3,4－聚异成二烯的合成及所得聚合物结构与性能表征

近二十多年来，在异成二烯的络合催化聚合中，由Ni、Co、Ti及稀土等过渡金属元素络合物组成的催化体系，研究报道得很多，有些已投入工业生产。但由最常见的过渡金属元素铁络合物组成的催化体系，对异成二烯聚的聚合却不多见。本工作研究了三乙酰基丙酮铁为主催化剂，烷基铝为助催化剂，添加含氮类给电子试剂组成三元体系，对异成二烯聚合的催化作用。Fe(a cac)_3 - Al(i-Bu)_3二元体系不能引起异成二烯聚合，而加入少量的含氮类给电子试剂如邻菲啰啉、α,α'－联吡啶等，催化活性显著提高。聚合活性与含氮类给电子试剂的性质有关，并随着下列顺序依次递减：邻菲啰啉、α,α'－联吡啶、对苯二胺、邻苯二胺，对硝基苯胺、邻硝基苯胺；吡啶和已二胺对催化活性的提高几乎没有贡献。烷基铝的不同对催化活性也有明显的影响。其活性顺序为：Al(i-Bu)_3 approx Al Eτ_3 > Al(i-Bu)_2H。首次合成了结晶的3,4－聚异成二烯，3,4－链节含量为70％左右时，Tm为121 ℃左右， Tc为65 ℃左右，透射电镜下观察到结晶的3,4－聚异成二烯具有球晶状结构。初步研究了铁系三元催化体系的反应机理，设想铁化合物和烷基铝生成的烷基铁必须与含氮类给电子试剂作用才能形成活性中心；可见光谱和催化活性实验数据证实了含氮类给电子试剂参与活性中心的形成，并起着稳定活性中心的作用。本文详细地研究了Fe(a cac)_3 - phen - Al(i-Bu)_3催化体系对异成二烯的聚合，考察了起始单体浓度、聚合温度，催化剂总用量以及催化剂各组分配比对聚合速率、聚合物的特性粘数和链节结构的影响，从实验结果讨论了Fe(a cac)_3 - phen - Al(i-Bu)_3体系催化异成二烯的聚合机理，并进行了一些动力学的基本计算，得到了与实验结果基本相符的结果，解释了一些实验现象。铁系聚异成二烯橡胶的表征工作未见诸文献，本工作对铁系聚异成二烯生胶的结晶、力学、流变及阻尼性能作了较系统的研究，并对硫化胶的物理机械性能，弹性及阻尼性能作了初步的表征。铁系聚异成二烯橡胶在室温具有较好的阻尼性能，并且生热值和冲击弹性均较低，可作为室温阻尼材料使用。

[Ni(Phen)_3][Pd(mnt)_2]·1.25 DMF的合成与晶体结构

报道标题化合物的合成、鉴定和单晶结构.晶体中含有数量相同的两种独立的阳离子,互为对映异构体,而且这两种八面体构型阳离子的畸变程度各不相同.晶胞中还存在三种独立的阴离子.不同阳离子中的四个平面型 Phen 配体之间通过π-π相互作用发生联系,形成四聚单元,每两个四聚单元又通过与平面共轭型的阴离子之间的π-π相互作用而相连,形成一种特殊的、准一维的链状结构.

n—C_(12)H_(25)NH_3Br固态相性质的DSC和拉曼光谱研究

用差示扫描量热(DSC)和拉曼光谱方法考察了n-C_(12)H_(25)NH_3Br(DoAB)的固相性质,确定了DoAB固-固结构相变的温度及其焓变,通过6种状态下所对应的拉曼光谱讨论了相变过程中分子构象的变化。

[n-C_(12)H_(25)NH_3]_2ZnCl_4配合物相变拉曼光谱研究

通式为[C_nH_(2n+1)NH_3]_2MX_4(M=Cu,Mn,Zn…、X=Cl,Br)(简写C_nM)四卤合金属酸二烷基铵系列化合物一般具有二维层结构。它是由薄的无机层阴离子MX_4~(2-)和厚的烷基铵阳离子[R-NH_3]~+组成的碳氢层规则交替构成的“夹心面包”型体系。这类化合物常存在固-固相变,并且有较大的相变潜热,有可能成为很有应用前景的一类新的低温储能材

