有机凝胶先驱体转化法制备CoNi合金微细纤维

本文以柠檬酸和金属盐为原料,采用有机凝胶先驱体转化法成功制备了CoNi合金微细纤维.通过FTIR、XRD、TG/DSC和SEM对纤维先躯体凝胶的结构、物相组成、热分解过程及热处理后产物的形貌进行了表 征.结果表明,在凝胶形成过程中金属离子可单齿配位于柠檬酸根阴离子,并形成线性分子结构,使凝胶有较好的可纺性;先驱体纤维经650℃氢气还原1小时后形成了晶粒细小、直径可以小于1μm,长度可达1m的均匀铁磁性CoNi合金微细纤维.CoNi合金微细纤维可用于先进聚合物基电磁屏蔽复合材料的填料和雷达吸波材料.     

纤维气凝胶的分类、制备工艺及应用现状

气凝胶具有高孔隙率、低密度、高比表面积和低热导率等优异性能,广泛应用于隔热、隔音和吸附等领域,已经成为21世纪以来新型纳米多孔材料的研究热点.但是由于气凝胶的网络结构导致其缺点也十分突出,首先,气凝胶的力学性能较差、脆性大,使其加工、处理变得困难,且易产生粉尘污染;其次,由于原料和制备工艺等限制,气凝胶的价格昂贵;另外往往只能静态成型难以连续生产,形态多是与模具或反应相对应的块状或粉末状,不能满足更多的应用.因此提高气凝胶的力学性能、寻找更简单廉价的合成方式和拓宽气凝胶形态等成为亟待解决的问题.设计制备纤维态气凝胶和纤维复合气凝胶是解决上述不足的方法之一.可通过湿法纺丝、管中浇铸、纤维状基材自组装、静电纺丝、纤维热解碳化、原纤化堆积等成型方法和超临界、冷冻、常压等干燥工艺,制备无机纤维气凝胶、有机纤维气凝胶、有机/无机杂化纤维气凝胶和纤维复合气凝胶材料,实现气凝胶的骨架结构的增强、纤维态气凝胶的成型和连续生产,可避免附聚并方便回收处理,还可设计调控特殊的中空结构和分级孔结构,或利用嵌入纤维的独特物理、化学特性,在保持气凝胶原有优秀性能的基础上,赋予其新的性能.本文对近五年纤维气凝胶及纤维复合气凝胶材料的研究现状进行了概览,介绍了纤维气凝胶的类型、制备方法及原理,说明了纤维气凝胶在吸附、隔热、传感、能量存储、催化和微波屏蔽等传统及新兴领域的应用,并提出了未来可尝试的研究方向,对纤维气凝胶的改进提出一些建议.     

复合纤维增强疏水SiO2气凝胶的制备及其性能

以正硅酸乙酯(TEOS)为前驱体,复合纤维为增强相,采用溶胶-凝胶法和常压干燥技术制备了纤维增强疏水SiO_2气凝胶复合材料。利用傅里叶变换红外光谱仪、扫描电子显微镜、比表面积分析仪等手段对气凝胶的化学组成、形貌及结构等进行了分析,并且测量了样品的密度和抗折强度。结果表明:经常压干燥制备的SiO_2气凝胶复合材料加工成块性较好,密度在0.27g/cm~3左右,比表面积达到878.544m~2/g;随着复合纤维的掺入,凝胶填充了纤维之间的大部分微米空隙,并与纤维形成了比较密实的结构,复合材料的抗折强度提高到了1.53 MPa,使得材料有较好的韧性,适用于不规则形状的隔热。     

