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.     

对3种典型铝硅合金熔体温度处理的对比分析

对3种典型成分的铝硅合金(Al-20%Si、Al-12%Si和Al-7%Si)进行了熔体温度处理凝固组织变化规律的比较研究.结果表明: 在Al-12%Si共晶合金熔体处理组织中存在α枝晶与初晶硅共存以及α枝晶在一定处理条件下可以完全消失的现象; 3种成分Al-Si合金的α枝晶及初晶硅的形态尺寸随过热温度、静置时间增加出现周期性的变化规律, 出现最小尺寸的温度、时间并不完全一致; 熔体温度处理对Al-7%Si中枝晶大小、形态等有一定影响, 但细化效果不明显.在铝硅合金中, 硅原子微观有序团簇和铝有序偏聚原子团簇可能存在于不同的温度区间, 铝有序偏聚原子团簇存在的温度区间更靠近温度轴, 硅原子微观有序团簇具有比铝有序偏聚原子团簇更强的结合能.     

氧化铝生产中“硅渣”的组成和结构研究

综合运用Ｘ射线衍射,红外光谱,差热分析等方法,研究氧化铝生产脱Ｓｉ反应生成物－－水合铝硅酸钠渣的组成和结构,证明其为有硅原子缺位的羟基方钠石,ＳｉＯ２与Ａｌ２Ｏ３摩尔比小于２．０主要系方钠石晶格骨架上硅原子缺位所致。     

Properties of poly(n‐butyl methacrylate) prepared by reverse atom transfer radical polymerization in an aqueous dispersed system

Reverse atom transfer radical polymerization (ATRP) of n‐butyl methacrylate (BMA) in waterborne media using Cu(II) complexes with azo initiators (i.e., reverse ATRP) was conducted. The influence of several factors, such as surfactant, catalyst, and reaction time, on the stability of the emulsion, the particle size, the morphology of the emulsion particles, and the control of the polymerization was investigated. The results showed great differences between ATRP and conventional emulsion polymerization, especially the nucleation mechanism and the kinetics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1542–1547, 2003     

有机碱对莰烯直接乙酰化的影响

研究了在含氮有机碱存在下的莰烯直接乙酰化反应，结果表明，在反应中加入与莰烯等摩尔的六氢吡啶，有利于莰烯乙酰化反应，在反应液中的酰化产物ω－乙酰基莰烯含量最高达到56％，大大超过异构化产物乙酸异冰片酯。     

原子转移自由基聚合法制备聚乳酸三嵌段共聚物的研究

以自制的双端羟基聚乳酸与α-溴代丙酰溴反应而制得的含溴端基的聚乳酸为大分子引发剂,溴化亚铜/2,2′-联吡啶为催化体系,研究了N-乙烯基吡咯烷酮的原子转移自由基聚合行为,制得了具有两亲性聚乳酸嵌段共聚物。随单体/引发剂摩尔比的增大、聚合温度的升高,共聚物溶液的特性黏度增大,共聚物薄膜的吸水率增加;共聚物在不同降解介质中的降解规律相似,均随降解时间的延长,共聚物薄膜的失重增加,且在不同介质中呈现的降解速率表现为碱液>酸液>水>缓冲液。对聚合物进行了结构表征。     

活性自由基乳液聚合的研究进展

活性自由基乳液聚合是一个非常新的研究领域。介绍了目前活性自由基乳液聚合领域的3种常用的方法及应用这些方法进行乳液聚合的研究进展,包括:原子转移自由基聚合(ATRP),氮氧调节自由基聚合(NMP)和可逆加成-断裂链转移自由基聚合(RAFT)。     

Synthesis and characterization of poly(vinyl chloride‐co‐vinyl acetate)‐graft‐poly[(meth)acrylates] by atom transfer radical polymerization

The graft polymerization of methyl methacrylate and butyl acrylate onto poly(vinyl chloride‐co‐vinyl acetate) with atom transfer radical polymerization (ATRP) was successfully carried out with copper(I) thiocyanate/N,N,N′,N′,N″‐pentamethyldiethylenetriamine and copper(I) chloride/2,2′‐bipyridine as catalysts in the solvent N,N‐dimethylformamide. For methyl methacrylate, a kinetic plot of ln([M]₀/[M]) (where [M]₀ is the initial monomer concentration and [M] is the monomer concentration) versus time for the graft polymerization was almost linear, and the molecular weight of the graft copolymer increased with increasing conversion, this being typical for ATRP. The formation of the graft polymer was confirmed with gel permeation chromatography, ¹H‐NMR, and Fourier transform infrared spectroscopy. The glass‐transition temperature of the copolymer increased with the concentration of methyl methacrylate. The graft copolymer was hydrolyzed, and its swelling capacity was measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 183–189, 2005     

Atom transfer radical polymerization of n‐butyl methacrylate in an aqueous dispersed system

Atom transfer radical polymerization of n‐butyl methacrylate (BMA) was conducted in an aqueous dispersed system with different kinds of copper complexes. The partitioning behavior of the copper complexes, including CuCl/4,4′‐di(5‐nonyl)‐2,2′‐bipydine (dNbpy), CuCl₂/dNbpy, CuCl/2,2′‐bipydine (bpy), CuCl₂/bpy, CuCl/bis(N,N′‐dimethylaminoethyl)ether (bde), and CuCl₂/bde between the monomer (BMA), and water was studied in detail with ultraviolet‐visible spectroscopy. The results show that with a less hydrophobic ligand, such as bpy or bde, most of the Cu(I) or the Cu(II) complexes migrated from the BMA phase to the aqueous phase, the atom transfer equilibrium was destroyed, and the polymerization was nearly not controlled; it converted to classical emulsion polymerization. As to the very hydrophobic ligand dNbpy, although the partitioning study of the copper complexes indicated that not all the copper species were restricted to the organic phase, the linear correlation between the molecular weight and the monomer conversion and the narrow polydispersities confirmed that the polymerization was still quite well controlled. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3175–3179, 2003     

离子化对SBS/聚(苯乙烯-甲基丙烯酸甲酯)热塑性互穿聚合物网络结构与力学性能影响的研究

采用原子转移自由基聚合（ATRP）法合成了聚（苯乙烯一甲基丙烯酸甲酯）[P（St—MMA）]，采用两步法制备了SBS／P（St—MMA）热塑性互穿聚合物网络（TIPN）。在双螺杆挤出机上通过熔融挤出方法对SBS／P（St—MMA）直接进行水解，制备了含有离子键的SBS／P（St—MMA）TIPN。离子化后TIPN的拉伸强度明显增加，在离子化程度为25％时达到最大，断裂伸长率明显下降。TIPN的中PB和PS嵌段的Tg均明显增加，PS嵌段增加更加明显，提高20℃；弹性模量E’均明显提高。