YP_5O_(14):Er~(3+),Tm~(3+)晶体的合成

研究了水热法合成晶体,浓度配比、生长温度对晶体生长习性的影响.合成了一系列化学计量比的Y_(1-x-0.3)Er_(0.3)Tm_xP_5O_(14)(x=0.01～0.1)晶体,观察和分析了晶体的缺陷及成因,测定和讨论了晶体结构.

蛋氨酸稀土配合物构象的~(13)C NMR研究

本文测量了在7种不同稀土离子(La~(3+)、Pr~(3+)、Nd~(3+)、Dy~(3+)、Ho~(3+)、Er~(3+)和Tm~(3+))的水溶液中蛋氨酸~(13)C稀土诱导位移。利用稀土诱导位移对蛋氨酸稀土配合物构象的模拟结果表明,蛋氨酸通过离子化的羧基与稀土离子配位,Ln~(3+)—O长度为2.7A在配合物中,蛋氨酸以伸展状态存在,C_0-C_α-C_β-C_γ和C_α-C_β-C_γ-S成反式构象,C_β-C_γ-S-C_δ成旁式构象。根据稀土诱导位移方法建立的构象模型符合~1H邻位质子偶合常数和~(13)C顺磁弛豫速率的结果。

三峡工程截流后长江口海区表层悬沙分布与河口锋带特征

本文收集了三峡截流前后长江口海区1988－2007年间十二景landsat TM遥感影像并进行了表层悬浮泥沙含量的反演，定性的描述了长江口海区洪、枯季的表层悬沙扩散外界和高浑浊水域范围的变化趋势，分析了河流泥沙输移入海形态的变化特征及表层悬沙浓度的变化特征。 通过对2002-2004年在长江口滨外区表层悬浮体取样数据的实验室处理，揭示了三峡截流后表层悬沙的分布特征；通过多船同步定点观测捕捉到了长江口河口锋带的位置并分析了河口锋带的动力特征，结果表明：长江口河口锋位于（122o10′E，30o50′N）至（122o20′E，31o00′N）一线附近，在河口锋带位置有着较为强烈的河海相互作用，流速不符合典型的对数流速曲线，河水与海水的相互消长局限于海面以下5m的表层范围，在河口锋面区悬浮泥沙为泥沙流伏在海水之上输运。长江口悬沙体浓度由于三峡蓄水作用表现为下降趋势，悬浮体扩散范围相比截流前向口门后退，长江口滨外区羽状锋带随之向口门后退。 利用二维潮流数值模型较成功地模拟出了每个季度长江河口外的流场情况及河口锋带的发育情况，模拟表明：春、夏、秋三季河口锋带较易出现，且小潮期间发育最好。冬季长江河口海洋动力较强，易于发生海水入侵，尤其是北支；夏季是长江三角洲的主要建设期，锋带作用的存在使得泥沙大部分在锋带的内外区域沉积；春秋两季是平衡期；冬季主要是冲刷的时期。

