基于静电纺丝技术的取向纳米纤维

纳米纤维作为一维纳米材料的一个重要分支,有着广泛的应用前景。静电纺丝技术是一种制备一维纳米纤维的有效方法。然而,传统制备工艺制得的纳米纤维常为无序排列的结构,极大限制了其应用。近十几年来,通过对喷丝装置、纤维分化区及接收装置的改进获得了取向纳米纤维(aligned nanofibers, ANFs),引发了研究者的广泛关注,但对于取向纳米纤维的制备与应用未见系统性的论述。本文系统总结了采用静电纺丝技术制备取向纳米纤维的方法,并评述了这种取向结构在生物组织工程修复、传感器、增强材料及能源等领域中的应用。鉴于ANFs在生物组织工程中得到广泛的关注,本文对其进行了着重介绍。而在能源领域,本文主要阐述在质子交换膜燃料电池方面的应用。最后,本文总结了ANFs存在的问题,并展望了其未来的发展。     

OBTAINING PRECISE CRITICAL DRAW RATIO OF DRAW RESONANCE IN MELT SPINING BY NUMERICAL SIMULATION OF DIFFERENCE EQUATIONS

Direct difference methods have been used to solve the simultaneous non-linear partial differential equations for melt spinning without recourse to linearisation or perturbation approximation. The stability of each difference schemes was studied by error analysis using the Taylor series, and by comparison of the results obtained from numerical simulation with the logical value in melt spinning. It is found that computation with 19 digit long double precision has significantly simplified the stability problem of difference equations. Using this method, the precise critical draw ratio of draw resonance in an isothermal and uniform tension spinning of Newtonian fluids can be obtained in between 20.218 and 21.219, a figure consistent with 20.218 which was obtained by a linear perturbation approximation method by Kase and Denn. It thus has paved the way to computation of full information for unsteady melt spinning processes using the difference method.     

季铵类离子液体催化熔融缩聚反应合成异山梨醇基聚碳酸酯

聚碳酸酯是一种性能优良的工程塑料,具有优异的透明性、绝缘性及无毒性等优点.目前实现大规模工业生产的是双酚A型聚碳酸酯,但是其生产原料双酚A具有毒性,限制了其应用.异山梨醇是一种生物基可再生单体,具有无毒、手性和刚性等特性,是双酚A的理想替代品.但是异山梨醇亲水性强,且羟基的活性低,导致碳酸二苯酯和异山梨醇通过熔融缩聚反应合成异山梨醇基聚碳酸酯(PIC)困难,因此选用合适的催化剂成为一个重要因素.目前报道的效果较好的催化剂是无机碱催化剂,这类催化剂催化活性差,容易引发副反应,在产品中残留影响产品质量.离子液体具有环境友好和阴阳离子可设计等优点,是无机碱催化剂的良好替代品.本文设计合成了六种季铵类的碱性离子液体(四乙铵二氰胺盐、四乙铵咪唑盐、四乙铵乳酸盐、四乙铵-1,2,4-三氮唑盐、四乙铵苯甲酸盐和四乙铵乙酸盐),用于催化熔融缩聚反应合成PIC.用核磁共振表征了PIC的结构,用凝胶色谱测定了PIC的分子量,通过对比PIC的重均分子量(Mw)和异山梨醇的转化率,研究了离子液体阴离子对催化剂活性的影响.发现催化活性不仅与离子液体的碱性强弱有关,还与离子液体阴离子的配位强度有关,催化效果最好的离子液体为四乙铵咪唑盐(TEAI).以TEAI为催化剂对合成PIC的条件进行了优化,得到的最优条件为:催化剂与异山梨醇的摩尔比为5×10-4,缩聚时间为5 h,缩聚温度为240 oC.合成PIC的Mw为25600 g/mol,异山梨醇的转化率为92%.由于均聚物PIC分子链刚性大,导致PIC熔体粘度大,不利于聚合,为了降低PIC的刚性和提高分子量,在分子链中引入了柔性基团(脂肪族二醇)来合成共聚碳酸酯(PAIC).以TEAI为催化剂,异山梨醇和脂肪族二醇投料摩尔比为1:1,通过熔融缩聚反应合成了PAICs.利用1H NMR和13C NMR详细表征了PAICs化学组成和微观结构,发现不同脂肪族二醇的羟基活性不同,合成的PAICs分子链中异山梨醇和脂肪族二醇的比例与投料比有所差异,得到的共聚物为无规共聚物.此外,对PAICs进行了凝胶色谱测试,发现PAICs的Mw与PIC相比均有所提高.通过差示扫描量热仪和热重分析仪对PIC和PAICs进行了热稳定性测试.结果表明,对于不同直链二醇制备的PAICs,随着二醇链中亚甲基数量的增加,其玻璃化转变温度(Tg)逐渐降低,但热稳定性逐渐提高;而对于用1,4-环己烷二甲醇合成的PCIC,其Tg值和热稳定性明显高于直链脂肪族二醇共聚物.这些性能为共聚碳酸酯用作高性能聚合材料提供了可能性.     

