一种新型含炔基的聚合2-乙基-2-噁唑啉引发剂的合成（英文）

本文利用2-苯基-1,3-二氧六环-5-醇合成了含有一个炔基和两个三氟甲磺酸酯基的三官能团引发剂.首先,2-苯基-1,3-二氧六环-5-醇与炔丙溴反应制得含炔基的中间体.然后在稀盐酸和四氢呋喃水溶液中反应制得含双羟基的中间体,最后在四氯化碳中与三氟甲磺酸酐反应制得新型引发剂.该引发剂的结构由核磁共振氢谱确认.并且用该引发剂引发2-乙基-2-噁唑啉的聚合,得到窄分布的聚合物.作为对比,本文同时合成了一种含两个甲苯磺酸基的引发剂,由于两个甲苯磺酸基之间存在较大的空间位阻,该引发剂聚合所得的聚(2-乙基-2-噁唑啉)分布较宽,并且在反应后的体系中存在大量的未反应的引发剂.为了进一步研究位阻效应对2-乙基-2-噁唑琳聚合的影响,合成了一种线性的含一个甲苯磺酸基的引发剂,用该引发剂引发聚合体系中仍有大量未反应的引发剂存在,说明位阻效应和亲电平衡均会影响2-乙基-2-噁唑啉的阳离子开环效率.聚合物分子量及分子量分布通过核磁共振氢谱,基质辅助激光解吸电离-时间飞行质谱和尺寸排阻色谱表征.     

全谱拟合法研究聚丙烯腈基碳纤维形成过程中晶态结构演变

通过全谱拟合法对碳纤维制备过程中不同阶段纤维的XRD谱图进行处理,得到不同阶段纤维的微观结构参数,研究了聚丙烯腈(PAN)基碳纤维制备过程中晶态结构的演变.全谱拟合法基于晶体衍射的严格物理理论,拟合目标为整个衍射谱,并不是个别衍射峰,所得结果具有更高的可信度.研究结果表明:PAN原丝中的高分子链沿纤维轴高度取向,表观晶粒尺寸为6.5 nm左右;经过预氧化处理,纤维中的有序结构遭到破坏,表观晶粒尺寸锐减.纤维中逐渐形成梯形结构并沿纤维轴取向,从而形成新的有序结构;经过碳化处理后,环状梯形结构转变为碳的层状结 关键词： 碳纤维 晶体结构 XRD 全谱拟合法     

PVP/洛美沙星-铽纳米粒子微波合成及其荧光特性研究

以PVP为表面修饰剂,用微波合成法制备了粒径分布均匀性能稳定的洛美沙星-铽(LELX-Tb3 )纳米粒子,用扫描电镜、红外光谱和荧光光谱进行了表征.重点分析了PVP的引入对洛美沙星-铽纳米粒子的粒径分布、粒子形貌、红外光谱和荧光光谱的影响,发现PVP修饰后的洛美沙星-铽纳米粒子具有更均匀的尺寸分布,荧光发射峰强度增强;确证了PVP的用量是制备洛美沙星-铽纳米粒子的一个重要因素;探讨了PVP对LFLX-Tb3 荧光的增敏机理.     

微乳液聚合制备纳米银/聚苯乙烯复合材料

采用柠檬酸钠为稳定剂、聚乙烯吡咯烷酮为分散剂,以水合肼还原银氨络离子制备出稳定的单分散胶态纳米银。以制得的纳米银溶胶,通过正相微乳液聚合,制备纳米银/聚苯乙烯复合材料。利用紫外-可见光(UV-Vis)吸收光谱研究了纳米银的光吸收特性,采用X射线衍射(XRD)和透射电镜(TEM)对产物的晶体结构、形貌及尺寸进行了分析。结果表明:所制得的银纳米颗粒属立方晶系,平均粒径约10 nm,且无团聚及氧化现象;聚合过程中,纳米银的晶体结构、形貌及尺寸未发生明显变化。凝胶渗透色谱(GPC)分析表明聚苯乙烯基体重均分子量达4.03106,分子量分布指数为1.21;热重-示差扫描量热(TG-DSC)分析表明所制备的复合材料具有优异的热稳定性。     

