OBSERVATIONS ON DEFORMATION BEHAVIOR OF HIGH PERFORMANCE FIBERS BY POLARIZING OPTICAL MICROSCOPY

By means of polarizing optical microscopy (POM), deformation behavior of four kinds of fibers, i.e. ultra highmolecular weight polyethylene (UHMW-PE) fiber, polyvinyl alcohol (PVA) fiber, polyethylene terephthalate (PET) fiber,and wholly aromatic (p-hydroxybenzoic acid/2-hydroxy-6-naphthoic acid) copolyester [P(HBA/HNA)]/PET (ACPET blend)fiber, in axial compression, axial impacting, and bending was observed. In compression, kink bands formed at an angle of55～60° to the fiber axis in 10-times-drawn UHMW-PE fiber, 75～80° in 40-times-drawn sample, 80° in PVA fiber, and 90°in the ACPET blend fiber. In impacting and bending, band angles of UHMW-PE, PVA and PET fibers are nearly the same asthose formed in compression, indicating that slip systems do not change. For any of the four kinds of fiber, band spacingexhibits great differences in compression, in impacting, and in bending, which may be attributed to the differences in thedegrees of strain or stress concentration.     

Preparation and Properties of Chitosan/Konjac Glucomannan Blend Fibers

Chitosan and konjac glucomannan (KGM) blend fibers were prepared by spinning their solution through a viscose‐type spinneret into a coagulating bath containing aqueous sodium hydroxide and ethanol. The structure and properties of the blend fibers were studied with the aids of infrared spectra (IR), scanning electron micrography (SEM) and X‐ray diffraction (XRD). The structure analysis indicated that there were strong interaction and good miscibility between the chitosan and KGM molecule which resulted from intermolecular hydrogen bonds. Mechanical properties and water‐retention properties were measured. Through controlling blend conditions, blend fibers can obtain better mechanical properties than the pure chitosan fiber. The water‐retention values (WRV) of blend fibers increase as the amount of KGM is raised. The fibers treated with alcoholic solution of acetic acid have good antibacterial activity to Staphylococcus aureus.     

Fiber‐forming blend polypropylene‐polyvinyl alcohol

The preparation of a fiber‐forming blend consisting of polypropylene and polyvinyl alcohol mixed with glycerol and with polypropylene grafted with maleic anhydride were studied. The physical and mechanical properties of blend fibers were also studied. The rheological measurements for semiquantitative evaluation of technological compatibility of the components and for processing the polymeric material in extruding and spinning process were carried out. The experimental results revealed the technological compatibility of the polypropylene‐polyvinyl alcohol blend in the presence of glycerol and polypropylene grafted with maleic anhydride. The colloidal structure of interface layer is assumed to be in a three‐ or four‐component system. The mixture of polyvinyl alcohol with glycerol allows for the preparation of well spun fiber‐forming polypropylene blends. Polypropylene‐polyvinyl alcohol blend fibers consisting of up to 20% polyvinyl alcohol with sufficient mechanical properties, higher porosity and significantly higher sorption of water than polypropylene fibers alone were prepared. Copyright © 2001 John Wiley & Sons, Ltd.     

Phase morphology and mechanical properties of the electrospun polyoxymethylene/polyurethane blend fiber mats

Polyoxymethylene/thermoplastic polyurethane (POM/TPU) blends containing 10–30 wt % of TPU were electrospun using hexafluoroisopropanol as the solvent. The average fiber diameter increases with the increase in TPU content from 0.68 μm for neat POM fibers to 0.92 μm for POM/TPU 7:3 blend fibers due to the increase in solution viscosity. Core/sheath structure with the major component POM as the core and the minor component TPU as the sheath was observed by transmission electron microscopy and further confirmed by surface N contents of the blend fiber mats. The crystalline melting point and the degree of crystallinity of POM have no obvious change by coelectrospinning with TPU due to lack of interaction between POM and TPU as revealed by Fourier transform infrared spectroscopy. Tensile tests showed that the unusual high ductility of POM fiber mat could be further increased by coelectrospinning with 10 or 20 wt % TPU without significantly decreasing the stiffness and strength. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1853–1859, 2009     

Facile and Large-scale Fabrication of Self-crimping Elastic Fibers for Large Strain Sensors

