铁体系催化丁二烯聚合的研究

本工作研究了以三氯化铁为主催化剂，三异丁基铝为助催化剂，吡啶、苯胺、丙烯腈、乙二胺、四甲基乙二胺、2,2'－联比啶和邻啡啰啉等含氮化合物为配位体的催化体系聚合丁二烯。发现邻啡啰啉做配位体时，该体系有很高的催化活性，Fe/BD为3.0 * 10~(-5)，Al/BD为2.0 * 10~(-3)时，聚合物收率可达90％以上。认为能与活性中心形成五圆或六圆螯合环的共轭含氮化合物做配位体，对聚合活性有非常显著的提高。而且共轭的程度愈高，活性愈高。故乙二胺、四甲基乙二胺、2,2'－联吡啶及邻啡啰啉虽然都能够与Fe形成五圆螯合物，但活性不一样：并用分子轨道理论进行了讨论。本文详细地研究了FeCl_3-Al(i-C_4H_9)_3-phen体系催化丁二烯聚合，考察了phen、Al(i-C_4H_9)_3的用量及聚合温度对催化活性、聚合物特性粘数及微观结构的影响。加入phen得到中乙烯基PBD(1,2-结构为40％－60％)，而不加入phen则得到顺式1,4－结构较高的PBD（顺式－1,4结构为74.4％）。该体系得到的PBD的特性粘数一般大于10，难以加工，故进行了分子量调节的尝试。体系中加入氯化正丁烷、溴代正丙烷、碘甲烷等卤代烷及三氯乙烯、氯代苯等卤代烃，均不能使PBD的分子量降低，而且用量较大时基本不影响聚合反应。卤代丙烯及氯代苄均可以降低PBD的分子量，其中氯丙烯的分子量调节效果最佳。若用量合适，可以使PBD的特性粘数从10以上降到4以下，而基本上不影响聚合物收率。PBD的分子量分布较窄，分布宽度指数为2.0左右，不随氯丙烯的用量而改变。从实验结果讨论了FeCl_3-AlCi-C_4H_9)_3-phen体系催化丁二烯聚合的机理及分子量调节剂的链传移机理。认为该体系催化丁二烯聚合的活性中心为：链转移是通过分子量调节剂对活性中心的氧化加成－还原消除反应进行的。在phen存在下，FeCl_3、Fe(acac)_3等与烷基铝作用，及(phen)_2FeCl_2与烷基铝作用，均可以生成烷基铁络合物：但只分离出(C_2H_5)_2Fe(phen)_2。(i_C_4H_9)_2(phen)_2及由氯化铁和(phen)_2FeCl_2合成的烷基铁络合物还未得到纯的产物，但从反应产物的易氧化性、水解产物的分析及红外光谱，证实产物中存在烷基铁。用元素分析、红外光谱、远红外光谱及气相色谱分析表征了(C_2H_5)_2Fe(phen)_2的结构。(C_2H_5)_2Fe(phen)_2单独使用不能使丁二烯聚合，需加少量的烷基铝，与其中一个配位体络合，使活性中心有供丁二烯配位的空轨道，聚合反应才能顺利进行：得到的PBD特性粘数为1.8～2.4左右，1,2－结构为40－60％，顺式－1,4结构为53～41％，反式－1,4结构很少。初步证明所提出的铁体系催化丁二烯聚合的机理基本上是正确的。初步表征了铁体系聚丁二烯硫化胶的性能，其抗张强度为203～205公斤／厘米~2，300％定伸强度为70～125公斤／厘米~2，伸长离为453～573％。

蹄蝠科的核型进化：比较染色体涂色、G带和C带分析

：与其姐妹科(菊头蝠科)相比，蹄蝠科的细胞遗传学研究较少。迄今为止，仅少数蹄蝠科几个物种有高分辨率的G带核型报道，且有关该科核型进化的大多数结论都是基于常规Giemsa染色研究而得。该研究利用三叶小蹄蝠的染色体特异探针，通过比较染色体涂色、G和C显带，建立了5种蹄蝠的染色体同源性图谱，并探讨了它们同源染色体间的G和C带异同。结果表明：罗伯逊易位、臂内倒位以及异染色质的扩增可能是蹄蝠科物种核型进化的主要机制。通过对这5种蹄蝠物种及其外群物种之间的同源染色体片段的比较分析，作者推测蹄蝠科的祖先核型并不像先前认为的全由端着丝粒染色体组成, 而应该含有中着丝粒染色体。

Fabrication of Silicon Condenser Microphone Using Oxidized Porous Silicon as Sacrificial Layer

A new technique to fabricate silicon condenser microphone is presented. The technique is based on the use of oxidized porous silicon as sacrificial layer for the air gap and the heavy p~+-doping silicon of approximately 15μm thickness for the stiff backplate. The measured sensitivity of the microphone fabricated with this technique is in the range from -45dB (5.6mV/Pa) to -55dB (1.78mV/Pa) under the frequency from 500Hz to 10kHz, and shows a gradual increase at high frequency. The cut-off frequency is above 20kHz.

一种新型的超导磁场单晶炉的研制

磁场对于半导体晶体生长过程中的熔体流动模式有着明显的影响，因而可以改善晶体的组分和杂质的分布。在半导体单晶生长过程当中利用超导磁场来抑制熔体的对流，采用这种方式既可以生长出优质的单晶又可以研究熔体的对流与扩散对生长半导体单晶的质量影响。报道了新近自行设计、制造的一种新型超导磁场直拉单晶炉。

Lasing of CdSSe quantum dots in glass spherical microcavity

Glass spherical microcavities containing CdSSe semiconductor quantum dots (QDs) of a few microns in diameter are fabricated using a physical method. When a single glass microspherical cavity is excited by a laser beam at room temperature, very strong and sharp whispering gallery modes are shown on the background of PL spectra of CdSSe QDs, which confirms that coupling between the optical emission of embedded QDs and spherical cavity modes is realized. For a glass microsphere only 4.6 mum in diameter, it was found that the energy separation is nearly up to 26 nm both for TE and TM modes. With the increasing excitation intensity, the excitation intensity dependence of the emission intensity is not linear in the double-logarithmic scale. Above the threshold value, the linewidths of resonance modes become narrower. The lasing behavior is achieved at relatively low excitation intensity at room temperature. High optical stability and low threshold value make this optical system promising in visible microlaser applications. (C) 2002 Elsevier Science B.V. All rights reserved.

Influences of initial nitridation process on the optical and structural characterization of GaN layer grown on sapphire (0001) by metalorganic chemical vapor deposition

In this paper. we investigate the influences of the initial nitridation of sapphire substrates on the optical and structural characterizations in GaN films. Two GaN samples with and without 3 min nitridation process were investigated by photoluminescence (PL) spectroscopy in the temperature range of 12-300 K and double-crystal X-ray diffraction (XRD). In the 12 K PL spectra of the GaN sample without nitridation, four dominant peaks at 3.476, 3.409 3.362 and 3.308 eV were observed, which were assigned to donor bound exciton, excitons bound to stacking faults and extended structural defects. In the sample with nitridation, three peaks at 3.453, 3.365. and 3.308 eV were observed at 12 K, no peak related to stacking faults. XRD results at different reflections showed that there are more stacking faults in the samples without nitridation.