静电纺丝法制备聚丙烯腈/银纳米粒子复合纳米纤维及其SERS特性

利用静电纺丝技术制备了一种聚丙烯腈/银纳米粒子复合纳米纤维的表面增强拉曼光谱基底。通过调节聚丙烯腈溶液的浓度可得到不同直径、不同厚度的纤维薄膜,将聚丙烯腈的N,N-二甲基甲酰胺溶液与硝酸银溶液混合得到聚丙烯腈/Ag种子溶液,然后利用静电纺丝技术制备聚丙烯腈/Ag种子/AgNO₃复合纳米纤维;加入AgNO₃并利用水合肼二次还原后可制备适合拉曼检测的聚丙烯腈/Ag纳米粒子复合纤维膜,聚合物纤维表面和内部的金属纳米粒子的密度可调节。通过调节不同的纳米粒子的密集程度,可构筑出具有较高的电磁场增强效果的特殊的“热”结构(高局域强电磁场的亚波长区域)。而聚合物纤维内部的银纳米粒子可通过溶胀作用吸附更多的探针分子,提高拉曼检测的灵敏度。该基底有很好的SERS信号,并且可大规模制备。     

ZnO纳米球的溶剂热合成及其结构和光学性质

针对目前采用溶剂热方法制备的ZnO纳米球尺寸比较大,而模板法制备技术又比较复杂的缺点,用六甲基次胺(HDA)作为辅助试剂,采用溶剂热法制备出了小尺寸的ZnO纳米球。本方法不采任何模板,制备过程简单易操作,重复性好。在场发射电子显微镜下可清楚地看到所制得纳米球尺寸分布比较均匀,每一个纳米球都是由许多粒径在20~30nm的小球共同组成的。X射线衍射结果表明所得产物均为六角纤锌矿结构的ZnO。用谢乐公式算得的粒子尺寸在5~11nm,而且随着制备时间的延长和制备温度的升高,ZnO激子吸收峰发生红移,显示出明显的量子限制效应,这表明那些小球可能是由尺寸更小的ZnO纳米粒子所组成。光致发光谱中紫外发射与可见发射的强度比随着制备时间的延长和制备温度的升高而大,表明ZnO纳米粒子的尺寸增大,结晶性变好。     

液相法制备金属纳米粒子

液相法是在均相溶液中，利用各种途径引发化学反应，通过均相或异相成核及随后的扩散生长而制备出粒径分布窄且表面功能化的纳米尺度材料．介绍了液-液两相法、反相胶束、高温液相法等制备单分散金属纳米粒子的方法和高温液相法制备金属纳米粒子的影响因素，以及近年来在金属纳米粒子的制备和性能研究上的进展，尤其是Co等多种磁性纳米粒子的制备、磁性研究．     

ZnO/MCM-41复合材料的制备及其光谱性质

以硅酸钠(NaSiO3·9H2O)为硅源,三甲基十六烷基溴化铵(CTAB)为模板剂在碱性条件下水热合成介孔分子筛MCM-41,然后以其为主体,采用锌盐浸渍-灼烧的方法.在介孔分子筛MCM-41上负载了氧化锌(ZnO)纳米微粒,并通过扫描电子显微镜,红外光谱(1R).紫外可见吸收光谱(UV-Vis),N2-吸附脱附和荧光光谱等手段对产品进行了系列表征.结果表明,分子筛平均直径约为1.7μm,对不同温度下灼烧后得到的ZnO/MCM-41组装体的光谱性质进行研究表明介孔分子筛MCM-41的尺寸所限,制备出的ZnO粒子粒径小于2 nm.量子尺寸效应使得ZnO/MCM-41组装体中的ZnO纳米粒子的紫外可见吸收光谱及荧光光谱均发生蓝移.通过红外光谱分析得知ZnO负载到MCM-41上并没有改变介孔分子筛原有的骨架结构.     

脉冲激光沉积纳米硅晶粒流体模型的推广

Yoshida等人提出的惯性流体模型只能解释脉冲激光烧蚀制备纳米硅晶粒平均尺寸随环境气压的变化规律.在此模型基础上,考虑到烧蚀粒子的初始速度分布(Maxwell分布),得到了纳米硅晶粒尺寸分布的解析表达式,数值模拟结果与Yoshida等人在不同环境氦气压下制备样品的晶粒尺寸分布的实验统计数据基本相符.还利用修正后的模型对不同环境气体种类(氦、氖、氩)中制备的纳米Si晶粒尺寸分布进行了模拟,模拟结果与实验数据相符.结论可为实现纳米硅晶粒尺寸的均匀可控提供理论依据. 关键词： 纳米硅晶粒 脉冲激光烧蚀 惯性流体模型 尺寸分布     

银镜反应制备纳米蛾眼减反结构法

为了降低光学表面的菲涅耳反射,提出了一种制备仿生减反结构的方法.利用银镜反应并结合退火处理在硬性材质基底表面制备银纳米粒子,经反应离子刻蚀工艺,在基底表面形成一层纳米蛾眼减反结构.分析了周期分布和随机分布纳米蛾眼的光学特性,实验研究了退火参量和刻蚀参量对银纳米颗粒直径、密度以及高度的影响,并在硅和石英基底上分别制备了随机减反结构.测试结果表明:硅基平均反射率小于4.5%,双面石英基透过率达98.1%.理论和实验均表明:随机分布的纳米仿生蛾眼结构具有宽光谱、广视角和高减反特性,所提出的制备方法具有简便易行、低成本、大幅面等优点,在光电器件中具有良好的潜在应用前景.     