Stretchable conductive fibers offer unparalleled advantages in the development of wearable strain sensors for smart textiles due to their excellent flexibility and weaveability.However,the practical applications of these fibers in wearable devices are hindered by either contradictory properties of conductive fibers(high stretchability versus high sensing stability),or lack of manufacturing scalability.Herein,we present a facile approach for highly stretchable self-crimping fiber strain sensors based on a polyether-ester(TPEE)elastomer matrix using a side-by-side bicomponent melt-spinning process involving two parallel but attached components with different shrinkage properties.The TPEE component serves as a highly elastic mechanical support layer within the bicomponent fibers,while the conductive component(E-TPEE)of carbon black(CB),multiwalled carbon nanotubes(MWCNTs)and TPEE works as a strain-sensitive layer.In addition to the intrinsic elasticity of the matrix,the TPEE/E-TPEE bicomponent fibers present an excellent form of elasticity due to self-crimping.The self-crimping elongation of the fibers can provide a large deformation,and after the crimp disappears,the intrinsic elastic deformation is responsible for monitoring the strain sensing.The reliable strain sensing range of the TPEE/E-TPEE composite fibers was 160％-270％and could be regulated by adjusting the crimp structure.More importantly,the TPEE/E-TPEE fibers had a diameter of 30-40 μm and tenacity of 40-50 MPa,showing the necessary practicality.This work introduces new possibilities for fiber strain sensors produced in standard industrial spinning machines.     

EFFECT OF PROCESSING METHOD ON THE IMPACT STRENGTH OF POM/TPU/CaCO3 TERNARY COMPOSITES

Polyoxymethylene （POM）/elastomer/filler ternary composites were prepared, in which thermoplastic polyurethane （TPU） and inorganic filler, namely, CaCO3, were used to achieve balanced mechanical properties of POM. The dispersion and phase morphology of POM/elastomer/filler composites were found to depend largely on processing method, CaCO3 content in masterbatch and the filler size. Two processing methods were employed to prepare POM/elastomer/filler ternary composites. One is called the one-step method, in which elastomer and the filler directly melt blended with POM matrix. The other is called the two-step method, in which the elastomer and the filler were mixed to get masterbatch first, which was then melt blended with pure POM of different content. The effect of phase morphology and processing method on impact strength was investigated. It was found that the two-step method results in an increase in impact strength but not for the one-step method. Additionally, the impact strength of POM ternary composites decreases with the increase in the size of CaCO3 particles.     

Towards understanding the increase in strength of thermotropic polyesters with heat treatment

Thermotropic copolyester fibers of oxynaphthoate and oxybenzoate have been subjected to conditions that promote solid-state polymerization as well as annealing. The annealing process causes the crystals to perfect with a simultaneous increase in heat of fusion and melting temperature. Solid-state polymerization, a reaction rate-controlled process, causes the polymer viscosity average molecular weight to increase by chain extension from about 14,000 g/mole to more than 87,000 g/mole with a simultaneous impressive increase in tenacity from about 10 g/d (1.2 GPa) to almost 30 g/d (3.7 GPa). To understand the changes in mechanical properties, we have modeled the fiber structure as short rod-like molecules poorly bonded to a continuous matrix of parallel molecules. Lengthening of the reinforcing molecules facilitates better transfer of load from matrix to molecules, resulting in higher tenacity fibers. © 1994 John Wiley & Sons, Inc.     

BPDA/PPD/OTOL聚酰亚胺纤维的力学性能、形貌和结构

在3,3’,4,4’-联苯四酸二酐(BPDA)和对苯二胺(PPD)体系中引入3,3’-二甲基联苯胺(OTOL),显著改善了纤维的力学性能。当n(PPD)∶n(OTOL)=70∶30时,纤维的拉伸强度可达到改性前的2倍,其拉伸强度和拉伸模量分别为1.50和80 GPa。SEM照片显示了纤维的断面为圆形且没有孔穴,也没有明显的"皮芯"结构和原纤结构。WAXD和SAXS分析表明,纤维的轴向堆积和分子链取向在热牵伸过程中得到改善。     

Toughening of polylactide by melt blending with a biodegradable poly(ether)urethane elastomer

