A phototaxis inhibition assay using barnacle larvae

The effects of sublethal concentrations of phenol and cadmium on the phototactic responses of the stage II nauplii of the barnacle Balanus amphitrite were investigated. Increased toxicant concentrations caused a reduction in phototactic responses. Balanus amphitrite nauplii exposed to nominal phenol concentrations of 100 ppm and higher for 1-12 h failed to exhibit phototactic responses, while longer exposure times of 24 and 48 h reduced the lowest observable effect concentration (LOECs) to 80 and 60 ppm, respectively. For cadmium, the LOECs, based on nominal concentrations, for B. amphitrite following 1, 6, 12, 24, and 48 h exposures were 20, 4.5, 4.0, 1, and 0.75 ppm, respectively. The LOECs can be significantly reduced by increasing the duration of exposure to the toxicants. A good relationship exists between the phototactic response and toxicant concentration as well as exposure time. Results of this study indicate that the toxicant-induced reduction in phototactic responses of barnacle larvae can be used in a sensitive, rapid screening test for ecotoxicological assessments. (C) 1997 by John Wiley & Sons, Inc.

New observations on the pressure dependence of luminescence from Eu2+-doped MF2 (M = Ca, Sr, Ba) fluorides

The luminescence from Eu2+ ions in MF2 (M = Ca, Sr, Ba) fluorides has been investigated under the pressure range of 0-8 GPa. The emission band originating from the 4f(6)5d(1) -> 4f(7) transition of Eu2+ ions in CaF2 and SrF2 shows the red-shift as increasing pressure with pressure coefficients of -17 meV/GPa for CaF2 and -18 meV/GPa for SrF2. At atmospheric pressure, the emission spectrum of BaF2:Eu2+ comprises two peaks at 2.20 and 2.75 eV from the impurity trapped exciton (ITE) and the self-trapped exciton (STE), respectively. As the pressure is increased, both emission peaks shift to higher energies, and the shifting rate is slowed by the phase transition from the cubic to orthorhombic phase at 4 GPa. Due to the phase transition at 4-5 GPa pressure, the ITE emission disappears gradually, and the STE emission is gradually replaced by the 4f(6)5d(1) -> 4f(7) transition of Eu2+. Above 5 GPa, the pressure behavior of the 4f(6)5d(1) -> 4f(7) transition of EU2+ in BaF2: EU2+ is the same as the normal emission of Eu2+ in CaF2 and SrF2 phosphors.

Structure, magnetization, and low-temperature spin dynamic behavior of zincblende Mn-rich Mn(Ga)As nanoclusters embedded in GaAs

We have fabricated a set of samples of zincblende Mn-rich Mn(Ga)As clusters embedded in GaAs matrices by annealing (Ga,Mn)As films with different nominal Mn content at 650 degrees C. For the samples with Mn content no more than 4.5%, the Curie temperature reaches nearly 360 K. However, when Mn content is higher than 5.4%, the samples exhibit a spin-glass-like behavior. We suggest that these different magnetic properties are caused by the competing result of dipolar and Ruderman-Kittel-Kasuya-Yosida interaction among clusters. The low-temperature spin dynamic behavior, especially the relaxation effect, shows the extreme creeping effect which is reflected by the time constant tau of similar to 10(11) s at 10 K. We explain this phenomenon by the hierarchical model based on the mean-field approach. We also explain the memory effect by the relationship between the correlation function and the susceptibility.

Holographic fabricated photonic-crystal distributed-feedback quantum cascade laser with near-diffraction-limited beam quality

We demonstrate the fabrication and characterization of photonic-crystal distributed-feedback quantum cascade laser emitting at 4.7 mu m. The tilted rectangular-lattice PCDFB structure was defined using a multi-exposure of two-beam holographic lithography. The devices exhibit the near-diffraction-limited beam emission with the full width at half maximum of the far-field divergence angles about 4.5 degrees and 2.5 degrees for stripe widths of 55 mu m and 95 mu m, respectively. Single-mode emission with a side mode suppression ratio of approximate to 20 dB is achieved in the temperature range (80-210 K). The single-facet output power is above 1 W for a 95 mu m x 2.5 mm laser bar at 85 K in pulsed operation. (C) 2009 Optical Society of America