尖晶石型铁氧体纤维的制备及磁性能

以柠檬酸和金属盐为原料, 采用有机凝胶-热分解法制备了MeFe₂O₄(Me=Zn, Ni_0.5Zn_0.5, Ni_0.4Zn_0.4Cu_0.2)铁氧体纤维.通过FT-IR、XRD、TG-DSC、SEM和VSM等测试技术对纤维前驱体凝胶的结构、热分解过程及热处理产物的物相、形貌以及纤维的磁性能等进行了表征.结果表明, 在凝胶形成过程中, 金属离子单齿或双齿螯合配位于柠檬酸根阴离子, 形成线型分子结构, 使凝胶有较好的可纺性. 所制得的纤维具有较大的长径比, 纤维直径在0.5～20.0μm之间.这些纤维在室温下都具有软磁特性, 化学组成、晶粒大小及形貌对纤维的磁性能有着显著影响.ZnFe₂O₄、Ni_0.5Zn_0.5Fe₂O₄和Ni_0.4Zn_0.4Cu_0.2Fe₂O₄纤维的饱和磁化强度分别为2.6、12.7和40.0A·m²·kg^-1, 相应的矫顽力分别为4.77、5.82和4.04kA·m^-1.     

PBMA-SiO2杂化纤维的制备及表征

以正硅酸乙酯(TEOS)和聚甲基丙烯酸丁酯(PBMA)为前躯体,乙烯基三乙氧基硅烷(VTEOS)为偶联剂,通过溶胶-凝胶法制备了SiO2纤维和PBMA/SiO2杂化纤维,并使用IR、SEM、TGA等进行了结构与性能表征,研究了溶胶的杂化反应机理、成纤性能.结果表明:硅烷偶联剂的引入使得PBMA-SiO2杂化纤维均匀性较好,纤维中有机相与无机相之间通过化学键连接,实现了有机-无机组分的充分贯穿;其耐热性能优于纯PBMA.     

La3+掺杂TiO2纳米纤维的制备、表征与光催化性能

结合溶胶-凝胶法、静电纺丝技术和高温煅烧制备了La3+掺杂TiO2纳米纤维.采用扫描电子显微镜、X射线能谱仪、比表面积及孔隙分析仪、X射线衍射仪和紫外分光光度计对纳米纤维的形貌、晶型、表面和孔隙结构以及光催化性能进行了表征和测试.结果表明,La3+掺杂TiO2纳米纤维表面为多孔的纤维状结构.La3+掺杂明显改善了TiO2纳米纤维的表面孔隙结构,对TiO2纳米纤维的粒子生长有一定的抑制作用.光催化降解性能测试结果表明,当La3+掺杂量为0.04%(质量分数)时,TiO2纳米纤维的光催化性能最佳.     

M型锶铁氧体中空纤维的制备和表征

以柠檬酸和金属盐为原料,采用有机凝胶先驱体转化法制备了M型锶铁氧体（SrFe₁₂O₁₉）中空纤维. 通过FTIR、TG/DSC、XRD、SEM和VSM等技术对所得纤维进行了表征. 结果表明,凝胶的可纺性与其化学组成和pH值有关,当柠檬酸与金属离子的摩尔比为1.5∶1.0,pH=4.2左右时,凝胶的可纺性最好. 经1100℃焙烧后,制备的M型锶铁氧体中空纤维具有较大的长径比,直径可小于1μm,中空孔径约为纤维直径的一半,组成纤维的晶粒形貌为六角片状,晶粒尺寸为236nm,在室温下的饱和磁化强度为53.5A·m²/kg,矫顽力为386.96kA/m. 纤维显示出一定的形状各向异性,当定向排列的纤维平行和垂直磁场时,矫顽力分别为391.66和358.72kA/m.     

