高分子化的茂金属催化剂的合成及乙烯聚合的研究

本论文合成了高分子化的茂金属烯烃聚合催化剂, 通过常规方法对催化剂和聚合物进行了表征, 并在常压和高压下采用不同的均相和非均相催化剂进行了乙烯聚合的研究. 采用相转移和富烯转化法合成了六种含烯烃基团的配体, 并利用这六种配体合成了均配和混配的茂金属化合物, 由于含烯烃基团的茂金属化合物在烯烃聚合方面的研究相对较少. 本文采用这些含烯烃基的茂金属化合物在不同温度, 不同Al/M(M=Ti,Zr)下进行了乙烯聚合的研究, 研究表明: 1. 含烯烃基的茂金属化合物在MAO的作用下对乙烯聚合具有较高的催化活性; 2. 在不同的温度和Al/M的情况下, 乙烯聚合活性有最佳值, 但变化规律同传统的取代的茂金属化合物有区别; 3. 提出了烯烃基取代的茂金属化合物上的烯烃基可以以分子间的形式聚合在聚乙烯分子链上而形成非均相催化剂的假设. 在自由基聚合引发剂偶氮二异丁腈(AIBN)的存在下, 含烯烃基的茂金属化合物与苯乙烯、二乙烯基苯共聚形成线性、网状和体型的高分子化的茂金属化合物. 改变不同单体的投料比, 得到一系列不同茂金属化合含量的高分子化的催化剂, 通过竞聚率和Q-e值的计算, 发现苯乙烯基取代的茂金属化合物与苯乙烯共聚能力最强, 其次是乙烯基取代的茂金属化合物。改变二乙烯基苯的含量得到的高分子化的催化剂的吸附表征发现当二乙烯基苯与乙烯投料比在0.08的情况下, 催化剂的吸附能力, 孔径和孔容积达到最优。在MAO存在下, 高分子化的茂金属化合物催化乙烯常压聚合的研究得到如下主要结论: 1. 线性的高分子化的催化剂比未高分子的茂金属化合物催化乙烯聚合的活性高; 2. 由于二乙烯基苯的存在而交联的高分子化的茂金属催化剂比线性的高分子化的催化剂化活性低; 3. 在不同的温度和Al/M下, 催化剂的催化活性有最佳值。为了提高取乙烯的形态和堆密度, 设计合成了壳一核结构的高分子化的茂金属催化剂。根据烯烃聚合的模板效应, 催化剂的形态影响聚合物的形态。因此将形态较好的SiO_2作为催化剂的核, 而高分子化的茂金属催化剂作为催化剂的壳, 目的是将SiO_2的优良的形态和高分子化催化剂的高催化活性结合在一起。SEM的表征表明催化剂的形态得到很大程度的提高, 由不规则的形态变成规整的球形。在常压下催化乙烯聚合的结果表明: 1. 壳一核结构高分子化的茂金属催化剂具有很高的乙烯聚合活性。2. 采用壳一核结构的高分子化的茂金属催化剂得到的聚乙烯在常压下的堆密度高于非均相的高分子化的茂金属催化剂。采用高分子化的茂金属催化剂和壳一核结构的高分子化的茂金属催化剂进行乙烯的2升釜高压聚合。研究了共单体, 温度, Al/M对聚合活性和堆密度的影响。得到如下主要结论: 1. 高分子化茂金属催化剂和壳一核结构高分子化的茂金属催化剂具有催化乙烯聚合的高活性(6.48 * 10~7gPE/molZr); 2. 催化聚合所得的聚乙烯分子量在16-18万, 分子量分布窄(2.7); 3. 催化聚合所得聚乙烯的堆密度可以达到0.341, 说明已经达到可以工业化的标准。4. 催化聚合所得的聚乙烯具有优良的物理性能。5. SEM表征结果表明, 采用非均相高分子化的茂金属催化剂催化所得的聚乙烯呈多孔状, 而采用壳一核结构的催化剂催化得到的聚乙烯要紧密得多, 这一点正符合烯烃聚合的模板效应。总之, 高分子化的茂金属催化剂和壳一核结构高分子化的茂金属催化剂是一类很有工业化前景的烯烃聚合催化剂。

