THERMAL-DECOMPOSITION PROCESS OF SOME RARE-EARTH NITRILOTRIACETIC ACID SERINE MIXED COMPLEXES

Thermal decomposition processes of the mixed complexes of nitrilotriacetates of Pr, Sm, Tb, Ho and Tm with 2-amino-3-hydroxypropionic acid have been investigated. The results indicate that serine may coordinate to the rare earth ion via its hydroxyl group, not by means of its carboxyl group. From the thermogravimetric and the derivative thermogravimetric curves it can be deduced that there may be six or seven steps in the thermal decomposition process of these mixed complexes, and that not all thermal decomposition processes in these mixed complexes are the same. Some possible thermal decomposition reactions have been proposed, and the differences between the thermal decomposition processes of these complexes are also discussed.

A STUDY OF MODE-I DELAMINATION RESISTANCE OF A THERMOPLASTIC COMPOSITE

This paper describes the mode I delamination behaviour of a unidirectional carbon-fibre/poly(phenylene ether ketone)(PEK-C) composite. Tests have been performed on double cantilever beam (DCB) specimens. Several data reduction schemes are used to obtain the critical strain energy release rate, G(IC), and the results are compared. It is shown that when using a DCB test to determine the fracture toughness, corrections must be employed. The experimental methods have been described for ascertaining the correction terms, and the results are consistent after modification. Some of the authors' results are different from those of other authors, particularly the negative correction term for crack length, the larger exponent (n > 3) in the relationship C = Ra(n), and decrements of flexural modulus with the crack growth when using the simple beam theory to predict the bending behaviour of DCB specimens. The possible reasons are discussed.

测汞仪用高效绿色稀土发光材料

在环保、地质、水文、科研等部门,测定水、土壤、气体及矿物中的汞含量、是一个十分普遍而重要的问题。在仪器分析中、冷原子吸收法测定汞,已在各个分析实验室获得广泛地应用。其特点是检出浓度低、重现性好,抗干扰性强。但随着人们对环境保护的日益重视需要检出更低的含汞量(如0.001—0.1μg/L),这就需要对测汞仪进行改进,其中一个重要问题是提高仪器中显示材料的灵敏度和稳定性。为此,我们研制了掺Ce、Tb、Mn的多铝酸盐发光材料,用于测汞仪后获得良好效果。

时间分辨激光荧光光谱分析方法研究——Ⅱ混合稀土中铽的测定

本文介绍了利用自装的时间分辨激光荧光光谱装置对混合稀土中铽的测定方法。装置采用氮分子激光器为激发光源,Boxcar积分器为信号处理系统,选择了Tb-Sal-乙醇溶液为荧光体系,用标准加入法对样品进样行了测定。并将已知样品的测定结果与其它方法测定结果进行了比较。本法测定铽的相对标准偏差为7.4％,检出限为1.3×10~(-4)μg/ml。

LnP_5O_(14)(Ln=La—Tb)晶体的相变和缺陷

本文用X射线衍射方法研究 LnP_5O_(14)(Ln=La,Pr,Nd,Sm,Tb)晶体相变表明,相变是晶轴 c 和α夹角β随温度升高逐渐减小的过程,也就是晶体的畸变角δ随温度下降而增加。相变温度随稀土离子半径由 La 到 Tb 减小呈线性增加,最后讨论了晶体缺陷随温度的变化关系。

稀土三氟乙酸络合物的快原子轰击质谱研究

本文首次报道Ln(OOCCF_3)_3(Ln=Pr、Nd、Sm、Eu、Gd、Tb、Ho、Er、Tm、Yb、Lu在甘油(G)中的正负离子FAB谱、总结了其离子特征。通过亚稳分析、探讨了某些离子的碎裂方式,提出了Ln(Ⅱ)→Ln(Ⅰ)可能的还原变价机制。

希土-HEDTA-蛋氨酸三元配合物研究

用pH电位法测定了希土与N-羟乙基乙二胺三乙酸(HEDTA)、蛋氨酸(Met)三元配合物在25℃和0.15mol/L(NaCl)离子强度下的稳定常数。以荧光光谱法研究了TbCl_3、Tb-Met、Tb-HEDTA以及Tb-HEDTA-Met体系,Tb~(3+)的三元配合物发射被两个配体同时敏化的Tb~(3+)特征荧光。讨论了三元体系中的配位作用以及能量传递特点。

EFFECT OF REPTATION ON FRACTURE-MECHANICS OF RUBBER NETWORKS

End-linked hydroxyl-terminated polybutadiene containing unattached linear polybutadiene was used to study the effect of reptating species on the fracture mechanics of rubber networks. The concentration of reptating species in the networks ranged from 0 to 100%. The fracture mechanics of the networks was described using the critical strain energy release rate in mode III testing, i.e. the tearing energy. The tearing energy was measured at room temperature using a 'trouser' specimen at a strain rate spanning five logarithmic decades. When the strain rate was as low as 10(-4) s-1, the tearing energy of the networks increased with reduction in reptating species. In this case the reptating species did not contribute to the tearing energy of the networks due to relaxation. Hence, the tearing energy increased with the number of crosslinked chains per unit volume in the networks. At a strain rate ranging from 10(-3) to 10(-1) s-1, the tearing energy of the networks was governed by local viscosity. The tearing energies of the networks containing various amounts of reptating species were superimposed to give a master curve based on the Williams-Landel-Ferry equation.