Melt blending of polylactide (PLA) and a biodegradable poly(ether)urethane (PU) elastomer has been performed in an effort to toughen the polylactide without compromising its biodegradability and biocompatibility. The miscibility, phase morphology, mechanical properties, and toughening mechanism of the blend were investigated. The blend was found by dynamic mechanical analysis to be a partially miscible system with shifted glass transition temperatures. The PU elastomer was dispersed in the PLA matrix with a domain size of sub-micrometer scale. The addition of PU elastomer not only accelerated the crystallization speed, but also decreased the crystallinity of the PLA. With an increase in PU content, the blend shows decreased tensile strength and modulus; however, the elongation at break and the impact strength were significantly increased, indicating the toughening effects of the PU elastomer on the PLA. The brittle fracture of neat PLA was gradually transformed into ductile fracture by the addition of PU elastomer. It was found that the PLA matrix demonstrates large area, plastic deformation (shear yielding) in the blend upon being subjected the tensile and impact tests, which is an important energy-dissipation process and leads to a toughened, biodegradable polymer blend.     

Electrospun poly(l-lactide)-grafted hydroxyapatite/poly(l-lactide) nanocomposite fibers

Composite fibers composed of poly(l-lactide)-grafted hydroxyapatite (PLA-g-HAP) nanoparticles and polylactide (PLA) matrix were prepared by electro-spinning. Environmental scanning electron microscope (ESEM) and transmission electron microscopy (TEM) were employed to investigate the morphology of the composite fibers and the distribution of PLA-g-HAP nanoparticles in the fibers, respectively. At a low content (∼4 wt%) of PLA-g-HAP, the nanoparticles dispersed uniformly in the fibers and the composite fibrous mats exhibited higher strength properties, compared with the pristine PLA fiber mats and the simple hydroxyapatite/PLA blend fiber mats. But when the content of PLA-g-HAP further increased, the nanoparticles began to aggregate, which resulted in the deterioration of the mechanical properties of the composite fiber mats. The degradation behaviors of the composite fiber mats were closely related to the content of PLA-g-HAP. At a low PLA-g-HAP content, degradation may be delayed due to the reduction of autocatalytic degradation of PLA. When PLA-g-HAP content was high, degradation rate increased because of the enhanced wettability of the composite fibers and the escape of the nanoparticles from fiber surfaces during incubation.     

Mechanical properties of rigid polyurethane composites reinforced with surface treated ultrahigh molecular weight polyethylene fibers

The mechanical properties of ultrahigh molecular weight polyethylene (UHMWPE) fibers reinforced rigid polyurethane (PU) composites were studied, and the effects of the fiber surface treatment and the mass fraction were discussed. Chromic acid was used to treat the UHMWPE fibers, and polyurethane composites were prepared with 0.1 to 0.6 wt% as‐received and treated UHMWPE fibers. Attenuated total reflection Fourier transform infrared demonstrated that oxygen‐containing functional groups were efficiently grafted to the fiber surface. The mechanical performance tests of the UHMWPE fibers/PU composites were conducted, and the results revealed that the treated UHMWPE fibers/PU composites had better tensile, compression, and bending properties than as‐received UHMWPE fibers/PU composites. Thermal gravimetric analyzer showed that the thermal stability of the treated fiber composites were improved. The interface bonding of PU composites were investigated by scanning electron microscopy and dynamic mechanical analysis, and the results indicated that the surface modification of UHMWPE fiber could improve the interaction between fiber and PU, which played a positive role in mechanical properties of composites.     

Preparation and physical properties of poly(trimethylene terephthalate)/metallocene isotactic polypropylene conjugated fibers

Poly(trimethylene terephthalate) (PTT) and metallocene isotactic polypropylene (MIPP) polymers were extruded (in the proportions of 75/25, 50/50, 25/75) from two melt twin-screw extruders to prepare three PTT/MIPP conjugated fibers. This study investigated the preparation and physical properties of PTT/MIPP conjugated fibers using gel permeation chromatograph (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), potentiometer, a rheometer, the density gradient, wide-angle X-ray diffraction (WAXD), extension stress-strain measurement and scanning electron microscope (SEM). Melting behavior of PTT/MIPP polyblended polymers exhibited negative-deviation blends (NDB) and the 50/50 blend of PTT/MIPP showed a minimum value of the melt viscosity. Experimental results of the DSC indicated PTT and MIPP molecules formed immiscible system. The tenacity of PTT/MIPP conjugated fibers decreased initially and then increased as the MIPP content increased. Crystallinities and densities of PTT/MIPP conjugated fibers were the linear relation with the blend ratio. PTT and MIPP polymers were proved to be an incompatible system. On the morphological observation, it was revealed that the blends were in a dispersed phase structure. The pore/fiber morphology of a larger size from 0.5 to 3 μm in diameter was observed after 1,1,1,3,3,3-hexafluoro-2-propanol (PTT was removed)/paraffin oil (MIPP was removed) treatment on the cross-section of PTT/MIPP conjugated fiber. In this paper, PTT micro fibers were produced successfully.     