SiO2纳米纤维的制备及其对亚甲基蓝染料的吸附性能

以溶胶-凝胶法为基础,通过静电纺丝方法制备PVP/SiO2复合纳米纤维膜,经600℃高温煅烧得到SiO2纳米纤维膜;利用扫描电子显微镜(SEM)观察了SiO2纳米纤维膜的结构形貌;傅里叶变换红外光谱(FT-IR)证实了SiO2纳米纤维的形成;通过X射线衍射(XRD)对SiO2纳米纤维的晶型及晶粒大小进行了分析。通过对其亚甲基蓝染料的吸附,研究了SiO2纳米纤维膜的吸附性能。结果表明制备的SiO2纳米纤维形貌稳定,并对亚甲基蓝染料具有良好的吸附性能。     

热处理有机聚合物螺旋纤维制备螺旋炭纤维及其表征

在400～800℃、氩气气氛下对有机聚合物螺旋纤维进行热处理制备螺旋炭纤维,采用SEM、XRD、FT-IR和热分析等手段对其微观形貌和结构组成进行了研究。结果表明,在上述条件下热处理有机聚合物螺旋纤维,其螺旋形貌基本保持不变,而化学成分却发生了变化;随着热处理温度升高,有机螺旋纤维逐渐转变为以石墨结构为主的螺旋炭纤维。     

表征PAN纤维和炭纤维微细结构的HRTEM样品制备方法

为用高分辨透射电子显微术(HRTEM)表征聚丙烯腈(PAN)纤维和炭纤维的微细结构，从纤维性能出发，探讨研碎、离子束减薄和超薄生物切片三种制备方法及其工艺步骤，结合实验结果，对比了三种制备方法的原理、优缺点，提出了制备方法的适用范围和选择原则，并推断适于表征预氧化纤维微细结构的样品制备方法。与生物样品的制备方法类似，把超薄生物切片法引入到纤维材料HRTEM样品制备领域，为系统研究炭纤维微细结构的演变提供了线索。     

SAPO-34分子筛的微波合成实验研究

分别利用传统的水热法及微波合成两种方法制备SAPO-34分子筛，并通过XRD、SEM分析手段对产物进行了表征，结果表明，微波合成法得到的产物与水热法相比，结晶程度高、晶粒尺寸分布均匀，且略显粗大，与水热法的分散不同，后者晶粒易于团聚。从效率上比较，水热法一个合成周期长达60h以上，而微波合成仅需100min，前者耗能约为后者的72倍，说明，微波加热合成SAPO-34分子筛具有高效、节能的巨大优势。     

Preparation of stable micron-sized crystalline irbesartan particles for the enhancement of dissolution rate

Purpose: In this study, micron-sized crystalline drug particles of irbesartan (IBS) were prepared to improve its stability and dissolution rate.

Method: The approach to crystalline particles was based on the liquid precipitation process by which the amorphous particles were prepared. Pharmaceutical acceptable additives were used as the crystallization agent to convert the amorphous drug into crystalline particles. High pressure homogenization (HPH) process has been employed to reduce the size of the crystalline particles, and the micron-sized particles were obtained by the freeze-drying process.

Results: Different additives show different influences on the polymorphic form of IBS. Polyvinylpyrrolidone (PVP) and hydroxypropyl methylcellulose (HPMC) were effective in stabilizing amorphous particles instead of converting amorphous drug into crystalline particles, while poloxamer407 (F127) and tween80 (T80) could convert the amorphous drug into crystalline particles. T80 was also effective in controlling the particle size than that of F127. After HPH, crystalline particles with an average of 0.8 μm were obtained. The freeze-dried micron-sized crystalline particles exhibited significantly enhanced in vitro dissolution rate when compared to the raw drug. SEM, FT-IR, XRD, DSC and dissolution rate studies indicated that the micron-sized particles were stable during 6 months storage.

Conclusion: The preparation of micron-sized crystalline drug particles is an effective way to improve the stability and dissolution rate of irbesartan.     