Investigation of phtoluminesecence under hydrostatic pressure in different sized ZnS : Mn nanoparticles

The PL spectra for the 10, 4. 5, 3. 5, 3, 1 nm sized ZnS:Mn2+ nanoparticles and corresponding bulk material under different pressures were investigated. The orange emission band originated from the T-4(1)-(6)A(1) transition of Mn2+ ions showed obvious red shift with the increasing of pressures. The pressure coefficients of Mn-related emissions measured from bulk, 10, 4. 5, 3.5 and 3 nm samples are -29.4 +/- 0.3, -30.1 +/- 0.3, -33.3 +/- 0.6, -34.6 +/- 0.8 and -39 +/- 1 meV/GPa, respectively. The absolute value of the pressure coefficient increases with the decrease of the size of particles. The size dependence of crystal field strength Dq and Racah parameter B accounts for the size behavior of the Mn-related emission in ZnS:Mn nanoparticles. The pressure behavior of Mn-related emission in the 1 nm sized sample is somewhat different from that of other nanoparticles. It may be due to smaller size of 1 nm sample and the special surface condition since ZnS nanoparticles are formed in the cavities of ziolite-Y for the 1 nm sample.

Pressure behavior of the alloy band edge and nitrogen-related centers in GaAs0.999N0.001

The photoluminescence of a GaAsN alloy with 0.1% nitrogen has been studied under pressures up to 8.5 GPa at 33, 70, and 130 K. At ambient pressure, emissions from both the GaAsN alloy conduction band edge and discrete nitrogen-related bound states are observed. Under applied pressure, these two types of emissions shift with rather different pressure coefficients: about 40 meV/GPa for the nitrogen-related features, and about 80 meV/GPa for the alloy band-edge emission. Beyond 1 GPa, these discrete nitrogen-related peaks broaden and evolve into a broad band. Three new photoluminescence bands emerge on the high-energy side of the broad band, when the pressure is above 2.5, 4.5, and 5.25 GPa, respectively, at 33 K. In view of their relative energy positions and pressure behavior, we have attributed these new emissions to the nitrogen-pair states NN3 and NN4, and the isolated nitrogen state N-x. In addition, we have attributed the high-energy component of the broad band formed above 1 GPa to resonant or near-resonant NN1 and NN2, and its main body to deeper cluster centers involving more than two nitrogen atoms. This study reveals the persistence of all the paired and isolated nitrogen-related impurity states, previously observed only in the dilute doping limit, into a rather high doping level. Additionally, we find that the responses of different N-related states to varying N-doping levels differ significantly and in a nontrivial manner.

Magnetism and luminescence evolution due to nitrogen doping in manganese-gallium oxide nanowires

We report a new method for large-scale production of GaMnN nanowires, by annealing manganese-gallium oxide nanowires in flowing ammonia at high temperature. Microstructure analysis indicates that the GaMnN nanowires have wurtzite GaN structure without Mn precipitates or Mn-related second phases. Magnetism evolution due to nitrogen doping in manganese-gallium oxide nanowires was evaluated by magnetic measurements. Magnetic measurement reveals that the magnetization increases with the increase of nitrogen concentration. Ferromagnetic ordering exists in the GaMnN nanowires, whose Curie temperature is above room temperature. Luminescence evolution was investigated by the cathodoluminesence measurement for a single nanowire and photoluminescence measurement in a temperature range between 10 and 300 K. Experimental results indicate that optical properties can be modulated by nitrogen doping in manganese-gallium oxide nanowires. (c) 2005 Elsevier B.V. All rights reserved.

