPP.     

Continuous spinning of a single-walled carbon nanotube-nylon composite fiber

We report a chemical processing technology that allows the continuous spinning of single-walled carbon nanotubes (SWNTs)-nylon 6 (PA6) fibers by the in-situ polymerization of caprolactam in the presence of SWNTs, which simultaneously optimizes the morphology of the composite. We show that caprolactam is an excellent solvent for carboxylic-acid-functionalized SWNTs (SWNT-COOH) and that this allows the efficient dispersal of the SWNTs and subsequent grafting of PA6 chains to the SWNTs through condensation reactions between the carboxylic-acid group on SWNT-COOH and the terminal amine group of PA6. The existence of a graft copolymer between the PA6 chains and the SWNTs is demonstrated by IR, TGA, and AFM studies, and we show that the solubility of the polymerized material in formic acid is controlled by the degree of graft copolymerization. The amount of grafted PA6 chains that are attached to the SWNTs can be adjusted by controlling the concentration of the initiator (6-aminocaproic acid). The process leads to a uniform dispersion of the SWNTs, and the presence of the graft copolymer increases the polymer/SWNT compatibility while strengthening the interfacial interaction between the nanotube and matrix. The Young's modulus, tensile strength, and thermal stability of the SWNT-reinforced composite fibers produced by this process are significantly improved.     

Rheological aspect on electrospinning of polyamide 6 solutions

Polyamide 6 (PA6) solutions in formic acid (FA) and deionized water cosolvent may behave as polyelectrolyte or neutral solutions depending on the cosolvent composition. In this study, both polyelectrolyte and neutral PA6 solutions were prepared for electrospinning, and their spinnability was correlated with their rheological properties. In addition, the effects of PA6 average molecular weight and carbon nanocapsule (CNC) nanoparticle addition on solution rheology and electrospinnability were investigated. Microstructure and thermal properties of the as-spun fibers were identified by wide-angle X-ray diffraction, polarized Fourier infrared spectroscopy, and differential scanning calorimetry (DSC). Due to the chain expansion, polyelectrolyte solutions with 99 vol.% FA solvent possess much lower entanglement concentration (?_e, ∼1 wt.%) than neutral solutions (∼7 wt.%) prepared by 90 and 85 vol.% FA solvent. Compared with the neutral solution, the polyelectrolyte solution is more advantageous because a lower concentration is sufficient to obtain bead-free PA6 fibers. However, at a concentrated regime of 15 wt.% solution, the obtained fibers exhibit a larger diameter due to the higher entanglement density. For the crystalline structure, the content and orientation of α-form crystals are higher in the PA6 fibers obtained from the polyelectrolyte than from the neutral solution. When PA6 with a lower molecular weight is used, a higher concentration is required to develop the entangled chains to produce bead-free fibers. Homogeneous PA6 solutions filled with CNCs exhibit more elastic behavior than unfilled solutions due to the presence of the CNC–CNC network, aside from the entangled network of PA6 chains. Electrospinning of the CNC-filled solutions yields PA6 fibers with CNC aggregates protruding from the fiber surface. The inclusion of CNC in the PA6/FA solution produces fibers possessing enhanced α-form crystals with reduced orientation. In all cases, DSC heating traces of the as-spun fibers identify a high melting temperature (HMT) phase of PA6. The amount of HMT phase decreases, provided that more water or CNCs are added into the PA6/FA solution for electrospinning.     

Preparation and characterization of novel crown ether functionalized ionic liquid-based solid-phase microextraction coatings by sol-gel technology

A novel crown ether functionalized ionic liquid (IL), 1-allyl-3-(6'-oxo-benzo-15-crown-5 hexyl) imidazolium hexafluorophosphate was synthesized and used as selective stationary phase to prepare task-specific IL-based solid phase microextraction (SPME) fibers by sol-gel method and free radical cross-linking technology. The underlying mechanism of the sol-gel reaction was proposed and the successful chemical bonding of the crown ether functionalized IL to the formed hybrid organic-inorganic copolymer coating was confirmed by FT-IR spectroscopy. The performance of this in situ created crown ether functionalized IL-based SPME fibers, was investigated in detail. The coating has porous surface structure, stable performance in high temperature (to 340 °C) and in different solutions (water, organic solvent, acid and alkali), and good coating preparation reproducibility. In contrast to the sol-gel derived 1-allyl-3-methyl imidazolium hexafluorophosphate-based coating prepared in our previous work with the identical procedure, the extraction performance of this newly developed sol-gel crown ether functionalized IL-based coating was superior for alcohols, phthalate esters, phenolic environmental estrogens, fatty acids and aromatic amines due to the introduction of benzo-15-crown-5 functional group in IL structure. Moreover, it was shown to provide higher or comparable extraction efficiencies for most analytes studied than did the commercial PDMS, PDMS/DVB and PA fibers.     