Determination of the thermal conductivity and diffusivity of thin fibres by the composite method

It is suggested that the thermal conductivity of very fine fibres can be evaluated indirectly with the aid of composite theory using the experimental data for the heat transport properties of an appropriate composite which contains the fibres. The feasibility of this approach was investigated by determining the thermal conductivity and diffusivity of fibres of amorphous silicon carbide from 25° C to 1000° C contained within a lithium aluminosilicate glass-ceramic using the laser-flash technique for measurement of the thermal diffusivity of the composite. Due to the amorphous nature of the fibres, values for their thermal conductivity and diffusivity were found to be far less than the corresponding data for crystalline silicon carbide. The positive temperature dependence of the thermal conductivity, coupled with the independent observation of an increase in thermal conductivity with specimen thickness, suggests that radiative heat transfer makes a significant contribution to the total heat transferred. A number of advantages and limitations of the composite method for the evaluation of thermal transport properties of fibres are discussed.     

Preparation of high-performance carbon fibres from PAN fibres modified with cobaltous chloride

Preparations of high-performance carbon fibres have been tested and the results are reported in this article. Polyacrylonitrile (PAN) fibres modified with cobaltous chloride have increased the crystal size, the crystallinity and the orientation, and also improved the tensile strength by about 15–40% and the modulus by about 10–20% of the resulting carbon fibres, which were carbonized at 1300 °C. The oxygen content, theAI value and the density for the modified PAN fibres are smaller than those for unmodified PAN fibres. Because the formation of the ladder polymer in the modified PAN fibres is slow and gradual during the stabilization process, the resulting carbon fibres have a better modulus than carbon fibres developed from unmodified PAN fibres. The activation energy of cyclization,E _a, is increased to 180.0 from 156.6 kJ mol^–1 after the modification process. The modified PAN fibres do not reduce the time required for stabilization. The carbon fibres developed from the modified PAN fibres have a greater stacking size,L _c, than those developed from unmodified PAN fibres. A higher stacking size, and therefore a higher number of crystalline carbon basal planes, is one of the reasons for the improved modulus of the carbon fibres.     

Crystallization of fibres inside a matrix: a new way of fabrication of composites

Fibrous composites are normally fabricated by inserting premade fibres into a matrix and trying to tailor mechanical or physical properties of the material by a proper choice of fibre arrangement, fibre volume fraction, structure and properties of interface, etc. As a rule, this method satisfies all the needs fairly well. But in many cases, particularly when heat-resistant composites are involved, it leads to complications which cause composite experts to refrain from being involved in technically very attractive projects. So the need for alternative methods of composite fabrication obviously exists. The process described here is an example of such an alternative. It is based on the fibres growing from the melt within the volume of the matrix. The matrix should have prefabricated continuous cylindrical channels to be filled with the melt of the fibre material. The process is described using as a model a composite with a molybdenum matrix and single crystalline sapphire fibres. It is shown that the productivity of oxide fibre fabrication based on the process described can be some orders of magnitude higher than that based on the well known Czochralsky's and Stepanov's methods. The strength of the single-crystalline sapphire fibres obtained has been studied, as well as the high-temperature creep strength of composites containing such fibres. Some of the results of these experiments are reported here.     

X-ray study of pre-treated regenerated cellulose fibres

Regenerated cellulose fibres have had an important role to play in the man-made fibre field. The very special characteristics of different types of regenerated cellulose fibres, e.g. mechanical properties, sorption characteristics, and aesthetics were conditioned by the differences in their fine structure due to fibre formation processes. Additionally, the finishing processes could influence the fibre structure. A study was done of the crystalline structures of a solvent-spun cellulose fibre type (Lenzing Lyocell), made according to the NMMO process, and two conventional cellulosic fibre types, made by the viscose process (Lenzing Viscose and Lenzing Modal). The fibres were pre-treated (bleached and slack mercerised) and structural changes were followed by wide angle and small angle x-ray scattering (WAXS and SAXS), respectively. The periodical structure, determined by long spacing, was nearly the same in all the different types of fibres. A slight increase was observed after the treatment of viscose and modal fibres, but an unpronounced fall of a long period accompanied the pre-treatment of lyocell fibres. Some changes in crystallinity and crystalline orientation occurred due to the treatment conditions. The structural changes were correlated to the iodinesorption and mechanical properties.     