Pressure dependence of Mn2+ luminescence in differently sized ZnS : Mn nanoparticles

The pressure behavior of Mn2+ emission in the 10-, 4.5-, 3.5-, 3-, and 1-nm-sized ZnS:Mn2+ nanoparticles is investigated. The emission shifts to lower energies with increasing pressure, and the shift rate (the absolute value of the pressure coefficient) is larger in the ZnS:Mn2+ nanoparticles than in bulk. The pressure coefficient increases with the decrease in particle size with the 1-nm-sized particles as an exception. Pressure coefficient calculations based on the crystal field theory are in agreement with the experimental results. The pressure dependence of the emission intensity is also size dependent. For nanoparticles 1 and 3 nm in size, the luminescence intensity of Mn2+ decreases dramatically with increasing pressure, while, for bulk and particles with average sizes of 3.5, 4.5, and 10 nm, the luminescence intensity of Mn2+ is virtually unchanged at different pressures. The bandwidth increases faster with increasing pressure for smaller particles. This is perhaps due to the fact that there are more Mn2+ ions at the near-surface sites and because the phonon frequency is greater for smaller particles. These new phenomena provide some insight into the luminescence behavior of Mn2+ in ZnS:Mn2+ nanoparticles.

Temperature behaviour of the orange and blue emissions in ZnS : Mn nanoparticles

The temperature dependences of the orange and blue emissions in 10, 4.5, and 3 nm ZnS:Mn nanoparticles were investigated. The orange emission is from the T-4(1)-(6)A(1) transition of Mn2+ ions and the blue emission is related to the donor-acceptor recombination in the ZnS host. With increasing temperature, the blue emission has a red-shift. On the other hand, the peak energy of the orange emission is only weakly dependent on temperature. The luminescence intensity of the orange emission decreases rapidly from 110 to 300 K for the 10 nm sample but increases obviously for the 3 nm sample, whereas the emission intensity is nearly, independent of temperature for the 4.5 nm sample. A thermally activated carrier-transfer model has been proposed to explain the observed abnormal temperature behaviour of the orange emission in ZnS:Mn nanoparticles.

Syntheses, crystallographic and magnetic properties of Nd3Fe29-xCrx and other associated compounds

A systematic study of syntheses and magnetic properties of the Nd-3 Fe29-xCrx (x=4.5, 4.7, 5.0, and 5.5) compounds has been performed. The single-phase compounds of Nd3Fe29-xCrx can be formed in the range 4.5 less than or equal to x less than or equal to 5.5. The Curie temperature Tc, the saturation magnetization M-S at 4.2 K, the anisotropy field H-A at 4.2 K and room temperature, and the intra-sublattice exchange coupling parameter j(FeFe) at 4.2 K for the Nd3Fe29-xCrx compounds decrease with increasing Cr composition from x=4.5 to 5.5, respectively. Nitrogenation and carbonation, unlike hydrogenation, result mainly in improvements of the Curie temperature, the saturation magnetization and the anisotropy field at 4.2 K and room temperature for the Nd3Fe29-xCrx compounds compared with their parent compounds.

后向无关联性的本地验证撤销群签名研究

数字签名，是密码理论的一个重要分支，在身份认证等方面举足轻重。但随着电子商务、电子政务等业务的不断展开，在多用户参与的应用环境中显得捉襟见肘。群数字签名应运而生，主要特点是保护了签名者的匿名性。 群签名撤销研究的两个主要方向：设计算量小的撤销成员算法，以及保证成员被撤销之前签名的匿名性和无关联性。目前主要有基于撤销列表（RL）和证据的撤销算法是两类主流算法，前者更适用于移动环境中。因此，在网络化、信化的今天，基于撤销列表的群签名的研究显得弥足重要。 本地验证撤销（VLR），是目前效率最高的一种基于撤销列表的方法。后向无关联性（BU），是指当成员即使在某个时段被撤销，以前的签名仍然保持匿名性。本论文主要工作，是对有群签名方案的分析和BU-VLR方案的设计，主要有以下几个方面： 1. 2007年IEEE Transactions on Vehicular Technology上的一个方案，建立在2004年Boneh等在 CRYPTO的群签名方案。本论文指出，方案使得同一成员的签名具有关联性，导致在VLR安全模型下方案不具有匿名性。 2. 分析的另外两个群签名方案，都是方案设计者在设计签名算法时由于设计不当，使得同一成员的签名具有关联性，从而导致方案在相应的安全模型下不具有匿名性。 3. 对一种基于身份的群签名方案，有文献曾对该签名方案做过分析，在本论文将给出另外一种方法来证明方案不具有匿名性。 4. 分析指出了一种新型群签名方案，其本身是建立在一个错误的签名方案之上，因而该方案不过是空中楼阁。此外，方案还存在其他缺陷。 5.构造了一个BU-VLR群签名方案，具有较短的签名长度和较低的运算量。利用k叉树扩展了方案以减少RL的数据量。最后，对2007年IEICE中一个BU-VLR方案加以改进，签名长度为原来的77.8%，运算量不变。 6.设计的第二个方案，针对现有BU-VLR方案中存在的缺陷，使得到的方案公钥长度不再与成员个数相关；撤销上的数据不再随着时间段的更新而更新，而只是在列表需要更新的时间段更新。 7.在q-SDH假设和困难性假设较强的XDH假设下，构造了一个BU-VLR群签名方案，性能上优于目前最高效的VLR方案，即BS04方案。