海相碳酸盐－稀土元素共沉淀过程中的分异作用研究

本文主要运用稳定加液－反应系统对海水中方解石和文石形成时稀土元素的共沉淀现象进行了分析，研究了稀土元素在固-液体系中的迁移、转化和分配。进而在对其定量描述的前提下，研究了稀土元素共沉淀对各种反应条件的响应，并对共沉淀行为的机制进行了探讨。 本实验首先运用pH测试、高精度滴定分析等手段测定了实验中的一些基本参数，如[H+]、碱度和[Ca2+]，根据计算结果获得了各碳酸体系要素，并以此为基础建立了5℃、15℃和25℃及pCO2=0.003atm下海水中方解石或文石的沉淀动力学方程。实验结果表明： 1）在各条件下，方解石或文石的沉淀速率（R）和其在海水中过饱和度（Ω）存在很好的线性相关性，即海相碳酸盐的沉淀动力学方程可以通过下面的基本表达式来表示：LogR=k*Log(Ω-1)+b ； 2）过高的稀土元素浓度会对文石或方解石的沉淀产生抑制作用，进而对共沉淀过程中YREEs的分异和分馏产生一定的影响。相比方解石而言，文石的沉淀动力学过程承受稀土元素的干扰能力更强； 3）不同温度下得到的方解石或文石各自的沉淀动力学方程存在明显的差异，表明这一过程受热力学因素控制。相对于方解石而言，温度对文石的沉淀动力学的影响更为显著。 与前人研究不同的是，本实验中YREEs的浓度设定在非常低的范围内，从而避免了过高浓度YREEs对方解石或文石沉淀动力学过程的干扰。在最终的反应液中，各种实验条件非常接近自然环境。有关稀土元素的共沉淀行为主要得出以下定性或定量化结论： 1）YREEs在随方解石或文石的共沉淀过程中，均发生了强烈的分异作用。在方解石实验中，稀土元素的分异系数分布曲线呈凸状分布；而在文石实验中，稀土元素的分异系数随原子序数的增加逐渐减小，遵循镧系收缩的规律。总的来说，稀土元素，尤其轻稀土元素在文石中的分异作用要强于方解石。 2）无论是方解石还是文石，沉淀速率对YREEs的分异作用都有着明显的影响。在方解石中，YREEs的分异系数随沉淀速率的增加呈一致性递减趋势；而在文石中，其分异系数对文石沉淀速率有着截然不同的响应：轻稀土元素（La, Ce, Nd, Sm, Eu, Gd）的分异系数随文石沉淀速率的增加而下降，而重稀土元素（Ho, Y, Tm, Yb , Lu）的分异系数则随文石沉淀速率的增加呈上升趋势。 3）在方解石中YREEs的分异系数之间存在非常好的相互关系，表明这些元素是以成比例的方式参与共沉淀。整个谱系呈现中等强度的分馏，MREE相对于LREE和HREE要更为富集；在文石中由于沉淀速率的作用不同，只有Y、Ho、Yb、Lu等元素的分异系数之间有较好的相互关系。YREEs出现了差异性的强烈分馏，在新生成沉淀中轻稀土元素相对于重稀土元素强烈富集。 4）YREEs在溶液中和碳酸盐晶体表面的碳酸根配位形式对YREEs在共沉淀过程中的分异作用极为重要，YREEs在碳酸盐晶体表面的吸附是整个谱系发生分馏效应的关键环节。对于文石来讲，晶体中有效YREE离子和Ca离子半价大小之间的相近程度是其分馏效应的关键因素；而对于方解石来说，YREEs在方解石晶格中的安置就是其分馏效应的关键控制因子，但在晶格安置中起到关键作用的是YREEs和方解石中O原子之间离子键M-O的键长，而非离子半径。 5）综合YREEs在方解石中的分异作用和分馏效应，我们认为M2(CO3)3-CaCO3和MNa(CO3)2-CaCO3是最为可能的两种固体溶液形成模式。 最为重要的是，对比我们的实验结果与前人在灰岩、叠层石、微生物成因碳酸盐等方解石质载体中的研究成果，两者之间出现了非常好的一致性。我们认为方解石质载体将是重建古海水中稀土元素相关信息的重要工具。相比之下，文石质载体不适合作为类似的载体。

