《液晶高分子材料》专辑序言——老学科的新活力

正19世纪80年代后期,奥地利植物学家Reinitzer和德国物理学家Lehmann共同发现了液晶,创立了液晶科学。20世纪70年代,液晶显示技术实现了革命性突破,风靡全球。液晶高分子的研究始于1937年的生物高分子液晶,随即受到广泛关注,尤其是杜邦公司基于溶致液晶芳香族聚酰胺的液晶纺丝技术在1972年推出的Kevlar系列高性能纤维产品,极大地推动了液晶高分子的飞速发展。近几十年来,基于热致液晶芳香族聚酯的高性能工程塑料如雨后春笋般不断涌现,高性能液晶高分子结构材料也成为全球研究热点。同时,侧链高分子液晶、聚合物分散液晶、聚合物稳定液晶、全息聚合物分散液晶以及新型结构的高分子液晶、超分子液晶在显示、传感、防伪、数据存储和电子封装等领域的应用也成为高性能液晶高分子功能材料的研究亮点。其中让我们倍感骄傲的是,我国科学家周其凤院士于1987年设计、合成了甲壳型液晶高分子,为液晶高分子科学与材料的发展做出了原创性贡献。当前,液晶材料的高分子化、高分子材料的液晶化已成为化学、材料、光学工程和信息工程等相关学科的重要研究方向,尤其近期在光存储、5G通讯领域中的应用备受关注。     

取向静电纺丝纳米纤维的制备及应用研究进展

简单描述了静电纺丝的基本装置、原理;为制得高性能的取向纳米纤维,对静电纺丝中出现的不稳定性进行了研究,介绍了三种不稳定状况,并分析了其产生原因.列举了通过改变接收装置、控制电场和附加磁场等方法,改进静电纺丝技术来制取连续取向的纳米纤维,并对各种方法进行了简单的评价,指出磁化静电纺丝(MES)是目前制备取向纳米纤维最具有发展前景的方法.简要介绍了取向纳米纤维在生物组织工程领域方面的应用,并对其未来作了展望.     

高性能聚酰胺6纤维的制备技术进展

聚酰胺6纤维具有良好的综合性能如力学性能、耐热性、耐磨损性和耐化学药品性等,同时具有很高的理论模量,如果开发制备出高强高模纤维,其在军用纤维和纺织上应用前景非常可观。但是聚酰胺分子间很强的氢键作用制约了分子的取向和纤维的高倍拉伸,从而限制了制备高强高模聚酰胺纤维技术的发展。所以要拉伸得到高取向聚酰胺纤维,需通过减少链间氢键的数量来实现。许多研究者已经通过各种工艺技术提高最大拉伸比,如增塑剂法、干法纺丝、冻胶纺丝、湿法纺丝、区域拉伸和退火等。鉴于已经通过冻胶纺丝法制备出了超高分子量聚乙烯纤维,因此目前冻胶纺丝法制备高强高模聚酰胺纤维具有较大的可行性。本文将介绍各种制备聚酰胺6纤维的工艺技术,主要突出冻胶法制备聚酰胺6纤维的技术。     

静电纺丝法制备胆固醇-g-聚乳酸液晶/ 聚乳酸复合纳米纤维膜

以辛酸亚锡为催化剂, 胆固醇(CHOL)为共引发剂引发D,L-丙交酯开环聚合, 制备了胆固醇-g-聚(D,L-乳酸)(CHOL-g-PDLLA)低聚物, 采用偏光显微镜(POM)和差示扫描量热(DSC)方法考察了其液晶特性. 通过静电纺丝技术制备了CHOL/PDLLA和CHOL-g-PDLLA /PDLLA复合纳米纤维膜, 对其形貌、界面相容性、孔隙率、拉伸性能和细胞相容性进行了研究. 结果表明, CHOL-g-PDLLA为一种热致胆甾型液晶, 液晶温度区间为21.8~74.5 ℃; CHOL-g-PDLLA/PDLLA复合纳米纤维膜的纤维形态良好, 表面均匀光滑, 孔隙率在70%~75%之间, 且其界面相容性优于相应的CHOL/PDLLA. 随着CHOL和CHOL-g-PDLLA含量的增加, 复合纳米纤维膜的拉伸强度逐渐下降, 但CHOL-g-PDLLA/PDLLA复合纳米纤维膜的拉伸强度显著大于CHOL/PDLLA. 体外骨髓间充质干细胞培养结果显示, CHOL-g-PDLLA/PDLLA复合纳米纤维膜具有良好的细胞相容性, 且优于相应的PDLLA和CHOL/PDLLA纳米纤维膜.     