群组通信环境中的密钥管理协议

随着群组通信业务的普及，群组通信的相关安全研究也随之兴起。群组密码学的概念首先由 Desmedt 提出。与传统通信中的密码学方案相比，群组密码学具有很多优点，并已经成功地运用到视频点播和分布式系统等一些应用场景中。群签名，环签名，广播加密等密码学体制作为群组密码学的重要分支都得到了学术界的密切关注。本文的研究工作集中在群组密码学的一个重要组成部分：群组密钥管理，即多个（群组）用户在不安全的开放网络环境中通过一定的协议产生一个共享的会话密钥，为后面的通信提供各种安全性保护。 本文的研究工作主要包含两个方面，群组密钥分发协议和可证明安全的认证群组密钥协商协议。在对已有的群组密钥管理方案进行了大量的调查与分析后，我们在此基础上提出了一些有价值的研究成果。本文的主要成果包括： 1. 在第二章中，提出了一种高效的长期 self-healing 群组密钥分发方案。和已有方案相比，新方案的优势包括：（1）我们避免了使用指数运算, 而只是域上多项式的相关运算；（2）群组管理者广播消息次数比 Staddon 等人和Blundo 等人的方案少一次；（3）用户端存储私钥数目比 Staddon 等人的方案少将近一半；（4）新协议的安全性为无条件安全。 2. 在第三章中，构造了一个从一般群组密钥协商协议向基于口令认证的群组密钥协商协议转换的编译器。编译器的构造利用了对称加密体制，NM-CCA2 和 IK-CCA2 安全的公钥加密体制，以及 UF-CMA 安全的数字签名体制，从而使得编译器可以避免在线/离线字典攻击。 3. 在第四章中，提出了一个基于口令认证的群组密钥协商协议，使得网关在认证服务器的协助下和多个用户之间建立一个会话密钥，同时认证服务器不知道此会话密钥的任何信息（网关和认证服务器之间的信道是专用信道）。由于意识到口令的泄露往往是由于用户的不当使用造成的，所以，不同于已有的基于口令认证的门限密钥协商机制，我们的门限方案是在用户端实施。我们的门限方案要求把用户群组和认证服务器预先共享的口令（称之为群组口令）以秘密共享方式分散共享在群组用户之间，并且每个用户所存储口令的子秘密（share）值依然是一个易记忆的口令（称之为用户口令）。只有不少于 k 个用户一起才能恢复出群组口令。 4. 在第五章中，利用了Unified 模型（把用户长期私钥嵌入到密钥协商过程）构造了一个在 Strong Corruption 模型下可证明安全的强健的认证群组密钥协商协议。和已有类似方案相比，新方案所需要的签名数量明显减少，从而，计算复杂度和通信复杂度也随之降低。另外，新协议是在 Strong Corruption 模型下可证明安全，在此模型下的类似协议比较少。 5. 在第六章中，对 Desmedt 等人提出的 BD-II（树型）群组密钥协商协议做出改进。利用在树中各个节点上应用遮罩函数，我们把由于群组关系变化而对密钥更新所产生的影响限制在一个比较小的群组范围中，从而提高了协议在动态情况下运行的效率。新协议通过四个子算法：初始化，成员加入，成员撤销，子群组合并来分别应对群组密钥协商过程中所遇到的各种（动态）情况。

