Novel dinitroxide mediating agent for stable free‐radical polymerization

A novel dinitroxide mediating agent that was suitable for stable free‐radical polymerization was synthesized and used in the block copolymerization of styrene and t‐butyl styrene. Quantitative yields of a novel dinitroxide based on 1,6‐hexamethylene diisocyanate and 4‐hydroxy‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy were obtained. Various experimental parameters, including the nitroxide‐to‐initiator molar ratio, were examined, and it was determined that the polymerization was most controlled under conditions similar to those of conventional 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated stable free‐radical polymerization. Moreover, the dinitroxide mediator proved to be a viable route for the facile two‐step synthesis of triblock copolymers of styrene and t‐butyl styrene. However, the dinitroxide mediation process resulted in a higher than expected level of nitroxide decomposition, which resulted in polymers possessing a terminal alkoxyamine and an adjacent hydroxylamine rather than a preferred internal bisalkoxyamine. This decomposition resulted in the formation of diblock copolymer species during the triblock copolymer synthesis. Gel permeation chromatography was used to monitor the chain‐end decomposition kinetics, and the determined observed rate constant (5.89 × 10^?5 s^?1) for decomposition agreed well with previous studies for other dinitroxide mediating agents. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1547–1556, 2004     

Adsorption Behaviour of 134Cs and 22Na Ions on Tin and Titanium Ferrocyanides

Tin and titanium ferrocyanides were studied as adsorbents for alkali metal ions, viz., ¹³⁴Cs and ²²Na, which represent radioactive wastes. The ferrocyanides were prepared in granular form. The tin version contained 11.2% water, while the titanium version contained 17.7% water. The exchange capacities for Cs⁺ and Na⁺ in the hydrated tin version were about 1.5 and 0.7 meq/g, respectively, while those in the titanium version were 2.2 and 1.2 meq/g, respectively. Drying at 250°C decimated those capacities. The diffusional time constant of Cs⁺ at 25°C, determined via Fick's second law, was of order of magnitude 1 × 10^–3 s^–1, though there were minor differences due to particle size and the form of ferrocyanide. Similarly, the effective diffusivity was of order of magnitude 1 × 10^–8 cm²/s. The titanium version responded slightly faster than the tin version. Likewise, equilibrium measurements in mixtures with sodium nitrate, potassium nitrate, or uranium oxide, showed that the titanium version exhibited significantly greater selectivity for Cs⁺ than did the tin version. Unfortunately, tests of complete elution of the Cs⁺ from the ferrocyanides were mostly disappointing. Work continues on that subject.     

Polyesterification of aromatic dicarboxylic acids and bisphenols with tosyl chloride/dimethylformamide/pyridine promoted by the improvement of the difficult solubility of the activated diacids with lithium chloride

The solution polyesterification of dicarboxylic acids in pyridine, the activated intermediates of which were difficult to dissolve in tosyl chloride/dimethylformamide/pyridine, was investigated in the presence of lithium chloride. The solubility of the activated dicarboxylic acids was largely improved by the presence of the salt, and the polycondensation with bisphenols was greatly facilitated. The salt was more effectively added to a pyridine solution of dicarboxylic acids than to the activated dicarboxylic acids in pyridine. The favorable additive effect on the improved solubility was attributed to a lowered degree of association of the activated dicarboxylic acids, which led to distributions of the resulting oligomers from bisphenols at an earlier stage closer to the theoretical ones and yielded better polycondensation results. The reaction, which proceeded through favorable distributions of the co‐oligomers, produced copolymers of higher inherent viscosities and slightly block sequence distributions determined by NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2725–2733, 2004     

聚焦慢速高荷态重离子束微束斑X射线源

利用电子束离子源(EBIS)或者电子束离子陷阱(EBIT)产生的慢速高电荷态重离子束轰击金属靶面,离子束与靶面作用并复合辐射特征X射线;并将高荷态离子束采用离子光学系统会聚为微细束后再与靶面作用,能够辐射出微米甚至亚微米级、纳米级的微束斑X射线.本文介绍这一新型微束斑X射线源的结构、机理及其特性等.     