High‐strength electrically conductive fibers: Functionalization of polyamide,aramid, and polyester fibers with PEDOT polymer

In this work, high‐performance fibers such as aramid (Twaron), polyamide (PA6), polyester (PET), and hybrid Twaron/PA6 fibers were transformed into electroactive fibers by coating them with conjugated polymer, poly(3,4‐ethylenedioxythiophene) (PEDOT) through vapor phase polymerization (VPP) method. The VPP is considered as an efficient technique for depositing CPs on different substrates regardless of their lower solubility in various solvents. In this paper, PEDOT‐coated high‐performance fibers were prepared under already optimized reaction conditions, and then a comparison between electrical, thermal, and mechanical properties of different fibers, before and after coating, was made. The obtained coated fibers were characterized through scanning electron microscope (SEM), thermogravimetric analysis (TGA), 2‐probe electrical resistance measurement method, and tensile testing. It was revealed that at particular reaction conditions, all high performance textile substrates were successfully converted into electroactive fibers. The voltage‐current (V‐I) characteristics showed that PEDOT‐coated polyester fibers exhibited highest conductivity value among all other substrate fibers. The active PEDOT layers on high performance fibers could behave as an antistatic coating to minimize the risks associated with static charges at work places. Also, the obtained fibers have potential to be used as smart materials for various medical, sports, and military applications.     

Mechanical properties, crystallization and melting behaviors of carbon fiber-reinforced PA6 composites

Polyamide-6 (PA6)/carbon fiber (CF) composites were prepared by melt-extrusion via continuous fiber fed during extruding. The mechanical, thermal properties, and crystallization behavior of PA6/CF composites were investigated. It was found that the tensile modulus and strength of the composites were increased with the addition of CF, while their elongations at break were decreased. Scanning electron microscopy observation on the fracture surfaces showed the fine dispersion of CF and strong interfacial adhesion between fibers and matrix. Dynamic mechanical analysis results showed that the storage modulus of PA6/CF composites was improved with the addition of CF. Non-isothermal crystallization analysis showed that the CF plays a role as nucleating agent in PA6 matrix, and the α-form crystalline structure was favorable in the PA6/CF composites, as confirmed from the X-ray diffraction analysis. A trans-crystallization layer around CF could be observed by polarizing optical microscopy, which proved the nucleation effect of carbon fiber surface on the crystallization of PA6. The thermal stability of PA6/CF composites was also enhanced.     

The effects of surface treated carbon fibers and CaCO<Subscript>3</Subscript> nanoparticles inclusions on the mechanical performances of PA6/ABS-based composites

The mechanical and morphological characteristics of PA6/ABS (60/40)-based hybrid composite containing HNO₃-treated short carbon fibers (HSCF) and CaCO₃ nanoparticles have been experimentally studied. A counter-rotating twin-screw extruder and an injection molding machine were employed to produce different samples containing 10 wt % of HSCF and 0, 2, 5 and 8 wt % of CaCO₃ nanoparticles. The SEM observations indicated high-quality adhesion between HNO₃-surface treated carbon fibers and PA6/ABS polymer matrix. In addition, the morphological studies showed that the inclusion of CaCO₃ nanoparticles caused a significant effect on the ABS particle dispersion in PA6/ABS matrix. The mechanical properties assessments revealed that the incorporation of 10 wt % HSCF into the PA6/ABS can significantly improve tensile strength (82%), tensile modulus (107%), flexural strength (98%), flexural modulus (104%) and impact resistance (24%). The inclusion of CaCO₃ nanoparticles, in the presence of 10 wt % HSCF, led to the noticeable improvements of tensile strength (128% for 2 wt % CaCO₃), tensile modulus (199% for 5 wt % CaCO₃), flexural strength (146% for 5 wt % CaCO₃), flexural modulus (204% for 5 wt % CaCO₃) and impact resistance (46% for 2 wt % CaCO₃). The surface treatment of carbon fibers, dispersion conditions of nanoparticles and ABS phase in polymeric matrix were found to be the major important factors affecting the mechanical properties.     

The tensile properties of HNO3‐treated carbon fiber reinforced ABS/PA6 composites

In this study, acrylonitrile‐butadiene‐styrene (ABS) terpolymer was reinforced with HNO₃‐treated short carbon fibers (SCFs) [(hollow carbon fibers (HCFs)]. The effects of HCF concentration on the tensile properties of the composites were examined. Increasing the HCF concentration in the ABS matrix from 10 to 30 wt% resulted in improved tensile strength and tensile modulus. To obtain a strong interaction at the interface, polyamide 6 (PA6) at varying concentrations was introduced into the ABS/10 wt% SCF composite. The incorporation and increasing amount of PA6 in the composites increased tensile properties of the ABS/PA6/HCF systems due to the improved adhesion at the interface, which was confirmed by the ratio of tensile strength as an adhesion parameter. These results were also supported by scanning electron micrographs of the ABS/PA6/HCF composites, which exhibited an improved adhesion between the SCFs and the ABS/PA6 matrix. Copyright © 2009 John Wiley & Sons, Ltd.