中空纤维膜基萃取稀土的研究：中空纤维膜基萃取Ce~(4+), Th~(4+)和RE~(3+)及其传质动力学

本文用中空纤维膜基萃取法研究了铈（IV）、钍和 RE（III）的膜基萃取；铈（IV）与 RE（III）、钍和 RE（III）的膜基萃取分离；铈（IV）与 RE（III）的界面化学反应动力学；膜基萃取中的流体动力学；萃取操作中乳化发生的机理；测定了中空纤维膜的孔率和孔径。在铈（IV）、钍和 RE（III）的膜基萃取过程中，研究了水相流量、油相流量、原料液中硫酸浓度、萃取剂 N1923浓度和水相溶质浓度对基于水相总传质系数的影响。钍的总传质系数受水相流量影响较大，不受油相流量影响，从而提出水相扩散层控制的膜基萃取传质机理；铈（IV）的传质系数受水相流量影响，油相流量影响较小，主要为水相扩散层控制的传质机理；RE（III）的传质系数受水相和油相的影响都比较小，为膜内传质过程的传质机理。酸浓度对钍和铈（IV）传质系数影响较小，是由于酸浓度影响分配系数，而对于水相扩散控制的传质过程，水相分传质系数与分配系数无关；酸浓度对 RE（III）的影响，是由于膜内传质阻力与分配系数在关；N1923 对 RE（III）萃取传质系数的影响进一步证明膜内过程控制的传质机理，同时对数曲线的斜率大于1 也说明界面反应为一复杂过程；水相溶质浓度不影响基于水相的总传质系数，进一步证实了传质速度与初始浓度无关，也从一个侧面反应了膜基萃取实验有较好的重复性。实验研究的结果，对铈（IV）的膜基萃取选择油相组成为 10%N1923+4%异辛醇+正庚烷（或煤油），水相酸浓度为 1～2mol/L，水相和油相流量可以在较大的范围内选择；钍的膜基萃取条件相似，只是油组成中萃取剂浓度为 1%N1923。在流体动力学部分，通过作用力分析，利用能量守恒原理，推导出了膜基萃取操作中的雷诺数，建立了层流流动模型；腔内外流体流速的径向分布模型和平均流速的计算式；腔内外压力沿管长度分布的数学模型，并得到了两相流体的压力差计算式。流体的动力学分析对于研究乳化发生的机理、传质的数学模型和扩散层厚度等皆有理论价值。通过流体动力学理论，结合膜破裂压和界面张力的实验方法研究了乳化发生的机理。水相进入有机相的乳化，对于非同级萃取，外压作用是乳化的主要原因，提出了类似于重力液滴形成的乳化模型；对于有机相进入水相的乳化，亲油膜的表面易形成油膜及界面张力形成的附加压力是乳化的基本原因，而随着有机相内溶质浓度增加界面张力降低使乳化在萃取操作的后期较易发生。膜破裂压和界面张力的研究方法使乳化的研究变得可以进行实验测定，这对于膜材的选择是很有价值的。界面反应动力学采用了上升单滴法，这种方法一般具有实验重复性较差的缺点。通过实验发现，影响重复性的因素主要是单滴形成速率的稳定性、聚结界面处油水界面位置的恒定和扩散传质的消除等。我们采用盘管式油加液管的设计，比较简单地解决了单滴形成速率稳定的问题，油水界面恒定是一个技术性问题，在实验中得到了较好的解决，通过传质时间与控制聚结界面的面积解决了消除扩散传质的难题。本论文的创新之处有如下几个方面：1．根据氟碳铈矿中钍、铈（IV）与稀土（III）分离的总目标，首次实现了伯胺 N1923对上述离子的中空纤维膜基萃取，提出了利用动力学差异的新型分离模式；2．对流量改变对传质系数的影响，所有文献报道的流量范围都没有达到流量增加使传质系数减小，而这一较高的流量揭示了油水界面随压力增加向膜内移动的事实，这对防止乳化时的压力控制是非常重要的。流量对扩散层厚度影响是对传质系数影响的主要原因，而混流的影响是次要的因素；3．铈（IV）和 RE（III）、钍和 RE（III）的分离表明，分离系数远远大于由总传质系数预计的结果，从而提出了动力学竞争萃取分离的机理；4．膜破裂压的测定方法是一个创新的设计。这种方法对于膜材选择和萃取时操作压力的控制是非常重要的。在现有文献中，都是直接在膜萃取操作时测定水相中的游离油或油相中游离水的体积的方法进行研究，这即不能研究乳化的机理，也不能测定准确的乳化时间。因此膜破裂压测定为乳化过程提供了一个新的研究方法；5．乳化机理的研究得到了较新的结论，尤其对于油相进入水相的乳化机理，较好地解释了在水相有超压存在下油相漏液的原因；6．界面反应动力学实验装置中盘管式油相加样解决了油滴形成稳定性的问题，提高了实验测定的可靠性的重复性。

