分子动力学模拟铜纳米团簇的结构稳定性

利用分子动力学研究了原子数为13～1 055的铜纳米团簇.结果表明:随着尺寸的减小,铜纳米团簇的结构发生晶体→非晶→晶体→非晶→晶体→非晶的转变.团簇平均原子结合能随着尺寸的减小而减小,且只依赖于短程有序,这说明了团簇平均原子结合能一般不能够作为非晶与密堆结构晶体转变的判据.平均原子间距不但依赖于团簇的尺寸,且对团簇结构的变化敏感,可以作为非晶与密堆结构晶体转变的一个判据.对偶分布函数的研究表明,大尺寸团簇的内部和表层原子结构都表现出晶格收缩效应,且不同于相应块体晶格,这表明了目前文献中关于团簇的块体加表面模型与壳核模型都有待改进.     

镍系聚丁二烯橡胶生产技术进展

介绍了近几年国内外镍系顺丁橡胶生产技术的进展情况，内容涉及分子量调节技术、催化剂配置技术、节能降耗的气相聚合、本体聚合工艺及橡胶后处理过程中使用的热泵技术、螺杆挤压工艺，同时也对国内外顺丁橡胶新型防老剂的使用情况及其新品种的开发进行了简要介绍。     

高性能纤维的弯曲疲劳断裂研究

在自制弯曲疲劳装置上 ,对 3种高强对位芳纶及超高相对分子质量聚乙烯纤维 (Dyneema SK65 )进行双面弯曲疲劳试验。结果表明 ,Twaron 2 0 0 0弯曲疲劳寿命的自然对数与预加应力、弯曲角度呈线性关系 ,Dyneema SK65弯曲疲劳寿命明显长于对位芳纶 ,Twaron 2 0 0 0 ,Kevlar 12 9相近 ,都比Kevlar 2 9略长 ;高强型对位芳纶的弯曲疲劳断裂断口芯层呈现出“毛笔头”或“拔丝形”原纤化分裂形态 ,超高相对分子质量聚乙烯纤维弯曲疲劳断裂断口有明显的脆性折断形态 ,无原纤出现。     

新型功能高分子材料及其应用

功能高分子是一类具有特殊用途的高分子材料 ,印迹高分子、敏感性水凝胶和固定化酶是三种较有特色的功能高分子材料。该文将对上述三种功能高分子材料以及它们在生化分离、生物催化、物质分析与检测以及药物控制释放中的应用做一介绍 ,同时也对它们的不足和发展前景进行了评述     

低截留分子质量新型聚芳醚腈酮超滤膜的研制

以新型聚芳醚腈酮为膜材料 ,以N -甲基 - 2 -吡咯烷酮 (NMP)为溶剂 ,研究了聚合物浓度、添加剂种类及含量、凝胶浴温度等对超滤膜性能的影响。结果表明 ,聚合物质量分数以 1 2 %～ 1 3 %为合适的制膜浓度 ,以聚乙二醇PEG - 4 0 0为添加剂时获得了高截留率和高水通量的超滤膜。随着凝胶浴温度的升高 ,水通量明显增大 ,而截留率有所下降 ,而共聚物的浓度增加则有相反的效果。制得的超滤膜具有较低的截留分子量 (PEG- 2 0 0 0 ) ,将制得的超滤膜用于达旦黄、黄X-G等染料的分离 ,截留率均达 90 %以上     

Synthesis and characterization of aromatic polyisoimides derived from PMDA and para-diamines. An approach to in situ generated rigid-rod molecular composites

A new concept for the processing and fabrication of rigid-rod molecular composites aiming at the elimination or minimization of phase separation is proposed. This approach calls for a coil-like aromatic polyisoimide which is soluble and compatible with an amorphous matrix polymer or thermosettable oligomer and can undergo facile transformation to the corresponding rigid-rod polyimide in solid composite state, thus imparting the inherently high strength/high modulus properties to the final form. To this end, various synthetic routes were explored to obtain para-diamines which could afford high molecular weight and aprotic-solvent-soluble polyisoimides upon polymerization with pyromellitic dianhydride (PMDA). Four such polyisoimides were prepared, with their inherent viscosities ranging from 0.25 to 1.89 dl g⁻¹ in dimethylacetamide at 30°C. Facile thermally induced isoimide-imide conversion was demonstrated by solid-state (film) Fourier transform infrared spectroscopy. A preliminary evaluation of the compatibility of the polyisoimide/matrix resin was made. In one instance, a film prepared from the polyisoimide derived from PMDA and 3,3′,5,5′-tetramethylbenzidine (TMB) showed no visually detectable phase separation.     

Adhesion Mechanisms of Polyurethanes to Glass Surfaces I. Structure-Property Relationships in Polyurethanes and Their Effects on Adhesion to Glass

Polyurethanes were prepared from toluene diisocyanate (TDI), 1-4-butane diol (BDO) and polycaprolactone-based triols with varying molecular weights. Among each molecular weight triol-based urethane, hard segment content was varied from 20% to 70%. Differential scanning calorimetry, tensile testing, and Iosipescu shear testing were done on all the various urethanes prepared. Thermal characterization data revealed the dependence of phase separation on hard segment content as well as on the triol molecular weight. Tensile data and Iosipescu shear data further confirmed the observations made from the DSC data. The data further indicated that phase separation can greatly improve the modulus of cross-linked segmented urethanes. Adhesion of these urethanes to glass surface was evaluated using soda-lime float glass plate. Urethane samples were cast on the air side of the glass plates and adhesion was measured in shear mode. Adhesion data indicated that in addition to hard segment content, modulus, cross-link density, and molecular weight of the triols, phase separation seems to be a major factor in controlling adhesion. Surfaces of the failed adhesion samples were also analyzed and the failure mode was found to be cohesive, in varying degree, with the different urethane systems.     

Hydroxyls nests in defective silicalites and strained structures derived upon dehydroxylation: vibrational properties and theoretical modelling

Defective silicalite, an efficient and selective catalyst in the gas phase Beckmann rearrangement reaction, has been characterised by infrared spectroscopy and by molecular modelling techniques. We report a detailed IR study on the effect of outgassing treatments at increasing temperature on silanols bands and on framework modes. The effect of a temperature decrease up to 100 K (during the IR measurement) on the H-bonding interactions has also been investigated. The interaction of silanols with mesitylene, a probe molecule which cannot penetrate the channels, has been studied in order to distinguish between internal and external OH groups. Molecular mechanics and ab initio methods have also been used to model the structure and the vibrational features of a properly designed nest in order to support the assignments of the IR spectrum.     

超高分子相对质量部分水解聚丙烯酰胺合成研究

选择AM均聚后水解工艺路线,采用新型复配引发体系,合成作为油田驱油剂的超高相对分子质量聚丙烯酰胺(简称PAM).在所选高效的引发体系下,考察了主要聚合反应因素对产品平均分子相对质量的影响,确定了聚合工艺条件溶液的pH值为11～11.5,W(单体)为45%,W(引发剂)为70×10-6,W(链转移剂)为1.3×10-6.在优化的聚合条件下,合成了相对分子质量高达25×106,水解度在20%～30%可调,过滤比小于1.3的聚丙烯酰胺.     

分子蒸馏过程模型化研究进展

介绍了分子蒸馏基本原理和常用分子蒸馏设备 ,系统地对分子蒸馏过程模型化的研究进展情况进行了叙述 ,重点介绍了蒸发系数法、液体内部传质传热和蒸馏区惰性气体压力对分子蒸馏的影响等方面的研究结果 ,并对其进行了评述 ,同时对分子蒸馏过程研究的进一步发展提出了一些展望。