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.     

提拉纺丝制备弹性离子液体凝胶纤维

规模化制备兼具高弹性和高离子电导率的可拉伸导电纤维极具挑战性.为此,我们开发了一步法提拉纺丝策略,可连续制备高弹性离子液体凝胶纤维.其中,离子液体与聚合物基质以非共价相互作用结合,在纤维中稳定存在,并可大幅调控纤维力学性能.得益于通过氢键自发纳米限域形成的多尺度相分离结构,所得离子液体凝胶纤维具有良好的拉伸性(707%)、高透明度(98%)、高回弹性(残余应变仅9%)、导电性(0.12 S·m^-1)以及抗冻性能.此外,该纤维还可对湿气、温度以及应变表现出极为灵敏的信号感知能力.这一工作为开发面向智能感知的高性能离子导电纤维材料提供了设计思路.     

4,4’-ODA改性含氯芳香族聚酰胺的合成与纺丝工艺研究

采用低温溶液缩聚的方法,在N-甲基吡咯烷酮(NMP)-氯化锂(LiCl)溶剂体系中引入了4,4’-二氨基二苯醚(4,4’-ODA)作为第三单体,与邻氯对苯二胺和对苯二甲酰氯(TPC)反应,得到可用于直接湿纺的共聚物纺丝溶液。将原液进行湿法纺丝,经水洗干燥后得到原丝,采用SEM和电子拉伸试验机表征纤维的结构与力学性能。研究结果表明,共缩聚后可以得到粘度高、分子量大、稳定性好的纺丝原液,通过湿法纺丝制得的纤维具有良好的取向度、结晶度和热性能。     

静电纺丝制备自修复功能纤维及其自愈合性能表征

应用静电纺丝技术,以聚苯乙烯和愈合剂的共混溶液为纺丝液,制备了含有愈合剂的功能纤维,并以其制备了具有自修复性能的纤维/树脂复合材料.通过扫描电子显微镜(SEM)、红外光谱(FTIR)、荧光显微镜等对纤维的形貌和结构进行了表征,探讨了纺丝溶液的组成对纤维形貌和结构的影响.纤维中愈合剂的含量随纺丝液中愈合剂浓度的增加而增大,但可纺性随之变差.通过SEM观察了所制备的复合材料表面预制裂纹的修复,在一定温度下裂纹处纤维中的愈合剂(分别为环氧和其固化剂)释放并进一步反应,经过愈合复合材料的拉伸强度提高了2.81 MPa,力学性能明显改善.     

分光光度法测PBO纤维中残留磷含量

溶致性液晶高分子聚苯撑苯并二嗯唑(PB0)在多聚磷酸溶液的液晶态下干喷湿纺,可制得具有超高比强度、高比模量、耐高温和环境稳定性优异的纤维。但PB0纤维中残留的多聚磷酸溶剂对纤维的性能有很大的影响。介绍了用分光光度法测定PB0纤维中残余磷含量的方法,该方法样品处理简便,测定结果可靠,为PB0纤维的纺丝工艺和洗涤条件的选择提供了有价值的依据。     

热致性液晶高分子

液晶高分子是高分子材料科学中一个比较新的研究领域。自杜邦公司商品名为Kevlar的高强高模芳香族纤维在1970年商品化以来,液晶高分子引起了人们越来越广泛的重视。在继以刚性链芳香族聚酰胺为代表的溶致性液晶     

Kink motion in poly(vinylidene fluoride) form I

The diffuse-streak x-ray scattering intensity from poly(vinylidene fluoride) form I, which is caused by kink bands with GT_n? (n odd) conformation contained in the crystallite, decreases with increasing temperature, while the intensity of the 001 reflection does not change. This is attributed to the disappearance of the kink bands in the crystallite, not to partial melting of crystallites containing kink bands. The disappearance of the kink bands suggests that kink motion takes place in the crystallite. Plots of the intensity of diffuse-streak scattering, estimated from the asymmetric part of the 001 reflection, against 1/T roughly give ΔH_v = ?4.6 kcal/mol. This suggests that the kink band is energetically more stable than the regular structure of form I.     