新型混桥配位聚合物的合成、晶体结构及表征

本论文对文献所报道的α,ω-二梭酸根的配位方式及其构象进行了概括，提出表示其配位方式的方法（暂定为琳L法）．随后报道20个新型配位聚合物的合成、晶体结构，并对部分配合物做了红外、差热热重、磁性质和元素分析等表征．配合物Zn（bpy）（CSH6O4）1和Cu（bpy）（CSH6o4）2为异质同晶结构，五配位的金属原子通过戊二酸根的桥联作用形成一条带状链，相邻链间通过4，4七联毗睫形成二维层．配合物Mll（bpy）（CSH12O4）·HZO3具有与配合物1和2类似的却由辛二酸根桥联的二维层，层间存在结晶水分子．在配合物zn（bpy）（C6HSO4）4中，4，4，一联毗睫和己二酸根桥联锌原子形成具有纳米孔洞的三维框架结构，它们两度相互穿插构筑整个晶体结构．热分析表明配合物3在82一140oC区间失去结晶水分子．配合物4在180-320℃区间内失去4，4’-联毗陡．配合物3在5-30OK区间内的磁性遵循Curie-Weiss定律Xm-l＝4.265／（T+6.3），两个异质同晶结构配合物MZ（hmt）（HZO）2（C3HZO4）2（M＝Mn（II）5，Cu（II）6）中的金属原子通过丙二酸根的桥联和鳌合作用形成二维层。继而通过六次甲基四胺桥联作用形成三维框架结构．配合物5在5一30OK区间内的磁性遵循Curie一Weiss定律Xm-1＝8.99／（T+4.5）．配合物［Mn（HZO）4（bpy）］（C4H4O4）4H207、［Mn（H2O）4（bpy）］（c4HZO4）·4H208和［Zn（H2O）4（bpy）］（C4H4O4）·4H209为异质同晶结构，属于三斜晶系，均由∞1［M（H2O）4（ bpy）2/2］2+阳离子链、结晶水分子和二狡酸根（丁二酸根或反丁烯二酸根）组成．未配位的二梭酸根和结晶水分子通过氢键作用形成带状阴离子链，阴、阳离子链间存在广泛的氢键作用．属于单斜晶系的配合物［Cu（H2O）4（bpy）］（C4H2O4）4H2O 10和｛Ni（H2O）4（bpy）〕（C4H2O4）4HZO 11，具有和配合物7－－9类似的阳离子链二〔M（H2O）4（bpy）2／2］2＋，然而结晶水分子和反丁烯二酸根在氢键作用下形成二维负电荷层．配合物Cu（imid）2（H2O）L（L＝丁二酸根12，反丁烯二酸根13）为异质同晶型化合物，双端单齿的二梭酸根桥联［Cu（工mid）；（H2O）〕2+形成的一维多聚链通过氢键作用组装成三维结构．而配合物Cu（imid）2（C6H8O4）14中五配位的cu原子通过己二酸根的桥联作用形成的一维多聚链止｛［Cu（C3C3H4］2（ C6H8O4）3／3｝．配合物Cu（imid）2（C6H9O4）2巧中双端单齿的己二酸氢根桥联Cu原子形成的带状多聚链止［Cu（C3N2H4）2(C6H9O4)4/2〕，通过氢键作用组装成两度穿插的三维框架结构．配合物12的热分析表明在25一6000c区间内先脱水形成“Cu（imid）2（C4H4O4）”中间体，继而失去咪哩，残留物为CuO．配合物13和14有相似的TG曲线，加热时失去咪哇和“已二酸醉”．配合物14和15的磁性在5300K温度范围内遵循curie－w七155定律，关系式分别为m-＝0.371／（T-4.6）和Xm-l:0.4095／（T-1.2）．在配合物N处Cu（mal）2·ZHZO 16、KZCu（mal）2·3HZO 17、RbZCu（mal）2H2O 18和C82Cu（mal）2' 4H2O19中，丙二酸根桥联铜原子分别形成二维负电荷层（16，17）、一维阴离子链和一络阴离子．在16-19在合成过程中得到的副产物为配合物［Cu（imid）4Cl］Cl 21，它由CI一和［Cu（imid为CI］＋络阳离子组成，通过氢键和芳环堆积构筑整个晶体结构，热分析表明。配合物1企19在25一500℃的温度区间内可能具有以下的热分解过程：（I）脱水，（2）脱去丙二酸醉和甲烷，（3）草酸盐分解生成碳酸盐和CO气体．酉己合物16一19的磁性在5一300K测试温度范围内遵循Curie-Wesiss定律Xm-l＝C／（T-θ） 其中的韦斯常数夕分别为4．3（5）、4．2（6）、3 ．0（6）和4．3（9）K，相应的居里常数C分别为0.434（1）、0.417（2）、0.423（2）和0.411（3）cm3·K.mol-1．

