过硫酸盐和N,N,N′,N′-四甲基乙二胺体系引发烯类聚合机理的研究

<正> 过硫酸盐和N,N,N′,N′-四甲基乙二胺(TMEDA)体系用作烯类聚合的引发剂已有报道。本文报道该引发体系的反应机理。1.实验方法     

Initiation of polymer degradation via transfer of infectious species

A novel dual stage chemiluminescence detection system incorporating individually controlled hot stages has been developed and applied to probe for material interaction effects during polymer degradation. Utilization of this system has resulted in experimental confirmation for the first time that in an oxidizing environment a degrading polymer A (in this case polypropylene, PP) is capable of infecting a different polymer B (in this case polybutadiene, HTPB) over a relatively large distance. In the presence of the infectious degrading polymer A, the thermal degradation of polymer B is observed over a significantly shorter time period. Consistent with infectious volatiles from material A initiating the degradation process in material B it was demonstrated that traces (micrograms) of a thermally sensitive peroxide in the vicinity of PP could induce degradation remotely. This observation documents cross-infectious phenomena between different polymers and has major consequences for polymer interactions, understanding fundamental degradation processes and long-term aging effects under combined material exposures.     

过氧化氢与N—甲基苯胺盐酸盐引发体系的研究

在水介质中,研究了新型的过氧化氢/N-甲基苯胺盐酸盐引发体系对 AM 与 PVA 的接枝共聚。产物经紫外光谱、红外光谱和 ~1H-核磁共振进行表征,并提出了引发机理。     

含氧光敏引发体系的研究——Ⅶ.二苯酮羧酸胺盐的光谱性质和光引发作用

本文合成了一类新的二苯酮羧酸胺盐(BPAA),包括具有不同碳链长度的伯胺盐和叔胺盐二个系列共六种化合物。实验结果表明,BPAA和二苯酮(BP)的光物理性质相似,长碳链BPAA分子具有显著的两亲性质,在非水溶液中可发生分子缔合形成反胶束。由BPAA与叔胺(TEA)组成的体系,引发MMA光聚合反应,聚合速度(R_p)比单用BP快得多,其中BPAA叔胺盐比相应的伯胺盐活性高,长链BPAA比短链BPAA活性高。另外还对比了氧气和氮气条件下的聚合反应速度,氧存在时R_p可增加二倍以上。此外还研究了BPAA/TEA浓度对聚合反应的影响。     

光敏聚合中含二苯酮基高聚物的引发作用

合成了多种不同分子量和不同二苯酮侧基含量的高分子敏化剂PVB,从紫外吸收光谱及发射光谱的测定结果表明,PVB基本保持小分子二苯酮(BP)的光化学特性。采用PVB与叔胺组成光敏引发体系引发MMA光聚合时,聚合速度(R_ο)与小分子相比增加二倍以上。而且R_p随PVB分子中二苯酮基含量的增加而增加,当PVB分子量提高时引发聚合能力加强,这和高分子敏化剂分子链中高效率的能量传递以及色基的密集分布特性有关。     

平面火花隙三电极开关研制及性能测试

 研制了一种适用于平行板传输连接的平面火花隙三电极开关，开关正负电极为半圆形状，触发电极为细条状。将之替代立体式（半球形电极）火花隙三电极开关并应用于爆炸箔起爆装置中，装置回路参数将得以优化。实验测试了空气间隙为4.12， 3.14和2.2 mm的平面火花隙三电极开关的性能。结果表明，在开关间隙间距一定的情况下，随着电压的升高，开关间隙的放电时延和分散时间呈指数降低，开关电感小于15 nH；对于不同范围内的应用电压，使用不同间隙间距的开关，其分散时间不大于10 ns。该开关应用于较低充电电压（小于10 kV）的脉冲功率装置中，与立体式火花隙三电极开关相比，回路电感降低了约50 nH，放电周期缩短近1/3，峰值电流增加约1/3。     

On kinetics of hysteresis

An initiation criterion and a kinetic relation describing hysteresis in shape memory alloys consistent with non-equilibrium thermodynamics are proposed. The initiation of phase transition begins always at zero driving force, defined as the negative derivative of free energy with respect to the volume fraction of high strain phase. The kinetic relation is obtained from the dissipation potential which is proportional to the magnitude of the volume fraction rate times the newly formed volume fraction. The proposed theory turns out to be rate-independent, but history dependent, and can describe all features of hysteresis loops observed in experiments.      