Plateau–Rayleigh Instability Morphology Evolution (PRIME): From Electrospun Core–Shell Polymer Fibers to Polymer Microbowls

Electrospun core–shell fibers have great potentials in many areas, such as tissue engineering, drug delivery, and organic solar cells. Although many core–shell fibers have been prepared and studied, the morphology transformation of core–shell fibers have been rarely studied. In this work, the morphology evolution of electrospun core–shell polymer fibers driven by the Plateau–Rayleigh instability is investigated. Polystyrene/poly(methyl methacrylate) (PS/PMMA) core–shell fibers are first prepared by using blend solutions and a single axial electrospinning setup. After PS/PMMA core–shell fibers are annealed on a PS film, the fibers undulate and sink into the polymer film, forming core–shell hemispheres. The evolution process, which can be observed in situ by optical microscopy, is mainly driven by achieving lower surface and interfacial energies. The morphologies of the transformed structures can be confirmed by a selective removal technique, and polymer microbowls can be obtained.

     

聚全氟乙丙烯中空纤维膜的制备及性能

以聚全氟乙丙烯(FEP)为成膜聚合物,MT-Ⅱ型复合粉为致孔剂,邻苯二甲酸二辛酯(DOP)为稀释剂,采用熔融纺丝拉伸法制备了FEP中空纤维膜,研究了其耐酸碱等性能.结果表明,FEP中空纤维膜的表面具有由拉伸孔、界面孔及溶出孔组成的多重孔结构,而其横截面为均匀分布的海绵状孔结构.FEP中空纤维膜经质量分数为25%的硫酸水溶液和25%的氢氧化钠水溶液分别处理60 d后,膜的化学结构未发生变化,而且平均孔径增大,孔径分布变窄,断裂强度保持率分别在86.8%及80.8%以上,耐酸碱性明显优于商业化聚偏氟乙烯(PVDF)中空纤维膜,显示出优异的化学稳定性及良好的热稳定性.     

PEGylated poly(ester amide) elastomer scaffolds for soft tissue engineering

Biodegradable synthetic elastomers with tunable mechanical and physicochemical properties remain attractive materials for soft tissue engineering. We have recently synthesized novel poly(1,3‐diamino‐2‐hydroxypropane‐co‐glycerol sebacate)‐co‐poly(ethylene glycol) (APS‐co‐PEG) biodegradable elastomers. This class of PEGylated elastomers has widely tunable mechanical and degradation properties compared wtih currently available biodegradable elastomers. To further investigate the biological application of this class of elastomers, we fabricated hybrid APS‐co‐PEG/polycaprolactone (PCL) porous scaffolds by electrospinning. The fiber morphology, chemical composition, mechanical properties, degradability, and cytocompatibility of hybrid APS‐co‐PEG/PCL electrospun scaffolds were characterized. These scaffolds exhibited a wide range of mechanical properties and similar cytocompatibility to PCL scaffolds. Importantly, PEGylation inhibited platelet adhesion on all APS‐co‐PEG/PCL electrospun scaffolds when compared with PCL and APS/PCL scaffolds, suggesting a potential role in mitigating thrombogenicity in vivo. Additionally, APS‐25PEG/PCL scaffolds were found to be mechanically analogous to human heart valve leaflet and supported attachment of human aortic valve cells. These results reveal that hybrid APS‐co‐PEG/PCL scaffolds may serve as promising constructs for soft tissue engineering, especially heart valve tissue engineering. Copyright © 2017 John Wiley & Sons, Ltd.     