Formation of kink bands by compression of the extrudate of solid linear polyethylene

Extrudates of solid linear polyethylene prepared under proper pressure and temperature conditions have a high c axis orientation along the extrusion direction, with lamellar crystals and amorphous layers stacked alternately along the extrusion direction. Kink bands were formed by compressing the oriented extrudate at room temperature along the extrusion direction. Inspection of the kink bands by wide-angle and small-angle x-ray diffraction and electron microscopy revealed that the fiber axis was rotated from the original axis direction by 70–75° and that the lamellar crystals were inclined to the fiber axis in the kink band by 55–60° and stacked nearly parallel to the kink boundary. The superstructural change during the formation of the kink band could not be interpreted in terms of uniform c axis shear alone. In addition to such a mechanism, it was necessary to take into account intermicrofibril and/or intercrystallite slip.     

有机高性能纤维材料的轴向压缩变形行为

介绍了利用偏光显微镜、扫描电子显微镜及Ｘ射线衍射等方法研究具有伸直链结构的有机高性能纤维及膜材料的轴向压缩变形行为。在初级变形阶段，因晶面滑移形成与纤维轴呈一定角度并较有规则的变形带。变形带内大分子受剪切作用发生挫屈或折断。随变形程度增加，变形带堆积厚度以及分布密度增大。如果继续增大变形程度，微原纤维间的相对滑移使材料大分子发生剧烈的侧向位移、高度取向和结晶材料所特有的结构各向异性同性化，试样轴向长度明显缩短，最终导致破坏。     

Structural relationships and mechanisms for the stoichiometry change from MX3 (YF3-type) through MX2 (fluorite-type) to M2X3 (C-type sesquioxide)

Structures produced by inducing stoichiometry changes in crystalline fluorides and oxide-fluorides of yttrium by pyrohydrolysis have been studied by X-ray powder diffraction and electron microscopy. The structures of YF₃, various fluorite-related intermediates and the ultimate product of hydrolysis, Y₂O₃, are all closely related. The pyrohydrolysis is topotactic; the anion sublattice remains intact and vacancies and oxygen substitute for fluorine on the anion sublattice in an ordered, cooperative way to produce fully ordered product structures. A ‘unit slip’ mechanism, involving the most favourable slip systems for a primitive cubic sublattice, 〈001〉{110} and 〈001〉{110}, is postulated as a possible mechanism for the process.     

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.     

The influence of A-site rare-earth for barium substitution on the chemical structure and ferroelectric properties of BZT thin films

Rare-earth (RE) doped Ba(Zr,Ti)O₃ (BZT) thin films were prepared by rf-magnetron sputtering from a Ba_0.90Ln_0.067Zr_0.09Ti_0.91O₃ (Ln=La, Nd) target. The films were deposited at a substrate temperature of 600 °C in a high oxygen pressure atmosphere. X-ray diffraction (XRD) patterns of RE-BZT films revealed a 〈001〉 epitaxial crystal growth on Nb-doped SrTiO₃, 〈001〉 and 〈011〉 growth on single-crystal Si, and a 〈111〉-preferred orientation on Pt-coated Si substrates. Scanning electron microscopy (SEM) showed uniform growth of the films deposited, along with the presence of crystals of about half-micron size on the film's surface. Transmission electron microscopy (TEM) evidenced high crystalline films with thicknesses of about 100 nm for 30 min of sputtering. Electron-probe microanalysis (EPMA) corroborated the growth rate (3.0-3.5 nm/min) of films deposited on Pt-coated Si substrates. X-ray photoelectron spectroscopy (XPS), in depth profile mode, showed variations in photoelectron Ti 2p doublet positions at lower energies with spin-orbital distances characteristic of BaTiO₃-based compounds. The XPS analysis revealed that lanthanide ions positioned onto the A-site of the BZT-perovskite structure increasing the MO₆-octahedra distortion (M=Ti, Zr) and, thereby, modifying the Ti-O binding length. Polarization-electric field hysteresis loops on Ag/RE-doped BZT/Pt capacitor showed good ferroelectric behavior and higher remanent polarization values than corresponding non-doped system.     