汶川震区北川9.24暴雨泥石流特征研究

2008年9月24日汶川震区的北川县暴雨导致区域性泥石流发生,这次9.24暴雨泥石流灾害导致了42人死亡,对公路和其他基础设施造成严重损毁。本研究采用地面调查和遥感解译方法分析地震与暴雨共同作用下的泥石流特征,获取的气象数据用于分析泥石流起动的临界雨量条件。本文探讨了研究区泥石流起动和输移过程,并根据野外调查,分析了泥石流形成的降雨、岩石和断层作用,特别是强降雨过程与物源区对泥石流发生的作用。根据应急调查发现北川县境内暴雨诱发的泥石流72处,其分布受岩石类型、发震断层和河流等因素控制。根据对研究区震前和震后泥石流发生的临界雨量和雨强的初步分析,汶川地震后,该区域泥石流起动的前期累积雨量降低了14.8%～22.1%,小时雨强降低25.4 %～31.6%。震区泥石流起动方式主要有二种,一是由于暴雨过程形成的斜坡表层径流导致悬挂于斜坡上的滑坡体表面和前缘松散物质向下输移,进入沟道后转为泥石流过程;二是"消防水管效应"使沟道水流快速集中,并强烈冲刷沟床中松散固体物质,导致沟床物质起动并形成泥石流过程。调查和分析发现沟内堆积的滑坡坝对泥石流的阻塞明显,溃决后可导致瞬时洪峰流量特别大。研究结果表明了汶川震区已进入一个新的活跃期。因此,应该开展对汶川地震区的泥石流风险评估和监测、早期预警,采取有效的工程措施控制泥石流的发生和危害。     

Detonation formation in H $_2$-O $_2$/He/Ar mixtures at elevated initial pressures

In this paper the formation of detonation in H-O/He/Ar mixtures at elevated initial pressures was investigated in an initiation tube for a detonation driver with an exploding wire as the ignition source. In most experiments the detonation wave was formed by a DDT process in which a reactive shock wave accelerates behind the leading shock wave and eventually leads to the onset of detonation. The onset position was found to be at the leading shock wave or behind it. Only in very sensitive mixtures at high initial pressure the direct initiation of detonation was observed. The influence of ignition energy, initial pressure and composition on the detonation induction distance was determined. The results show that the detonation induction distance increases with the decrease of ignition energy and initial pressure and with the increase of the mole fraction of helium or argon. With the same mole fraction, argon increases the induction distance more than helium. In the facility utilized the DDT upper and lower limits of hydrogen in H-O mixtures are in the ranges from 36 to 40 % and from 78 to 82 %, respectively, and the upper limits for helium and argon in stoichiometric H-O mixtures are 40 % and 36 %, respectively. High pressure peaks generated by the DDT process were measured, especially in mixtures near the DDT limits. Statistical results show that such peak pressures can be up to 6 times of the CJ-pressures. Received 1 March 2000 / Accepted 25 May 2000     

RADICAL PHOTOPOLYMERIZATION USING ARYLIODONIUM SALT/TERTIARY AMINE COMPLEX SYSTEM AS THE PHOTOINITIATOR

The diphenyliodonium salt (DPIOC)/triethylamine (TEA) is used as photoinitiator for radical photopolymerization. It was found that a ground state CT complex formed between DPIOC as electron acceptor and TEA as electron donor, which results in extending the photosensitivity range of DPIOC/TEA system up to above 500nm compared with DPIOC alone. The kinetic studies on photopolymerization of methyl methacrylate (MMA) were carried out in CH_3CN: H_2O (14: 1, v/v) mixture solution at 30℃by dilatometer. The results obtained show that the polymerization rate (R_p) increases with increasing concentrations of DPIOC and TEA with exponent 0. 65 and 0. 62 respectively. The activation energy E_a and k_p/k_~(1/2) value were determined to be 4.1 Kcal mol~(-1) and 0.045 respectively. The other influence factors and reaction mechanism were also discussed.