基于微波图像的辽东湾海冰典型要素信息提取

业务化海冰遥感监测的要素主要包括海冰类型、海冰厚度和海冰范围（冰缘线）。本文针对辽东湾海冰的特点，结合星载合成孔径雷达（SAR）、机载微波辐射计（ABMR）和星载微波辐射计遥感图像观测辽东湾海冰，发展海冰要素探测算法，提取海冰类型、海冰厚度和冰缘线信息。 海冰类型SAR信息提取方面，首先分析了双极化ENVISAT ASAR数据不同极化方式的海冰探测能力。然后利用SAR图像，结合同步TM数据和航空照片，开展辽东湾地区不同类型海冰的电磁特性研究。研究结果表明，SAR图像可较好地区分沿岸固定冰、平整冰和碎冰堆积区，但在探测初生冰方面并不可靠，探测结果与海冰生长阶段以及海冰周围环境条件有关。根据SAR图像中海冰类型的分析，将PCNN神经网络用于海冰SAR图像的分割和海冰分类，并对PCNN做了简化和改进。经SAR图像分类结果测试，简化和改进后的PCNN可较好地区分SAR图像中的海冰类型。通过分析了PCNN网络各参数对SAR图像分割结果的影响，指出了各参数的取值范围，并在此基础上建立了基于PCNN神经网络的海冰SAR图像半自动分类判读系统。 海冰厚度机载微波辐射计信息提取方面，推导了非相干模式的ABMR海冰厚度反演模型，并首次得到了模型中高阶亮温辐射项的计算表达式。通过对模型的分析，指出ABMR只能测量一定范围内的海冰厚度。其中，最大海冰探测厚度不仅决定于ABMR的波长，而且还受到仪器精度的限制；最小海冰探测厚度只与仪器的波长有关。在此基础上，定量计算了我国几种常用波长ABMR的海冰厚度探测范围。并结合辽东湾海冰冰情等级，指出适合不同海冰冰情等级的ABMR的选择。最后分析了海冰厚度反演模型的影响因素和模型的适应范围。 海冰边缘线星载微波辐射计信息提取方面，首次将PSSM算法用于AMSR数据，提取辽东湾海冰边缘线信息，可得到空间分辨率为2.5km、重复周期为1d的辽东湾海冰边缘线信息。通过提取结果与Jason-1高度计和SAR探测海冰边缘线的比较，验证了PSSM方法探测辽东湾海冰边缘线的有效性。 论文的最后对全文做了总结，并提出和讨论了需要进一步开展的工作。

Study on growth factors of intermetallic layer within hot-dipped 25% Al-Zn alloy coating on steel

25%Al-Zn alloy coating performs better than hot dip galvanized coating and 55%Al-Zn-Si coating with regard to general seawater corrosion protection. This study deals with the interfacial intermetallic layer's growth, which affects considerably the corrosion resistance and mechanical properties of 25%Al-Zn alloy coatings, by means of three-factor quadratic regressive orthogonal experiments, The regression equation shows that the intermetallic layer thickness decreases rapidly with increasing content of Si added to the Zn-Al alloy bath, increases with rise in bath temperature and prolonging dip time. The most effective factor that determined the thickness of intermetallic layer was the amount of Si added to Zn-Al alloy bath, while the effect of bath temperature and dip time on the thickness of intermetallic layer were not very obvious.

Effect of nano-TiO(2)on MP-25 resin

MP-25 resin is a chlorine-containing polymer widely used in coatings. The effects of two types of nano-TiO2 (P-25 and RM301 LP) on MP-25 were studied with saline immersion, UV irradiation, and electrochemical impedance spectroscopy. UV irradiation was evaluated in terms of gloss change and X-ray photoelectron spectroscopy (XPS). The results indicate that, compared to pigment R-930 TiO2, P-25 reduced the immersion resistance and accelerated UV aging of the MP-25 coating, whereas RM301 LP showed the opposite effects. XPS analysis showed that MP-25 resin degraded under UV irradiation via dechlorination and C-C bond breakage, similarly to poly(vinyl chloride), but RM301 LP could inhibit the aging of MP-25 to a certain extent. A skin effect of oxygen and chlorine was identified in MP-25 resin by XPS. RM301 LP could improve the impedance of the MP-25 coating because of its excellent fill capacity. Hence, rutile nano-TiO2 RM301 LP represents an excellent additive for MP-25 resin. (c) 2007 Wiley Periodicals, Inc.