Characterization of the nanopore structures of PAN-based carbon fiber precursors by small angle X-ray scattering

The nanopore structures in precursors are crucial to the performance of PAN-based carbon fibers. Four carbon-fiber precursors are prepared. They are bath-fed filaments (A), water-washing filaments (B), hot-stretching filaments (C) and drying-densification filaments (D). Synchrotron radiation small angle X-ray scattering is used to probe and compare the nanopore structures of the four fibers. The nanopore size, discrete volume distribution, nanopore orientation degree along the fiber axis and the porosity are obtained. The results demonstrate that the nanopores are mainly formed in the water-washing stage. During the processes of the subsequent production technologies, the slenderness ratio of nanopores and their orientation degree along the fiber axis increase further and simultaneously, the porosity decreases. These results are helpful for improving the performance of the final carbon fibers.     

Electrospinning of biodegradable poly-3-hydroxybutyrate. Effect of the characteristics of the polymer solution

The effect of viscosity and electric conductivity of the polymer solution of poly-3-hydrobutyrate (PHB) on the formation of ultrafine fibers was studied. It was found that these parameters largely determine the geometrical parameters and morphology of the ultrafine fibers of PHB obtained by electrostatic forming. The increase in the viscosity of solutions at increased concentration and/or molecular mass of the polymer leads to an increase in the thickness uniformity of fibers and affects the diameter and diameter distribution width of the ultrathin fibers. Modification of the solutions with an ionogen electrolyte and hydrolytic agent (formic acid) decreases the initial molecular mass of the polymer and leads to increased viscosity of the system. The obtained fibers have found use in biomedicine, in particular, in the design of the elements of the locomotor system.     

一种新型含炔基的聚合2-乙基-2-噁唑啉引发剂的合成

A novel trifunctional initiator with one alkyne and two trifluoromethanesulfonate moieties was synthesized from a protected alcohol 5-hydroxyl-2-phenyl-1, 3-dioxane. The alkyne functionalized intermediate with two protected alcohol groups was synthesized by reacting with propargyl bromide. The alcohol groups were cleaved using a mixture of tetrahydrofuran and hydrochloric acid aqueous solution. In the last step the initiator was synthesized using triflic anhydride in carbon tetrachloride. The initiator was characterized by ¹H NMR and used for the polymerization of 2-ethyl-2-oxazoline which gives polymers with narrow distribution. For comparison a similar initiator with two tosylates was prepared and used for the polymerization of the monomer 2-ethyl-2-oxazoline, the resulting product has a wide molecular weight distribution and most of the initiator remains unreacted after 24 h which may be due to the steric hindrance between the two tosylate groups. To further explore the steric hindrance phenomenon, a linear tosylate initiator was synthesized, but still some of the initiator remains unreacted, illustrating that both steric hindrance and electrophilic balance affect the efficiency of the cationic ring-opening polymerization. All of the polymers were characterized in detail by using ¹H NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy, and size exclusion chromatography to confirm the purity and distribution of the polymers.     

Roles of interfaces between carbon fibers and epoxy matrix on interlaminar fracture toughness of composites

The effect of atmospheric-pressure plasma treatment on high strength PAN-based carbon fibers had been studied in terms of fiber surface energetics and mode I and II interlaminar fracture toughness of unidirectional carbon fibers/epoxy matrix composites. The surface characterization of plasma treated carbon fibers was investigated by X-ray photoelectron spectroscopy (XPS) and contact angles. As a result, the plasma treatment changed the surface properties of the carbon fibers, mainly through formation of oxygen functional groups like hydroxyl, carbonyl, and carboxyl groups. According to contact angle measurements, it was observed that plasma treatment led to an increase in surface free energy of the fibers, mainly due to the increase of its specific component. Fracture toughness test results employing double-cantilever beam (DCB) and end notched flexure (ENF) specimens also showed that the increase in specific components or hydrogen bonding between the –OH groups on carbon fibers and the =O ring in epoxy matrix resins played an important role in improving the degree of adhesion at interfaces, resulting in an increase in the interfacial fracture toughness of the composites studied.     