STUDY ON RARE EARTH-HEDTA-SERINE TERNARY SYSTEM BY POTENTIOMETRY AND FLUORESCENCE SPECTROSCOPY

In this pare earth-HEDTA-serine (Ser) ternary system has been studied by potentiometric titration at 25 degrees C with an ionic strength of 0.15 mol.L-1 (NaCl). The excitation and fluorescence spectra of TbCl3, Tb-Ser, Tb-HEDTA and Tb-HEDTA-Ser have hem determined at room temperature. The stability constants of these ternary complexes have been obtained, It lieu been found that Tb-HEDTA-Ser ternary system exhibit characteriatic fluorescence spectrum of Tb3+ sensitized by two ligands,The results mean that the chemical hood between the control ion and the ligand in this ternary system is predominantly ionic in character,and the energy transfer from ligand to Tb8+ is performed by a kind of abort-range electron exchange action.

钙钛矿型稀土镓酸盐的光谱性质

本文得到LaGaO_3晶体室温下的激发光谱和荧光光谱,发现LaGaO_3晶体能够产生可见荧光,并且荧光谱线比粉末状LaGaO_3变窄.测定了室温下LnGaO_3(Ln=La,Pr,Na)晶体的吸收光谱,对红外吸收光谱给出了理论点阵振动数目和对称类型,研究了晶体经退火处理对吸收光谱的影响.对粉末状 LaGaO_3:Ln(Ln=Ce,Sm,Tb)研究了合成温度及掺杂稀土离子浓度对光谱结构的影响.

Ce_xGd_yTb_(1-x-y)P_5O_(14)晶体生长及其光谱

采用蒸发溶液法从磷酸溶液中生长出一系列Ce_xGd_yTb_(1-x-y)P_5O_(14)晶体.测定了它们的结构.它们属于单斜晶系,空间群P2_(1/c).测定了Ce_(0.9)Gd_(0.1)P_5O_(14)、Ce_(0.9)Tb_(0.1)P_5O_(14)和La_(0.8)Gd_(0.1)Tb_(0.1)P_5O_(14)等晶体的光谱.首次观察到,将Gd加入Ce_xTb_(1-x)P_5O_(14)晶体中形成.Ce_xGd_yTb_(1-x-y)P_5O_(14)时阻碍了Ce~(3+)→Tb~(3+)的能量传递,导致Ce~(3+)的发射峰增强,Tb~(3+)的~5D_4—~F_J发射峰减弱、而~5D_3—~7F_J发射峰增强.

π-烯丙基稀土配合物的合成、结构及其催化烯烃聚合反应机理的研究——Ⅱ.LiY(π-C_3H_5)_4·2.5D催化异戊二烯聚合反应机理的研究

在稀土配位共轭双烯烃聚合反应机理的研究中,一般认为按π-烯丙基机理进行,但迄今为止尚缺乏足够的实验证据。我们曾用~1H-NMR、一维~(13)C-NMR和二维~(13)C-NMR系统地研究了(CF_3COO)_2LnCl·EtoH-(i-Bu)_2AIH-共轭双烯烃(Ln=La、Pr、Nd、Sm、Tb、Ho、Sc和Y)均相聚合体系的聚合机理,提出了η~4-共轭双烯(顺式-反式-)和η~3-烯丙基(同式-对式-)机理。但由于广烯丙基稀土配合物稳定性差,难于合成,加之聚合体系中很难直接分离出π-烯丙基稀土配合物活性体,为此,至今尚未能用模型π-烯丙基稀土配合物对上述机理进行研究。我们已合成一系列π-烯丙基稀土配合物LiLn

稀土与L-谷氨酰胺配合物的电子能谱研究

合成了通式为LnL_3Cl_3·2H_2O(Ln=Eu,Tb,Ho,Tm;L=L-谷氨酰胺)的固体配合物。用XPS辅以元素分析、热分析及IR光谱研究了配合物的组成及性质。观察到配合物中O_(1a)、Ln_(3d)、Ln_(4d)和Cl_(2p)结合能的变化,并发现Eu配合物Eu_(3d)谱峰的伴峰结构,讨论了伴峰产生的机理。

助熔剂法生长YVO_4:RE~(3+)晶体

稀土钒酸盐是很好的发光和激光材料。本文探讨了助熔剂法生长YVO_4:RE~(3+)(RE~(3+)=Pr~(3+),Sm~(3+),Tb~(3+))晶体的工艺条件。讨论了V_2O_5与Pb_2P_2O_7为助熔剂和温度对晶体成核,生长习性和缺陷的影响。并测定了晶体的结构参数。分别以V_2O_5和Pb_2P_2O_7为助熔剂进行YVO_4:RE~(3+)晶体的生长,结果表明用V_2O_5为助熔剂比用Pb_2P_2O_7为助熔剂要优越得多。以

Ce~(3+)-Gd~(3+)在某些稀土硼酸盐体系中的能量传递

Ce~(3+)离子有一个宽而强的4f-5d吸收带,它能有效地吸收能量。Ce~(3+)离子的荧光寿命非常短,能将能量有效地传递给其它离子起敏化作用。对于Ce~(3+)→Tb~3+),Ce~(3+)→EU~(3+)和Ce~(2+)→Mn~(3+)的敏化作用已有许多报导,并在灯用发光材料上获得应用。Blasse等提出在Ce~(3+)敏化Tb~(3+)时。用Gd~(3+)作中间体能获得高效发光材料。由于Ce~(3+)的5d能级强烈地依赖于基质,其发射波长可以从紫外到红区,而Gd~(3+)的4f-4f跃迁的激发和发射峰值随基质的变化改变不大,因此将有可能呈现不同的Ce~(3+)-Gd~(3+)的能量转移过程。