Phase separation, cation ordering and nano-structural complexities in Nd2/3−xLi3xTiO3 with x=0.14

Transmission electron microscopy (TEM) investigations on Nd_2/3−xLi_3xTiO₃ with x=0.14 reveal a rich variety of structural features in the samples prepared under different conditions, such as superstructures, anti-phase domains, and nano-chessboard structures. Our careful analysis shows that these structural phenomena can be fundamentally understood as the combination of structural effects of (Nd, Li)-ordering along the 〈001〉_p direction and the spinodal decomposition along the 〈100〉_p/〈010〉_p direction. The coexistence of phase separation and cation ordering can lead to visible nano-structural complexities in many crystals, as the typical results, the regular lamella structure, nano-chessboard structures and anti-phase boundaries have been extensively studied.     

Composition-dependent microhardness and its relationship to bonding in sodium tungsten bronzes

The technique of microhardness measurements using diamond indenters is outlined and assessed for its potential use in quantifying bonding changes and studying reactions in nonstoichiometric crystals. Results are presented for both Vickers and Knoop hardness values on {001} and {011} crystal planes of cubic sodium tungsten bronzes, Na_xWO₃, with x in the range 0.5 to 0.75. The Knoop data show that in only one direction, 〈110〉 on {001}, is the hardness sensitive to changes in composition. Hardness in the 〈110〉 directions and the degree of anisotropy increase as the sodium content of the bronze increases. All the crystal faces examined showed marked anisotropic behavior, with 〈110〉 being about 50% harder than 〈100〉 on {001} faces, while on {011} planes hardness increases in the sequence $\text{〈100〉:〈21}\text{1}\text{〉:〈11}\text{1}\text{〉 ≈ 〈01}\text{1}\text{〉}$. Hardness results from isomorphous and isoelectronic ReO₃ are considered with the Na_xWO₃ data to show the dominant role played by Na⁺WO₃ matrix interactions in determining the properties of these materials. The results are discussed in terms of current bonding theories for bronzes.     

Structured diffuse scattering and polar nano-regions in the Ba(Ti1−xSnx)O3 relaxor ferroelectric system

The observation via electron diffraction of relatively sharp G±{001}* sheets of diffuse intensity arising from the large amplitude excitation of inherently polar, transverse optical modes of distortion in Ba(Ti_1−xSn_x)O₃ (BTS), 0.1?x?0.5, samples, both at room temperature as well as liquid nitrogen temperature, shows that the polar nano-regions (PNRs) in these relaxor ferroelectric materials correspond to the same highly anisotropic 〈001〉 chain dipoles as are characteristic of the normal ferroelectric end member BaTiO₃ itself. The correlation length along the chain of these 1-d PNRs can, in principle, be determined from the width of the observed {001}* diffuse sheets in reciprocal space and is estimated to be at least 5 nm even for the higher x samples. The distribution of the substitutional Sn ions thus appears to have only a minor effect upon the correlation length along the 〈001〉 chain dipole directions. It is suggested that the role of the dopant Sn ions is not to directly induce PNRs but rather to set up random local strain fields preventing the condensation of long wavelength homogeneous strain distortions of the unit cell thereby suppressing transverse correlations of the 〈001〉 chain dipoles and the development of long-range ordered ferroelectric state/s.     

An Electron Diffraction and Crystal Chemical Investigation of Oxygen/Fluorine Ordering in Niobium Oxyfluoride, NbO2F

A careful electron diffraction study of the ReO₃-type oxyfluoride NbO₂F has revealed the presence of characteristic transverse polarized planes of diffuse intensity running through the G±〈hk(1/3)〉^* regions of reciprocal space as well as continuous rods of diffuse intensity running through the G±〈(1/2)(1/2)ξ〉^* regions of reciprocal space. The continuous planes of diffuse intensity in reciprocal space (perpendicular to each of the major crystal directions a, b and c) imply the existence of one-dimensional, oxygen/fluorine-ordered columns of atoms along 〈001〉 in real space but with no lateral correlation in the ordering from such 〈001〉 column to the next. The continuous lines of diffuse intensity along the 〈(1/2)(1/2)ξ〉^* directions of reciprocal space are ascribed to Rigid Unit Mode (RUM) rotations of the constituent MX₆ octahedral framework. A combination of bond-valence arguments and simple structure factor calculations are used to support this argument.