Hydrophobic coatings from photochemically prepared hydrophilic polymethacrylates via electrospraying

Linear poly(hydroxyethyl methacrylate‐co‐methyl methacrylate) P(HEMA‐co‐MMA) and poly(dimehylaminoethyl methacrylate‐co‐methyl methacrylate) P(DMAEMA‐co‐MMA) and their corresponding hyperbranched copolymers were synthesized by conventional photoinitiated free radical polymerization and self‐condensing vinyl polymerization (SCVP) using Type I and Type II photoinitiators, respectively. Then, the polymers were processed by electrospraying in N, N‐dimethylformamide. The surface of the resulting electrospray coatings was examined by SEM, XPS, and WCA then compared with those prepared by drop casting. Regardless of the structural nature of the polymers, electrospraying allows the preparation of rough surface that shows more hydrophobic behavior. Electrospray coatings with linear and hyperbranched copolymers exhibited WCA as ～150° and ～130°, respectively, indicating that branching reduces the WCA. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1338–1344     

Photo and Thermal Cured Silicon‐Containing Diethynylbenzene Fibers via Melt Electrospinning with Enhanced Thermal Stability

An inorganic–organic hybrid material, poly(dimethylsilylene ethynylenephenyleneethynylene) (PMSEPE), was synthesized in a mild condition and its microfiber was successfully produced by melt electrospinning. The electrospinning parameters, which affected the morphology and diameter of fibers, were well investigated. To maintain the fiber structure at thermal cured temperature (above melting point), the PMSEPE fibers were enhanced via thiol‐yne photo polymerization. Followed by the thermal curing reaction, the heat‐resistance and mechanical properties of fibers were enhanced. The mechanism of two‐step curing was explored and confirmed by means of Fourier transform infrared, differential scanning calorimetry, and X‐ray photoelectron spectroscopy (XPS). Thermaogravimetric analysis and scanning electron microscopy results show that after carbonization at 800 °C, the two‐step cured fibers had only a small weight loss (20%) and the fibers can still maintain the original morphology. Moreover, the two‐step cured fiber exhibited a high tensile strength (55.4 MPa) and a small elongation at break (0.02%). All the results indicate that the fibers could be applied as fiber‐reinforced materials. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2815–2823     

Electrohydrodynamics of spherical polyampholyte‐grafted nanoparticles: Multiscale simulations by coupling of molecular dynamics and lattice‐boltzmann method

We perform multiscale simulations based on the coupling of molecular dynamics and lattice‐Boltzmann (LB) method to study the electrohydrodynamics of a polyampholyte‐grafted spherical nanoparticle. The long‐range hydrodynamic interactions are modeled by coupling the movement of particles to a LB fluid. Our results indicate that the net‐neutral soft particle moves with a nonzero mobility under applied electric fields. We systematically explore the effects of different parameters, including the chain length, grafting density, electric field, and charge sequence, on the structures of the polymer layer and the electrophoretic mobility of the soft particle. It shows that the mobility of nanoparticles has remarkable dependence on these parameters. We find that the deformation of the polyampholyte chains and the ion distribution play dominant roles in modulating the electrokinetic behavior of the polyampholyte‐grafted particle. The enhancement or reduction in the accumulation of counterions around monomers can be attributed to the polymer layer structure and the conformational transition of the chains in the electric field. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1435–1447