新型后过渡金属铁系烯烃聚合催化剂的合成及乙烯聚合

合成了五种新型的含烯烃基的后过渡金属烯烃聚合催化剂，并通过催化剂结构中的烯烃基，在自由基引发剂的作用下与苯乙烯共聚，生成高分子化烯烃聚合催化剂。详细研究了高分子化催化剂在不同条件下催化乙烯聚合的反应。用所合成的五种催化剂以及相应高分子化催化剂与MAO组成催化体系进行乙烯聚合得到以下结论：1.苯环邻位线型高分子链没有明显的大取代基的位阻效应。2.由于聚合物链对催化活性中心的包裹效应使得相同催化条件下，不同链结构的高分子化催化剂活性不同。为了提高聚乙烯的形态和堆密度设计合成了壳核结构催化剂，目的是将Si02的优良形态同高分子化催化剂的高活性结合在一起。表征表明催化剂形态得到很大提高，由不规则形态变成规整的球型。其催化乙烯聚合表明壳核催化剂具有很高的催化活性且得到意想不到的高分子量的聚乙烯。本论文根据铁系毗陡二亚胺化合物的结构可调的特点使之与茂金属催化剂结合设计并合成出两类双活性中心催化剂，其中一种催化剂催化所得聚乙烯具有独特的支链类型，另一种催化剂催化乙烯聚合得到分子量呈双峰分布的聚乙烯，但双峰之间距离略大，降低了材料的强度，为得到性能优越的聚乙烯材料需优化双中心之间的组合。

Effect of cryoprotectants on hatching rate of red seabream (Pagrus major) embryos

The objectives were to investigate the effect of cryoprotectants on the hatching rate of red seabream embryos. Heart-beat embryos were immersed in: five permeable cryoprotectants, dimethyl sulfoxide (DMSO), glycerol (Gly), methanol (MeOH), 1,2-propylene glycol (PG), and ethylene glycol (EG). in concentrations of 5-30% for 10, 30, or 60 min; and two non-permeable cryoprotectants: polyvinylpyrrolidone (PVP), and sucrose (in concentrations of 5-20% for 10 or 30 min). The embryos were then washed and incubated in filtered seawater until hatching occurred. The hatching rate of the embryos treated with permeable cryoprotectants decreased (P < 0.05) with increased concentration and duration of exposure. In addition, PG was the least toxic permeable cryoprotectant, followed by DMSO and EG, whereas Gly and MeOH were the most toxic. At a concentration of 15% and 30 min exposure, the hatching rate of the embryos immersed in PG was 93.3 +/- 7.0% (mean +/- S.D.), however. in DMSO. EG, Gly. and MeOH, it was 82.7 +/- 10.4, 22.0 +/- 5.7, 0.0 +/- 0.0, and 0.0 +/- 0.0%, respectively. Hatching rate of embryos treated with PVP decreased (P < 0.05) with the increase of concentration and exposure time, whereas for embryos treated with sucrose, there was no significant decrease in comparison with the control at the concentrations used. (C) 2008 Elsevier Inc. All rights reserved.

Comparative cytogenetics of bats (Chiroptera): The prevalence of Robertsonian translocations limits the power of chromosomal characters in resolving interfamily phylogenetic relationships