Effects of compatibility of poly(l‐lactic‐acid) and thermoplastic polyurethane on mechanical property of blend fiber

Blending poly(l ‐lactic‐acid) (PLLA) and thermoplastic polyurethane (TPU) has been performed in an effort to toughen PLLA without compromising its biodegradability and biocompatibility. The mixing enthalpy calculation of PLLA and TPU predicted that the blend was a thermodynamic miscible system. The viscoelastic properties and phase morphologies of PLLA/TPU blends were investigated further by dynamic mechanical analysis and scanning electron microscopy. It was found that the blend was a partially miscible system. The dynamic mechanical analysis showed that T_g of PLLA and TPU shifted toward with TPU content increasing. Scanning electron microscopy photos showed that the morphologies of the blends changed from a sea island structure to a bicontinuous structure as an increment in TPU content, which suggested that the miscibility of PLLA and TPU was enhanced when the TPU increased. PLLA/TPU blend fibers were fabricated. With the TPU content increasing from 0 wt% to 30 wt%, the tensile strength and initial modulus of blend fibers decreased first then increased, while elongation at break and fracture work gradually increased. The change of tensile properties indicated the toughening effects of TPU on PLLA fibers, also suggested that the formation of blend fibers was influenced by the blend rheological behavior other than the compatibility. Copyright © 2014 John Wiley & Sons, Ltd.     

Effects of take‐up speed on the structure and properties of melt‐spun poly(L‐lactic acid) fibers

Poly(L ‐lactic acid) (PLLA) filament fibers were prepared by one‐step melt spinning process and the effects of variations in take‐up speed on their thermal properties, mechanical properties, and crystalline structures were investigated. Differential scanning calorimetry (DSC) results revealed that the PLLA fibers showed multiple melting peaks and that the melting peak appearing at a lower temperature moved lower while that at a higher temperature moved higher with increasing take‐up speed. The glass transition temperature (T_g) obtained from dynamic mechanical analysis (DMA) increased with increasing take‐up speed. The tenacity increased and the boiling water shrinkage (BWS) decreased with increasing take‐up speed. However, these mechanical and thermal properties were stabilized at take‐up speeds over 3500 m/min. The melt‐spun PLLA fibers of this study showed an α‐form crystal structure which was not affected by the take‐up speed. The change in the tendency of the thermal and mechanical properties at around 3500 m/min did not appear to result from the change in crystal form but rather from the change in crystallite size and crystallite orientation. Copyright © 2008 John Wiley & Sons, Ltd.     

Anisotropic mechanical properties of thermoplastic elastomers in situ reinforced with thermotropic liquid‐crystalline polymer fibers revealed by biaxial deformations

The anisotropic mechanical properties of the thermoplastic elastomer (TPE) in situ reinforced with thermotropic liquid‐crystalline polymer (TLCP) fibers were investigated by uniaxial, strip‐biaxial, and equibiaxial tensile measurements. The in situ composite sheets were prepared from an immiscible blend of a TLCP, Rodrun LC3000, and a TPE, styrene‐(ethylene butylene)‐styrene (SEBS) triblock copolymer, by a melt extrusion process. The uniaxial orientation of the TLCP fibers in the TPE matrix generated during processing yielded a significant mechanical anisotropy in the composites. The biaxial tensile measurements clearly demonstrated the anisotropic mechanical properties of the composites: The modulus in the direction parallel to the machine direction (MD) was considerably higher than that in the transverse direction (TD), even at large deformations; in equibiaxial stretching, the yield strain in the MD was smaller than that in the TD; the composite containing 10 wt % of TLCP exhibited the highest mechanical anisotropy among the composites, with 0–30 wt % TLCP. The latter result was in accord with the SEM observation that the composite with 10 wt % of TLCP possessed the best fibrillar morphology and the highest degree of uniaxial orientation of the TLCP fibers. The yield strains in uni‐ and biaxial elongation for the composite containing 10 wt % of TLCP were almost the same as those for the neat styrene‐ethylene butylene‐styrene. The TLCP phase with good fibrillation did not appreciably alter the original yielding characteristics of the elastomer matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 135–144, 2005     

