氧化镧中放射性的去除——Ⅳ.P_(507)-HNO_3体系萃取法去除氧化镧中放射性的扩大试验

本文给出了在P_(507)-HNO_3体系中去除氧化镧中放射性的工艺流程及用混合澄清槽作为萃取设备,在上海跃龙化工厂完成的扩大试验结果。试验表明:α放射性、铁和钙的去污系数都大于1000,镧的回收率大于96％,产品中α放射性小于1计数/h,Fe_2O_3<5ppm,CaO<50ppm,达到了荧光级氧化镧的要求。该流程操作简便、设备简单、稳定性好,可以应用于工业生产。     

热场致发射电子源曝光系统的技术现状和应用前景

高亮度、长寿命的热场致发射(Thermal field emitter)阴极自七十年代中期已受到人们的关注和重视,历经十多年在理论分析、工艺制备和实验研究上做了大量工作之后,于1988年在电子束曝光机上的应用中取得了突破性进展。用晶向为(100)的钨和具有低逸出功的锆制成的(Zr/O/W)热场致发射阴极在四千小时的使用寿命下亮度值超过六硼化镧阴极一个数量级以上,最近的实验结果表明:在工件台上小束斑下能得到接近两千安培每平方厘米的束流密度,而且四十小时内束流稳定度接近千分之一。显然,这几个表征曝光系统综合技术性能的重要指标,说明多年困扰于各种电子束曝光系统(特别是高斯圆斑电子束系统)在高分辨率情况下生产率较低的技术难题已经得到了比较圆满的解决。 八十年代末期,当热场致发射电子源曝光系统的技术关键解决后,这项技术就成为技术发达国家,特别是美国和日本,在电子束曝光领域进行技术竞争的热点;九一年五月底在美国召开的国际三束会议上有关场致发射阴极和MEBES—4型机已经采用TFE的最新报道充分证实了这项技术在电子束曝光技术应用中的重要地位和发展潜力。     

LaMgAl11O19-La2Ce2O7 复合陶瓷的高温相稳定性

La2Ce2O7(LC) 和 LaMgAl11O19(LMA) 是两种新型热障涂层材料。 LC 具有优良的热物理及抗腐蚀性能, 但 其断裂韧性差。 LMA 具有良好的综合性能, 特别是力学性能优良。 基于复合材料设计理念, 为充分利用 LC 和 LMA 的优势, 本文探究了制备 LMA-LC 双相复合陶瓷的可行性。 采用高温固相法合成了 LMA 和 LC 粉末, 重 点研究了 LMA 和 LC 的高温稳定性, 初步研究了 LMA-LC 复合陶瓷块材的力学性能。 结果表明： LMA 和 LC 在 高温下发生了化学反应, 反应程度随温度升高而加剧, 主要反应产物为 LaAlO3, 其在低温下的铁弹性可能是复 合陶瓷在室温下具有良好力学性能的原因。     

Novel lanthanide salicylaldimine complexes with unusual coordination mode

The one-step metal promoted reaction between salicylaldehyde and 4-methyl-1,3-phenylenediamine in the presence of lanthanum(III) or gadolinium(III) nitrate yields new salicylaldimine complexes containing N,N′-bis(salicylidene)-4-methyl-1,3-phenylenediamine as a result of the [2 + 1] Schiff base condensation. The crystal structure of the gadolinium complex reveals a dinuclear species with four unionized ligands coordinating in the monodentate and bridging bidentate fashion, using exclusively the oxygens as donor atoms with the nitrogen atoms not being involved in coordination. The coordination number of nine is achieved by involving three bidentate nitrate counterions in the coordination sphere.     

Preparation and structural characterization of perovskite-type LaxLn1−x″CoO3 by the thermal decomposition of heteronuclear complexes, LaxLn1−x″| Co(CN)6| · nH2O (Ln″ = Sm and Ho)

Perovskite-type La_xLn_1−x″CoO₃ oxides are prepared by the thermal decomposition of La_xLn_1−x″ [Co(CN)₆] · nH₂O hetero-nuclear complexes. Except for LaCoO₃ (hexagonal), the structures observed for La_xSm_1−xCoO₃ are othorhombic. While the perovskite-type oxide HoCoO₃ is not formed by decomposition at 1000°C of the corresponding hexacyano complex, the partial replacing of Ho with La is effective in forming the pervoskite-type oxide having an orthorhombic structure containing Ho even at 800°C. A monotonous correlation (quasi-linear relationship) was found between the b- and c-lattice constants of the orthorhombic structures of the perovskite-type oxides and the effective radii of Ln ions, defined as r_eff = xr_1.a + (1 − x)r_1.0″. The distortion parameter for the orthorhombie cell (3″a/b−1) increaseswith decrease in r_eff and is expected to be 0.270 for perovskite-type HoCoO₃. The crystal structure of the La_xLn_1−x″, CoO₃ oxides is mainly controlled by the effective radii of Ln ions.     

