超高分子量聚苯乙烯的合成和聚合反应动力学

杯芳烃钕与Mg(n Bu) 2 、HMPA所组成的三元络合催化剂用于苯乙烯配位聚合能以高收率制得超高分子量聚苯乙烯 .以甲苯为溶剂 ,在一定条件下制成三元配位催化剂 ,当 [Nd]=8× 10 - 4mol L ,[St]=4 .0mol L ,Mg Nd =2 0 .0 (摩尔比 ) ,HMPA Mg =1.0 (摩尔比 ) ,5 0℃聚合 4 5min ,聚合转化率可达到 80 %左右 .所得聚苯乙烯的重均分子量高达 2 10× 10 4 ,分子量分布指数为 1.6 1.间规聚苯乙烯含量为 81% .动力学研究表明 ,聚合反应速率与单体和主催化剂 杯 [6 ]芳烃钕的浓度分别呈 1次方关系 ,聚合反应的表观活化能为 4 1.7kJ mol     

Prospects of Sol-Gel Process for Spectral Hole-Burning Glasses

Persistent spectral hole burning was studied in Eu³⁺ ions-doped Al₂O₃-SiO₂ glass prepared by a sol-gel method. The gel synthesized by the hydrolysis of Si- and Al-alkoxides and EuCl₃·6H₂O was heated in air and hydrogen gas atmospheres. For the glass heated in air to contain OH bonds, the hole was formed by the photoinduced rearrangement of the OH bonds surrounding the Eu³⁺ ions, and was thermally refilled and erased above 200 K. On the other hand, the glass heated in hydrogen gas showed the hole spectrum above 200 K. It was found that the hole depth was independent of the temperature and was 7% of the total intensity at room temperature. The proposed mechanism was the electron transfer between the Eu³⁺ ions and the defect centers formed in glass matrix.     

稀土高氯酸盐-谷氨酸配合物[Pr2(L-α-Glu)2(ClO4)(H2O)7](ClO4)3•4H2O的低温热容和热化学研究

合成了一种稀土高氯酸盐-谷氨酸配合物. 经TG/DTG、化学和元素分析、FTIR及与相关文献对比, 确定其组成为[Pr₂(L-α-Glu)₂(ClO₄)(H₂O)₇](ClO₄)₃•4H₂O, 纯度为99.0%以上. 利用显微熔点仪分析发现其没有熔点. 在78～370 K温区, 用精密绝热量热仪测量其低温热容, 在285～306 K温区发现一明显吸热峰, 归结为固-固相变过程. 通过相变温区三次重复热容测量, 得到相变温度T_tr、相变焓Δ_trH_m和相变熵Δ_trS_m分别为(297.158±0.280) K, (12.338±0.016) kJ•mol^－1和(41.520±0.156) J•K^－1•mol^－1. 用最小二乘法将非相变温区的热容对温度进行拟合, 得到了热容随温度变化的两个多项式方程. 用此方程进行数值积分, 得到每隔5 K的舒平热容值和相对于273.15 K的热力学函数值. 根据TG/DTG结果, 推测了该配合物的热分解机理. 依据Hess定律, 选择1 mol•dm^－3盐酸为量热溶剂, 利用等温环境溶解-反应量热计, 测定了该配合物的标准摩尔生成焓为: Δ_fH_m⁰＝－(7223.1±2.4) kJ•mol^－1.     

Iron-Cobalt-Silica Aerogel Nanocomposite Materials

Iron-Cobalt-Silica nanocomposites were prepared in form of aerogels. X-ray diffraction, transmission electron microscopy and N₂ physisorption at 77 K were used to investigate the structure, size and dispersion of the nanocrystals and the porous structure in the aerogels and in the final composites. The variation of the supercritical drying conditions gives rise to differences in the morphological features of the aerogels. These differences influence the size of the cobalt oxide nanoparticles in the aerogels. On the other hand, after the reduction treatment the average size of the alloy nanoparticles is the same in all the aerogel nanocomposites. The effect of reduction temperature on alloy formation and particle size is also discussed.     