Although the monophyly of Chiroptera is well supported by many independent studies, higher-level systematics, e.g. the monophyly of microbats, remains disputed by morphological and molecular studies. Chromosomal rearrangements, as one type of rare genomic changes, have become increasingly popular in phylogenetic studies as alternatives to molecular and other morphological characters. Here, the representatives of families Megadermatidae and Emballonuridae are studied by comparative chromosome painting for the first time. The results have been integrated into published comparative maps, providing an opportunity to assess genome-wide chromosomal homologies between the representatives of eight bat families. Our results further substantiate the wide occurrence of Robertsonian translocations in bats, with the possible involvement of whole-arm reciprocal translocations (WARTs). In order to search for valid cytogenetic signature(s) for each family and superfamily, evolutionary chromosomal rearrangements identified by chromosomal painting and/or banding comparison are subjected to two independent analyses: (1) a cladistic analysis using parsimony and (2) the mapping of these chromosomal changes onto the molecularly defined phylogenetic tree available fromthe literature. Both analyses clearly indicate the prevalence of homoplasic events that reduce the reliability of chromosomal characters for resolving interfamily relationships in bats.

ON THE DANGLING-BOND RELAXATION PROBLEM IN HYDROGENATED AMORPHOUS-SILICON

The influence of pulsed bias light excitation on the absorption in the defect region of undoped a-Si:H film has been investigated. Ac constant photocurrent method has been used to measure the absorption spectrum. The absorption in the defect region increases with the light pulse duration.The analysis of obtained results does not support the existence of a long time relaxation process of dangling-bond states in a-Si:H.

SIMULATION OF LATERAL CONFINEMENT IN VERY NARROW CHANNELS

A theoretical study is presented of the lateral confinement potential (CP) in the very narrow mesa channels fabricated in the conventional two-dimensional (2D) electron gas in GaAs-AlxGa1-xAs heterostructures. The ID electronic structures are calculated in the framework of the confinement potential: V(x) = m* omega0(2)x2/2 for Absolute value of x

CONTROLLING OF SCHOTTKY-BARRIER HEIGHTS FOR AU/N-GAAS AND TI/N-GAAS WITH HYDROGEN INTRODUCED AFTER METAL-DEPOSITION BY BIAS ANNEALING

Up to now, in most of the research work done on the effect of hydrogen on a Schottky barrier, the hydrogen was introduced into the semiconductor before metal deposition. This letter reports that hydrogen can be effectively introduced into the Schottky barriers (SBs) of Au/n-GaAs and Ti/n-GaAs by plasma hydrogen treatment (PHT) after metal deposition on [100] oriented n-GaAs substrates. The Schottky barrier height (SBH) of a SB containing hydrogen shows the zero/reverse bias annealing (ZBA/RBA) effect. ZBA makes the SBH decrease and RBA makes it increase. The variations in the SBHs are reversible. In order to obtain obvious ZBA/RBA effects, selection of the temperature for plasma hydrogen treatment is important, and it is indicated that 100-degrees-C for Au/n-GaAs and 150-degrees-C for Ti/n-GaAs are suitable temperatures. It is concluded from the analysis of experimental results that only the hydrogen located at or near the metal-semiconductor interface, rather than the hydrogen in the bulk of either the semiconductor or the metal, is responsible for the ZBA/RBA effect on SBH.

CHARACTERISTICS OF THE MAGNETIC DEPOPULATION OF SUBBANDS IN VERY NARROW SYSTEMS

We present a model for electrons confined in narrow conducting channels by a parabolic well under moderate to high magnetic fields which takes into account a cutoff in the filling of the subbands. Such a cutoff gives rise to energy-separated subbands and a two-dimensional (2D) like subband depopulation, resulting in a relation between sublevel index n and inverse magnetic field B-1 such that in the high-field regime it changes over to the well-known 2D form as expected, and in the moderate field regime it shows pronounced deviation from linearity. This agrees well with the experimental results. The linear region of the n-B-1 experimental plot is believed to arise from the two dimensionality of the system. Calculations show that no resolvable 1D sublevel exists in the 0.5-mu-m-wide wire at very small magnetic fields (including zero field), which agrees qualitatively with the experimental results found in other wires that the Hall resistance, R(H), approaches its classical value B/n(e)e in this region and R(H) = 0 at B = 0, where n(e) is the electron concentration. In this model the linear and nonlinear regions in the experimental n-B-1 plot are used to extract the characteristic frequency omega-0, and the effective 2D electron concentration N(e)2D, respectively.