丁二烯在稀土配位催化剂中的“活性”聚合

本文较详细地回顾和评述了阴离子、自由基、阳离子和配位型活性聚合。研究了丁二烯在NdCl_3·3λ-PrOH-AlEt_3庚烷非均相体系中配位聚合的链转移规律。分别用Doi、键谷勤、上野治夫提出的三种动力学方法处理-70 ℃下聚合数据，都得相同的结论；聚合体系中不存在可检测出的链转移和链终止反应。产物微观结构规整（顺1.4含量99.4%以上），分子量分布较窄（(M-bar)_w/(M-bar)_n = 1.75-2.45）。在这种条件下，实现了配位“活性”聚合。讨论了各种因素对活性聚合的影响。发现随聚合温度的升高，配位“活性”聚合对理想活性聚合有所偏离。而丁二烯在本体系中-70 ℃下的配位“活性”聚合是较理想的活性聚合。聚合反应速度和单体浓度呈一级关系。用Boucher和上野治夫二种方法求得-70 ℃下聚合时活性链浓度（活性中心浓度）结果相同（[C~*]=（5 ± 0.7）* 10~(-5)克分子/升）。-70 ℃下聚合的稀土利用率α = 13.5%，聚合速率常数K = 4.1 * 10~(-7)秒~(-1)。用Natta方法计算了在30 ℃、-30 ℃和-70 ℃下聚合时，平均活性链寿命分别是8.5、90分钟和无穷大。-70 ℃下聚合。平均活性链寿命乙趋于无穷大，也证实了活性聚合的结论是正确的。估算了30 ℃和0 ℃聚合时，活性链对单体和对烷基铝的链转移常数（30 ℃下k_(trm)/k_p=1.15 * 10~(-5)，k_(trAl)/k_p = 3.80 * 10~(-5)(克分子/升)~（1/2）；0 ℃下，k_(trm)/k_p=0.62 * 10~(-5), k_(trAl)k_p = 1.72 * 10~(-5)(克分子/升)~（1/2））。30 ℃下，丁二烯聚合一天，封管室温放置72天，再加异戊二烯单体仍百分之百聚合以及丁二烯-异戊二烯嵌段共聚物的合成和表征，也都证明了在-70 ℃下聚合是按活性机理进行的。