Thermodynamic assessment of the La-Mg system

A thermodynamic modeling and optimization of the La-Mg system is carried out by means of the CALPHAD method taking into account the latest experimental results. The liquid, bcc-La, fcc-La, dhcp-La and hcp-Mg solutions are modeled as substitutional solutions (La, Mg) using the Redlich-Kister formalism. The LaMg, LaMg₂, La₅Mg₄₁, La₂Mg₁₇ and LaMg₁₂ phases are treated as stoichiometric compounds, and the non-stoichiometry of LaMg₃ is described as (La,Mg)_0.25Mg_0.75. The results are in good agreement with the set of experimental data which were carefully discussed and selected.     

NOx adsorption behavior of LaFeO3 and LaMnO3+δ and its influence on potentiometric sensor response

NO_x adsorption behavior on LaFeO₃ (LFO) and LaMnO_3+δ (LMO) was characterized using temperature controlled methods and mass spectrometry. Temperature program desorption revealed decomposition of complex surface species formation when NO or NO₂ was adsorbed on LFO and LMO. LFO exhibited higher adsorption capacity for NO_x species than LMO and was shown to be more active for NO_x surface conversion. Both effects were attributed to the different B-site cations, with iron in LFO in the 3+ valence state, and manganese in LMO in the 3+ and 4+ valence states. Results from diffuse reflectance infrared spectroscopy were used to identify specific nitrite and nitrate species that are formed on the surfaces of LFO and LMO at room temperature. Temperature programmed reaction revealed a complex NO₂ decomposition mechanism to NO and O₂ for LFO and LMO in which the formation of nitrite and nitrate species serve as intermediates below ∼600 °C. NO_x sensing mechanisms were considered and predicted based on the types and quantities of surface species formed.     

Hemocompatibility of lanthanum oxide films fabricated by dual plasma deposition

Lanthanum oxide films were fabricated using dual plasma deposition. X-ray photoelectron spectroscopy (XPS) showed that La existed in the + 3 oxidation state. X-ray diffraction (XRD) revealed a (101) oriented hexagonal structure. Blood platelet adhesion tests and endothelial cell cultures were used to evaluate the hemocompatibility of the as-deposited films. Scanning electron microscopy (SEM) and optical microscopy were employed to evaluate the surface morphology of the blood platelets and endothelial cells on the films. The results showed that the number of adhered, aggregated and morphologically changed platelets was reduced compared to that observed on low-temperature isotropic carbon (LTIC). Endothelial cells culture tests indicated good adhesion and proliferation of human umbilical vein endothelial (HUVE) cells in vitro. Our study suggests that lanthanum oxide films are potential blood-contacting biomedical materials.     

纳米锆酸镧团聚体特性及等离子涂层性能的研究

采用喷雾干燥法制备了纳米锆酸镧团聚体粉末,采用大气等离子喷涂制备了纳米锆酸镧涂层,并用扫描电镜和XRD对涂层的微观组织结构进行了研究。结果表明:喷雾干燥法制备的纳米La_2Zr_2O_7团聚体,粒度接近正态分布,流动性好,松装密度较大。采用大气等离子喷涂制备纳米锆酸镧涂层中存在一定量的孔隙和微裂纹,利于隔热。纳米锆酸镧热障涂层在1473K烧蚀8h后的相结构稳定。     

LaO_x(OH)_y supported platinum catalysts for CO oxidation:Deactivation by formation of lanthanum carbonate

Platinum catalyst for CO oxidation has been studied for decades,due to its high activity and good stability.In this work,we prepared three different lantha num oxide or hydroxide supports(LaO_x(OH)_y),and deposited platinum(Pt) with 0.5 at% via an impregnation approach to synthesize Pt/LaO_x(OH)_y catalysts.However,we find that these catalysts perform a poor stability for the CO oxidation reaction.The fresh and used samples were comprehensively characterized by multiple techniques including power X-ray diffraction(XRD),X-ray absorption fine structure(XAFS),transmission electron microscopy(TEM),temperature-programmed reduction by carbon monoxide(CO-TPR) and thermogravimetric analysis(TGA),to demonstrate that the oxidized platinum atoms or clusters,without any component of Pt-Pt metallic bond,are highly dispersed on the surface of LaO_x(OH)_y.Furthermore,the as-formed lanthanum carbonate(La₂O₂CO₃) during the exposure to ambient circumstances or in the reaction atmosphere of CO+O₂,severely impair the reactivity of Pt/LaO_x(OH)_y.On the basis of the obtained experimental results,we have drawn a conclusion that the oxidized P_tO_x atoms or PtxOy clusters are the active species for CO oxidation,while the formation of lanthanum carbonate is the origin of deactivation on reactivity.