Synthesis, structure and X-ray excited luminescence of Ce-doped AREP2O7-type alkali rare earth diphosphates (A=Na, K, Rb, Cs; RE=Y, Lu)

The crystal structures of five new alkali rare earth diphosphates were obtained by Rietveld refinement of powder X-ray diffraction (XRD) profiles, including four alkali lutetium diphosphates ALuP₂O₇ (A=Na, K, Rb, Cs) and the low temperature phase of KYP₂O₇. The scintillation properties of Ce³⁺-doped AREP₂O₇ (A=Na, K, Rb, Cs; RE=Y, Lu) powder samples were studied under static and pulsed X-ray excitations, and featured outstanding scintillation properties with light yields 1–2 times of that of Bi₄(GeO₄)₃ and relatively short decay time of 20–28 ns. Considering the suitable emission wavelength range, large light yield, short decay time, and non-hygroscopic nature, Ce³⁺-doped AREP₂O₇-type alkali rare earth diphosphates are potential candidates for high-counting-rate scintillation applications.     

交联聚异丁烯酸甲酯型负载树脂的孔结构与分离稀土性能的关系

本文报导异丁烯酸甲酯型负载树脂的交联度、致孔剂组成和含量对负载树脂孔结构的影响.结果指出,良溶剂和劣溶剂按一定比例混合作为致孔剂,可制备不同孔结构的树脂.致孔剂量增加,树脂表观比重减小,而比表面积、孔体积与平均孔径均增加.交联度从10％增加到35%,表观比重和比表面积增加,而孔体积与平均孔径减小.增加致孔剂所含良溶剂的比例,树脂的表观比重、比表面积增加,而孔体积与平均孔径减小.已制备一系列不同孔结构的2-乙己基膦酸单2-乙己基酯(P507)负载树脂,比较了它们分离La、Ce、Pr、Nd的性能.结果表明,适当孔结构的负载树脂用于萃取色层分离稀土元素具有优良的分离性能.     

Carbometallate: Komplexe Anionenverbände [MoC4/26—] in der Kristallstruktur von Pr[MoIIC2]

Carbometalates: Complex Anions equation/tex2gif-stack-4.gif [MoC_4/2^6—] in the Crystal Structure of Pr equation/tex2gif-stack-5.gif [Mo^IIC₂] Criteria for the existence of carbometalates are established and discussed in a broader context. The concept is then applied to the novel compound Pr₂[MoC₂], which is characterized by chemical analyses, X‐ray diffraction and metallography. The crystal structure (tetragonal, P4₂/mnm, Z = 4, a = 581.29(8) pm, c = 1032.53(14) pm) consists of layered polyanions equation/tex2gif-stack-6.gif[MoC_4/2^6—] of distorted vertex and edge sharing MoC₄ tetrahedra. Praseodymium is also in a distorted tetrahedral coordination by carbon. The physical properties show “bad metal” behaviour and localized magnetic 4f‐moments in agreement with the existence of Pr³⁺‐species. A detailed bonding analysis using both the electron localization function ELF and the COHP method justifies the interpretation of the title compound as a carbomolybdate(II).     

三元稀土萃取分离工艺中有效分离系数的研究

本文通过计算机模拟计算,对恒定混合萃取比的三元稀土萃取分离工艺中有效分离系数的变化规律进行了研究,并在串级萃取理论的基础上提出了一种采用有效分离系数确定三元稀土萃取分离工艺参数的方法。     

端视式全谱直读电感耦合等离子体发射光谱法测定高纯氧化镧中稀土杂质

电感耦合等离子体发射光谱(ICP-AES)测定高纯氧化镧中14个稀土元素杂质,镧对其它稀土元素的光谱干扰比较严重,要求光谱仪单色器有较高的分辨率。使用端视式全谱直读ICP-AES仪,选择测定波长,工作参数优化,讨论了镧和酸度的影响。大部分稀土元素测定使用曲线拟合(FACT)的背景校正方法。该方法的稀土元素氧化物检出限达到3×10-4~0.022 mg.L-1(3σ)。     

植酸与稀土元素的固态配合物的研究

植酸（PllytiC。Cid）又称肌醇六磷酸酯（myo－iflOSitdhX。hSPhOSPh。ie）（简写为H12lHP］常以钙、镁复盐（菲汀Phntin）形式存在于植物中,尤其在谷类和植物的种子中含量较高［'j．植酸具有惊人的骛合能力,除碱金属外几乎能与所有金属离子生成沉淀,一些高价金属离于甚至在强酸性介质中也可定量沉淀［如Ti、Zr、Hf、Th、Ce（IV）和In、Sc等〕,这些性质已初用于Th'"的定量测定L'和SC'"的分离提取「",Gd'"与植酸的配合物被用作核磁共振成倍（MRI）的对比剂［'j．然而,对有关配合物的固态组成及性质研究尚无文献报道．本文…