介质靶表面的充电效应对等离子体浸没离子注入过程中鞘层特性的影响

针对等离子体浸没离子注入技术在绝缘体表面制备硅薄膜工艺，采用一维脉冲鞘层模型描述介质靶表面的充电效应对鞘层厚度、注入剂量及靶表面电位等物理量的影响.数值模拟结果表明：随着等离子体密度的增高，表面的充电效应将导致鞘层厚度变薄、表面电位下降以及注入剂量增加，而介质的厚度对鞘层特性的影响则相对较小. 关键词： 等离子体浸没离子注入 脉冲鞘层 绝缘介质 充电效应     

强流束晕-混沌的外部磁场开关控制

研究了强流离子束在周期聚焦磁场通道中束晕-混沌的外部磁场开关参数控制方法. 将该方法应用在多粒子模型中，实现了对5种不同初始分布质子束的束晕-混沌的有效控制，得到了消除束晕及其再生现象的理想结果.在强流加速器系统中，由于外部磁场是可测和可调 的物理量，因此该控制方法有利于实验研究，可为强流质子加速器中周期聚焦磁场的设计和实验提供参考. 关键词： 强流离子束 周期聚焦磁场通道 束晕_混沌 混沌控制 开 关控制     

离子束增强沉积VO2多晶薄膜的温度系数

用改进的离子束增强沉积方法和恰当的退火从V2O5粉末直接制备了VO2多晶薄膜.实验测试表明，薄膜的取向单一、相变特性显著、结构致密、界面结合牢固、工艺性能良好，薄膜的电阻温度系数（TCR）最高可达4.23%/K.从成膜机理出发，较详细地讨论了离子束增强沉积 VO2多晶薄膜的TCR高于VOx薄膜的TCR的原因.分析认为，单一取向的VO2结构使薄膜晶粒具有较高的电导激活能，致密的薄膜结构减少了氧空位和晶界宽度，使离子束增强沉积 VO2多晶薄膜结构比其他方法制备的VOx薄膜更接近于单晶VO2是其具有高TCR的原 关键词： VO2多晶薄膜 离子束增强沉积 热电阻温度系数     

强流离子束离子径向密度分布的模拟研究

对初始分布为K-V分布的离子束进行模拟研究.除观察到存在束晕现象外，还发现离子束在通 道内运行过程中，离子沿径向密度分布发生了变化. 通过延迟反馈控制，不仅可以消除束晕 ，而且只要控制参数适当，也可以使束中心部分呈均匀分布状态. 关键词： 强流离子束 束晕 填充因子 离子密度分布     

稀土粉末Eu∶Y_2O_3的自由感应衰减量子拍

稀土固体是重要的激光和光电子材料。目前 ,由于以宽带信号和太赫兹比特数据传输率为特征的信息技术的发展 ,稀土固体材料的相干瞬态动力学过程成为宽带与高速信息光子学的基本物理问题之一。研究了室温下稀土粉末样品Eu3+ ∶Y2 O3自由感应衰减的相干瞬态光谱 ,这有助于理解有效的光吸收动力学、激发态弛豫、相干能量传递和超短光脉冲在稀土固体中的传播。用一对紫外飞秒相干光脉冲作用于稀土粉末样品Eu3+ ∶Y2 O3,然后监测物质激发态的布居数随两个激发脉冲之间的延时的变化 ,测量到其自由感应衰减量子拍 (FID) ,从拍频周期分析确定了其能级精细结构 ,能级的退相时间长达皮秒量级。理论分析和实验结果符合得很好。对稀土离子的量子干涉的研究 ,表明其在受激受控光放大方面具有潜在的应用前景     

超短脉冲超强激光与固体靶相互作用中高能离子的产生

 用2D3V PIC粒子模拟方法得到了超短脉冲超强激光与固体靶相互作用中高能离子产生的图像，并对其机理进行了研究。在靶前后表面都观察到了高能离子的产生，并诊断了离子能谱。模拟结果表明，在靶前表面所产生的高能离子，角分布较大，在向靶内输运过程中会损失能量；在靶后表面产生的高能离子，定向性很好，能获得很高的能量。模拟得到的离子能量和实验观测结果在量级上相符。