自治水下机器人控制方法研究及滑模模糊控制的应用研究

本论文在参阅大量国内外文献的基础上，进行了两方面的研究工作：自治水下机器人控制方法研究和滑模模糊控制的应用研究。全文分两部分对所做工作进行，总结论述。在第一部分“滑模模糊控制方法在自治水下机器人中的应用研究”中，本文总结了自治水下机器人控制方法的新进展；研究了模糊滑模控制和滑模模糊控制的原理，并针对6000米自治水下机器人“cR－01”的数学模型进行了仿真。仿真结果表明滑模与模糊控制相结合的方法减少了模糊控制规则的数目，参数较易调整，而且可以消除普通滑模控制中的颤振现象。在仿真的基础上进行了滑模模糊控制水池实验，对实验结果进行了分析。实验结果表明，滑模模糊控制可以大大提高自治水下机器人控制系统的性能。在第二部分“自治水下机器人控制方法研究”中，本文进行了解祸控制、BackStepping控制、“CR－01’，控制方法的仿真和水下机器人六自由度仿真的研究。分析了自治水下机器人运动中存在的藕合作用，就解祸控制进行了分析和仿真，仿真结果表明解藕控制可以很好地实现同一平面内各祸合变量的解藕。分析了BackStepping鲁棒控制算法，在自治水下机器人运动存在模型摄动和外界千扰时进行了仿真，仿真结果表明基于全状态反馈的B ackStepping控制算法具有很强的鲁棒性，对模型摄动和干扰有较强的适应性。在进行论文工作的过程中，作者建立了大量的基于MATLAB TM下S INIULINKIrm的6000米自治水下机器人"CR－01”的控制方法仿真模块。本文建立了一个全自由度的自治水下机器人仿真模块，为路径规划和高层使命仿真打下了基础。

有源电磁扩散场克希霍夫积分偏移

As active electromagnetic method, field data of CSAMT method follow the equation of diffusion. Propagting in solid earth media, diffusion EM signal has strong attenuation and dispersion, otherwise seismic wave shows weak attenuation and dispersion, therefore the resolution power of CSAMT method is not better than seismic reflection method. However, there is consistence and similarity between EM signal and seismic wave in wave equation, we can apply Kirchhoff integral migration technique, a proven one in seismic method in time domain, to carry out seduo-seismic processing for CSAMT signal in frequency domain so that the attenuation and dispersion could be made compensated in some extent, and the resolution power and interpretation precision of active EM wave could be improved. Satisfying passive homogeneous Helmholtz quation, we proceed with Green theorem and combine the active inhomogenous Helmholtz quation, the Kirchhoff integral formula could be derived. Given practical problems, if we only consider the surface integral value, and assume that the intergral value in other interface is zero, combined with Green theorem in uniform half space, the expression could be simplified, and we can obtain frequency-domain Kirchhoff integral formula in surface, which is also called downward continuation of EM field in frequency domain. With image conditions and energy compensation considered, in order to get image conditions in time domain Fourier inverse transformation in frequency domain can be performed, so we can formulate the active Kirchhoff integral migration expression. At first, we construct relative stratified model, with different frequency series taken into account, then we change the distances between transmitter and reciever, the EM response can be obtained. Analyzing the EM properties, we can clarify near and far zone that can instruct us to carry out transmitter layout in practical application. Combined with field data surveyed in far zone, We perform Kirchhoff integral migration and compare the results with model to interpret. Secondly, with far field EM data, we apply TM mode to get EM response of given 2D model, then apply Kirchhoff integral migration on modelling data and interpret the results.