A High Speed, 12-Channel Parallel, Monolithic Integrated CMOS OEIC Receiver

The design and fabrication of a high speed, 12-channel monolithic integrated CMOS optoelectronic integrated circuit(OEIC) receiver are reported.Each channel of the receiver consists of a photodetector,a transimpedance amplifier,and a post-amplifier.The double photodiode structure speeds up the receiver but hinders responsivity.The adoption of active inductors in the TIA circuit extends the-3dB bandwidth to a higher level.The receiver has been realized in a CSMC 0.6μm standard CMOS process.The measured results show that a single channel of the receiver is able to work at bit rates of 0.8～1.4Gb/s. Altogether, the 12-channel OEIC receiver chip can be operated at 15Gb/s.

A 1.1GHz LC VCO with Automatic Amplitude Control for Tuner Applications

This paper presents an LC VCO with auto-amplitude control （AAC）, in which pMOS FETs are used,and the varactors are directly connected to ground to widen the linear range of Kvco. The AAC circuitry adds little noise to the VCO but provides it with robust performance over a wide temperature and carrier frequency range.The VCO is fabricated in a chartered 50GHz 0.35μm SiGe BiCMOS process. The measurements show that it has - 127. 27dBc/Hz phase noise at 1MHz offset and a linear gain of 32.4MHz/V between 990MHz and 1.14GHz.The whole circuit draws 6. 6mA current from 5V supply.

Monolithically Integrated Optoelectronic Receivers Implemented in 0. 25μm MS/RF CMOS

A monolithically integrated optoelectronic receiver is presented. A silicon-based photo-diode and receiver circuits are integrated on identical substrates in order to eliminate the parasitics induced by hybrid packaging. Implemented in the present deep sub-micron MS/RF （mixed signal, radio frequency） CMOS,this monolithically OEIC takes advantage of several new features to improve the performance of the photo-diode and eventually the whole OEIC.

Bandwidth Design for CMOS Monolithic Photoreceiver

A monolithic photoreceiver which consists of a double photodiode (DPD) detector and a regulated cascade(RGC) transimpedance amplifier (TIA) is designed. The small signal circuit model of DPD is given and the band width design method of a monolithic photoreceiver is presented. An important factor which limits the bandwidth of DPD detector and the photoreceiver is presented and analyzed in detail. A monolithic photoreceiver with 1.71GHz bandwidth and 49dB transimpedance gain is designed and simulated by applying a low-cost 0. 6um CMOS process and the test result is given.

Fabrication of 1.55μm Si-Based Resonant Cavity Enhanced Photodetectors

A novel bonding method using silicate gel as bonding medium is developed.High reflective SiO2/Si mirrors deposited on silicon substrates by e-beam deposition are bonded to the active layers at a low temperature of 350℃ without any special treatment on bonding surfaces.The reflectivities of the mirrors can be as high as 99.9%.A Si-based narrow band response InGaAs photodetector is successfully fabricated,with a quantum efficiency of 22.6% at the peak wavelength of 1.54μm,and a full width at half maximum of about 27nm.This method has a great potential for industry processes.

Fabrication of SiGe/Si Multi-Quantum Wells Resonant-Cavity-Enhanced Detector

A SiGe/Si multi-quantum wells resonant-cavity-enhanced(RCE) detector with high reflectivity bottom mirror is fabricated by a new method.The bottom mirror is deposited in the hole,which is etched from the backside of the sample by ethylenediamine-pyrocatechol-water(EPW) solution with the buried SiO2 layer in SOI substrate as the etching-stop layer.Reflectivity spectrum indicates that the mirror deposited in the hole has a reflectivity as high as 99% in the range of 1.2～1.5μm.The peak responsivity of the RCE detector at 1.344μm is 1.2mA/W and the full width at half maximum is 12nm.Compared with the conventional p-i-n photodetector,the responsivity of RCE detector is enhanced 8 times.