Novel aqueous sol–gel preparation and characterization of barium M ferrite, BaFe12O19 fibres

Gel fibres of barium M ferrite, BaFe12O19, were blow spun from an aqueous inorganic sol and calcined at temperatures up to 1200°C. The ceramic fibres were shown by X-ray diffraction to be single phase crystalline M ferrite at 1000°C, and surface area and porosity measurements indicated an unusually high degree of sintering at this temperature. The fibres also demonstrated a favourable grain structure of less than 0.1 m at this temperature and maintained a small grain size of less than 4 m even up to 1200°C, an important factor in the magnetic properties of this material.     

球形铁基金属玻璃单分散粒子的制备及评价

利用脉冲小孔法在He气氛下制备出了球形粒径可控的[(Fe_0.5Co_0.5)_0.75B_0.2Si_0.05]₉₆Nb₄金属玻璃单分散微粒子, 这些粒子具有粒径均匀和圆球度高等优良特点. 通过XRD、DSC以及TEM对所获得的粒子进行了检测分析, 结果表明随着粒径尺寸的减小, 微粒子的微观结构从混合相逐渐向全金属玻璃相转变, 制备的粒子均为全玻璃相, 临界尺寸小于645 μm. 通过冷却速率的计算, 得到全玻璃相微粒子的临界冷却速率为800~1100 K/s, 该速度与环境气氛的改变无关, 并且该计算值低于同成分的大块金属玻璃合金TTT曲线的测量值.     

Rapid preparation of crystalline colloidal arrays using a strong electric field dialysis

We present a simple method for rapid preparation of crystalline colloidal arrays (CCAs) by a strong electric field dialysis (SEFD). This method is based on rapid removing of ionic impurities in colloidal suspensions by applying a strong electric field. In a SEFD process, the negatively charged ions in colloidal suspensions are rapidly driven to the anode, the positively charged ones are rapidly driven to the cathode, and the colloidal particles are withheld in the dialysis tube. It was shown that the colloidal particles aggregated on the wall of the dialysis tube could block the SEFD process, which could be overcome by reversing the direction of the electric field. The purified colloidal particles can self-assemble into a crystalline colloidal array, which has an electrostatically stabilized three-dimensional periodic array of colloidal particles with a characteristic lattice spacing that can be varied by dilution. The reflection spectra show distinct peaks due to diffraction from CCAs. Atomic force microscopy (AFM) image illustrates the non-contacted ordering of the colloidal particles in the CCAs embedded in gels. This indicates the formation of high-quality single CCAs. Using a SEFD method, the preparation time of CCAs can be reduced. This new technique will greatly speed up the process of preparing polymerized crystalline colloidal arrays (PCCAs) into real-world application in the analytical field.     

Re-crystallization of silicalite-1 crystals from a crystalline layered silicate using nanosized seeds

Crystallization of silicalite-1 guided by nanosized seeds has been carried out from a crystalline layered silicate. The crystallization process was investigated by crystallinity of silicalite-1 obtained by hydrothermal treatments of the seeds/crystalline layered silicate mixtures with H₂O/Si ratios of 2, 6, and 12, respectively, at 423 K. Time courses of the crystallinity revealed the improved crystallization rate: the crystallization with the seeds was completed for 24 h although it spent more than 48 h without the seeds. SEM observation of the products showed well-crystallized particles with a coffin-like shape reflecting the crystal growth of the seeds. The particles sizes were 2-4 μm for the products by the treatment with the H₂O/Si ratio of 6 and 12, although the size was < 2 μm for the product with the H₂O/Si ratio of 2, suggesting that less H₂O content brings about the limited growth. As a result, we have succeeded to control the crystallization process of silicalite-1 from the crystalline layered silicate by impregnation of the seeds.