高力学强度细菌纤维素气凝胶纤维的连续化制备

气凝胶纤维因其高外表面积和高柔韧性在能量管理系统中具有潜在应用而引起了广泛关注.但是,目前制备的气凝胶纤维力学强度较低,限制了其实际应用.为提高气凝胶纤维力学性能,在始终保持细菌纤维素(BC)纳米纤维处于湿态下,利用NaOH/尿素/硫脲复合溶剂直接低温溶解原生BC,获得透明的BC纺丝原液;通过湿法纺丝制备了BC水凝胶纤维,经过水洗和冷冻干燥后处理,制得BC气凝胶纤维.采用偏光显微镜(POM)、13C核磁共振(13C-NMR)和高级旋转流变仪研究BC在复合溶剂中的溶解过程与状态;利用全反射傅里叶变换红外吸收光谱(ATR-FTIR)、X射线衍射(XRD)和热失重(TG)研究BC溶解前后结构与性能变化;利用场发射扫描电镜(FESEM)、全自动比表面积和孔径分布分析仪、单丝强力仪对获得的BC气凝胶纤维结构与性能进行表征.结果表明,复合溶剂在?15℃条件下可以直接溶解原生湿态BC,最高溶解浓度为3 wt%;采用湿法纺丝制得高度多孔的连续BC气凝胶纤维,比表面积高达192 m^2/g且具有优异的力学性能,断裂强度和杨氏模量高达(9.36±1.68)MPa和(176±17.55)MPa,如0.4 mg BC气凝胶纤维可以支撑高于其本身质量5×10^4倍的重物.     

Compatibilization of PBT/PP Blends by Adding Side-chain Liquid Crystalline Ionomer with Quaternary Pyridinium Groups

A side-chain liquid crystalline ionomer(SLCI) was synthesized by grafting copolymerization of 4-(4-ethoxybenzoyloxy)-4′-allyloxybiphenyl and N-allyl-pyridium bromide on polymethylhydrosiloxane. The SLCI was blended with polypropylene(PP) and polybutylene terephthalate(PBT) by melt mixing. The thermal behavior, liquid crystalline properties, morphological structure, and mechanical properties of the blends were investigated by differential scanning calorimetry(DSC), polarizing optical microscopy(POM), scannin...     

聚合物二元体系动态力学性能的估算

动态热机械分析是多相聚合物体系的一个重要研究手段.分析动态力学性能可以研究共混高聚物的相容性、复合材料的界面特性以及高分子运动机理等.本文综述了聚合物二元体系,即填充、纤维增强、共混体系动态力学性能的估算方法.在填充体系中,分别概述有无界面作用两种情况,当存在界面作用时,界面作用越强,模量越大,阻尼越小.对纤维增强体系,讨论了玻璃纤维有无取向的情况下模量和阻尼的估算.特别对于聚合物二元共混体系,分"海-岛"结构和双连续相两种情况,分别讨论了模量与阻尼的估算.     

Influence of silver nano‐additive amount on the supramolecular structure,porosity, and properties of polyacrylonitrile precursor fibers

This work examines the influence of the amount of silver nanoparticles added to polyacrylonitrile spinning solutions on their rheological properties as well as the structure and properties of the fibers produced. The influence of the amount of silver nanoparticles on the supramolecular structure of nanocomposite polyacrylonitrile precursor fibers, their porosity, as well as thermal and tensile strength properties was determined. The distribution of the nano‐ additive in fiber cross‐sections and on the surface was estimated. It was found that the addition of silver nanoparticles to polyacrylonitrile precursor fibers in an amount of up to 1.5% does not cause a decrease in the susceptibility of the fiber matter to deformation at the drawing stage. The produced fibers were characterized by an increased total volume of pores of 0.35 cm³/g and tenacity of more than 34 cN/tex. Copyright © 2009 John Wiley & Sons, Ltd.