Polymerization of Kraft lignin via ultrasonication for high-molecular-weight applications

Kraft lignin is an inexpensive and abundant byproduct of pulp mills that can be used in the synthesis of adhesives and carbon fibers along with energy production. Some of these material applications favor the utilization of high molecular weight (HMW) lignin. This study investigates the use of ultrasonics as a means to increase the degree of polymerization (DP) of highly purified Kraft lignin. Treated samples were characterized by gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, ¹³C and ³¹P nuclear magnetic resonance (NMR). After 15 min of sustained cavitation, ultrasonicated lignin generated a high molecular-weight fraction (～35%) that had a weight-average molecular weight (M_w) over 450-fold greater than the initial Kraft lignin sample. ¹³C-NMR and ³¹P-NMR analysis indicated that the highly-polymerized fraction was enriched with C5 condensed phenolic structures.     

PAN基活性炭纤维的表面及其孔隙结构解析

通过氮吸附等温线、Ｘ射线光电子能谱以及扫描电子显微镜（ＳＥＭ）对聚丙烯腈（ＰＡＮ－Ｐｏｌｙａｃｒｙｌｏｎｉｔｒｉｌｅ）－基活性炭纤维（ＡＣＦ－Ａｃｔｉｖａｔｅｄ Ｃａｒｂｏｎ Ｆｉｂｅｒ）的表面和孔隙结构进行了分析，结果表明吸附测量可以提供有关碳质吸附剂的孔结构复杂性；通过ＸＰＳ对ＰＡＮ基ＡＣＦ的表面官能团的种类及含量进行了表征，由ＳＥＭ对ＰＡＮ基ＡＣＦ的表面以及断面的孔隙结构进行直拉观察，提供了     

利用TG-FTIR联用技术对Kevlar纤维的热解过程的分析

现代工业应用与技术领域要求材料具有良好的机械性质与热学性质,Kevlar纤维做为近年来材料领域研究的热点纤维材料,具有高强度、耐高温等良好的性能。纤维材料的性质依赖于自身的结构和组成,热分解过程对于研究材料的结构和热学性质有着十分重要的意义。热红联用技术做为一种新型的联用技术,既能定量又能定性地进行分析,在研究材料的热分解过程中具有明显的优势。由于Kevlar纤维的热分解过程在文献中少有报道,本文首次利用TG-FTIR联用技术对Kevlar纤维在室温到800 ℃的热解过程进行分析,得到了Kevlar纤维热解过程的详细步骤及各个步骤的反应产物。结果表明,Kevlar纤维的热解经历了3个阶段,分别为100～240,240～420,420～800 ℃。在500 ℃之前Kevlar纤维失重很缓慢,第三个阶段是纤维的主要失重阶段,最终固体的残留质量为56.21%。红外光谱数据表明,Kevlar纤维热解过程先释放出游离水,随后发生脱水反应和解聚反应,使纤维分子链断裂。最后纤维碎片进一步反应生成小分子气体,水、氨气、一氧化碳、二氧化碳为主要产物。其中水的析出量逐渐增大;氨气的析出量保持基本一致;一氧化碳仅在515～630 ℃产生,随后即氧化生成二氧化碳;二氧化碳的析出量经历了一个由于一氧化碳转化而产生的增长后,又下降到一定值保持稳定。     

PAN基碳纤维在石墨化过程中的拉曼光谱

采用激光拉曼光谱研究了PAN基碳纤维在石墨化(2 000～3 000 ℃)过程中的结构变化;比较了石墨化前后纤维表面和断面拉曼光谱特征。结果表明：高温石墨化后,碳纤维的一级拉曼光谱有3个峰(D,G和D′),表征碳纤维结构有序程度的拉曼参数主要有D和G峰的半高宽(FWHM)、G峰的拉曼位移和D与G峰的积分强度比R(I_D/I_G)。随着热处理温度的提高,D和G峰的半高宽、G峰的拉曼位移和R值均逐渐减小,即使经过3 000 ℃高温处理后,D峰仍然存在,R值为0.19,说明纤维中仍存在无序结构。另外,R值与纤维中石墨微晶的基面宽度L_a成反比,石墨化后纤维取向性的增加使得表面和断面的拉曼光谱有明显的差异。因此,可利用激光拉曼光谱来定量表征碳纤维的石墨化程度和取向。     

裂解温度对CVD法制备多壁碳纳米管的影响

用SEM、TEM、HRTEM及拉曼光谱方法研究了催化裂解乙炔制备多壁碳纳米管过程中裂解温度的影响,结果表明,在650℃～700℃裂解乙炔,可获得产量高、直径分布均匀、石墨程度高的多壁碳纳米管,并对裂解温度影响机制进行了分析和探讨。