压力和铁含量对铁方镁石(Mg1-xFex)O(x<=0.25)弹性常数影响的第一性原理研究

By first principle methods based on density functional theory (DFT),the equation of state(EOS) and elastic constants of both periclase and ferropericlase are calculated. The pressure and iron doping effects on the elastic constants of ferropericlase are investigated systematically. Firstly, we calculate the elastic constants of periclase and compare the obtained results with experimental data and other theoretical calculations, which shows a encouraging consistence and demonstrates the practicability of first-principle methods. Secondly, by adding iron into periclase crystal model, we build up ferropericlase with iron contents ranging from 0% to 25% mole percent. The corresponding elastic constants are calculated in a large pressure range(0~120GPa). Emphatically, the strong correlation of 3d electrons in transitional elements, such as iron, is difficult to treat in first-principle methods for a long time. The current solution is to make additional correction. During the initial stage of this study, the strong correlation of 3d electrons in iron is not considered, and we observed that addition of iron decreases the volume of ferropericlase, which is totally contradictory to the experimental data. By applying LDA+U approximation in order to solve the strongly correlated 3d electron of iron, we observed the expansion of volume by iron as expected. On the basis of the LDA+U approximation, the elastic constants of ferropericlase are calculated. After a detailed analysis of data obtained from theoretical calculations, we have reached the following conclusions:(1)pressure imposes positive effects on all elastic constants, and the degree of effects is C11>C12>C44. (2) Iron has no distinctive effects on C11 and C12, although some fluctuations are observed around 60GPa. However, iron has obvious softening effects on C44 The softening effects on C44 are intensified as pressure increases. Above the 100GPa, the effects increase greatly, even surpasses the pressure's positive effects in ferropericlase crystal models with iron mole percent of having 12.5%, 18.75% and 25% iron content. (3)As to the modulus deprived from elastic constants, iron has no effect on the adiabatic bulk module BS, only a little fluctuation around 60GPa. We find iron's softening effects on shear modulus G. (4)We find out that, compared with low iron content, elastic constants with iron content approaching 25mole% is consistently fluctuated，which may be caused by the limitations of the LDA+U approximation method itself. (5)We investigate the pressure and Fe doping effects on elastic anisotropy factor（A=(2C44+C12-C11)/C11） of ferropericlase and find out that iron contents will lower the critical isotropic pressure. At the same pressure, when the pressure is below the isotropic pressure, iron softens the anisotropy factor ; when pressure surpasses the isotropic pressure, iron increases the anisotropy factor.

东营凹陷幔源流体对原油生物标志化合物的影响研究

A large number of mantle-derived fluid activities occurred in the Dongying Sag. On the basis of the studies on the geochemical characteristics of these fluids in this sag, the spatial distribution of biomarkers in petroleum and their relationships with the parameters of mantle-derived fluids were studied, to reveal the influence of mantle-derived fluids on the biomarkers and to evaluate the reliability of these biomarkers when applied to oil-source correlation and maturity analysis. Most biomarkers used in oil correlation kept the characteristics of their sources during burial thermal evolution. Even some of them were not influenced by mantle derived fluids, such as the relative content of C27-C29 steroid（ααα20R）and C21/C23 tricyclic terpane. However, Pr/Ph and C35/C34 hopanes were sensitive to both heat energy and materiel input by the mantle-derived fluids. γ-waxnae/C30hopanes and C24 tetracyclic terpanes /C26 tricyclic terpanes responded only to thermal influence by mantle-derived fluids. They did not chemically reacted with the mantle-derived fluids. Fluorene series compounds reacted with hydrogen and / or carbon dioxide from the mantle. Mantle-derived fluids affected most maturity index. The huge thermal energy with mantle-devied fluids weakened the relationship between the maturity parameters and depth. Among them, pregnane/C27-29 steroid and Ts/(Ts+Tm) were more sensitive to the heat of the fluids. ααα20S/(20S+20R) took the second place. αββ/(ααα+αββ) and 22S/(22S+22R) were not thermally influenced by the mantle-derived fluid. Besides, the substance of mantle-derived fluids reacted with fragrants, hopanes or moretanoids and thus altered the values of MPI1, MPI2, MPR, C30 hopanes/(C30 hopanes + moretanoids) and alkyl-diben zothiophene/diben zothiophene. The thermal alernation of phenanthrene series and their spatial distribution show that the heat energy carried by mantle-derived fluids was not fierce but spread widely in Dongying Sag, which is favorable to hydrocarbon generation with little destroy. In sum, mantle-derived fluids affected biomarkers through thermal energy and chemical reactions and changed the values of oil-source correlation and maturity parameters in the deep-seated fault belts. Therefore, in the deep-seated fault belts, oil-source correlation should be restudied and the new parameters need to be explored.