Heterogeneous equilibria in aqueous solutions of uranophosphates MII(PUO6)2·nH2O (MII = Mg2+, Ca2+, Sr2+, Ba2+)

The stability of uranophosphates M^II(PUO₆)₂·nH₂O (M^II = Mg, Ca, Sr, Ba) in aqueous solutions at pH from 0 to 14 was studied. These compounds preserve their composition and structure in the interval of pH 1–11 and congruently pass into the solution within the limits of their solubility. In strongly acidic media (pH < 1), alkaline-earth metal uranophosphates transform into uranophosphoric acid HPUO₆·4H₂O. In alkaline solutions at pH > 11, the uranophosphates MII(PUO₆)₂·nH₂O irreversibly transform into diuranates. Using the methods of equilibrium thermodynamics, the solubility products and Gibbs functions of formation of alkalineearth metal uranophosphates were calculated, the solubility curves were calculated and experimentally confirmed, and the speciation diagrams of U(VI) and P(V) in solutions and in equilibrium solid phases were constructed.     

冷冻干燥合成ZrO2-(Al2O3,Fe2O3)及其微观组织的变化

通过冷冻干燥方法制备了ZrO2-Al2O3,ZrO2-Fe2O3二元及ZrO2-(Al2O3,Fe2O3)三元体系的前驱物粉末，研究了不同温度下的相变及微观组织结构，证明Fe2O3具有球化晶粒的作用，并获得了具有均匀细小显微组织的三元体系。     

K2Ln(NO3)5·2H2O(Ln=La,Ce,Pr,Nd,Sm)的晶体生长和热重-差热分析研究

本文生长出了K₂Ln（NO₃）₅·2H₂O（Ln=La；Ce；Pr；Nd；Sm）的单晶，并对其进行了晶体结构及差热-热重分析研究．结果表明，K₂Ln（NO₃）₅.2H₂O（Ln=La；Ce；Pr；Nd）的晶体属正交晶系，Fdd2空间群．首次生长出KPrN单晶并用直接法解出其晶体结构．解得KPrN的晶胞参数为：a=11．2210（10）A, b=21．411（3）A，c=12．208（2）A,Z=6；R=0．0240．对KLnN加热，则依次出现脱水、熔化、不可逆相变和NO的分解过程（K₂Ce（NO₃）₅·2H₂O除外）K₂Ln（NO₃）₅·2H₂O（Ln＝La；Nd；Sm）的NO分三步分解，K₂Ln（NO₃）₅·2H₂O（Ln=Ce；Pr）的NO分两步分解·KNO₃和Ln（NO₃）₃·nH₂O的混合物在225℃左右生成K₂Ln（NO₃）₅     

阴离子粘土LiAl2(OH)6X·2H2O(X=OH-,1/2CO32-)的离子交换特性

本文研究了阴离子粘土ＬｉＡｌ２（ＯＨ）６－Ｘ．２Ｈ２Ｏ（Ｘ＝ＯＨ＾－，１／２ＣＯ３＾２）的离子交换特性，结构分析表明，ＬｉＡｌ２－ＬＤＨ含水分隔层内的ＯＨ和ＣＯ３＾２－离子容易与酸性溶液中的Ｃｌ、ＮＯ３等离子进行交换，且保持ＬｉＡｌ２－ＬＤＨ的水滑石型层状结构不变，其中Ｃｌ－离子型表现较高的离子交换速率，在阴离子交换的同时，氢氧化以内的Ｌｉ＾＋离子也被Ｈ离子部分取代，但交换率较低，进一步讨论说明，     

Crystal structure of uranyl μ3-oxoacetate [(UO2)3(μ3-O)2(OOCCH3)2(H2O)2]

The crystal structure of [(UO₂)₃(₃-O)₂(OOCCH₃)₂(H₂O)₂] consists of uranium coordination polyhedra (CPs) combined via common equatorial edges into ribbons, with ₃-O atoms being common for three CPs. The structure was compared with that of known complexes with ₃-oxo atoms.Translated from Radiokhimiya, Vol. 46, No. 5, 2004, pp. 396–400.Original Russian Text Copyright © 2004 by Charushnikova, Krot, Starikova.     

纳米热障涂层材料Ln2(Zr0.7Ce0.3)2O7(Ln=La,Nd,Sm,Gd)的热物性能

用水热合成法制备纳米热障涂层材料Ln₂(Zr_0.7Ce_0.3)₂O₇ (Ln=La,Nd,Sm,Gd),表征其晶体结构、形貌、晶格参数、平均粒径尺寸和比表面积并研究了相关的热物性能及其机理。对XRD谱和Raman谱的分析表明,La₂(Zr_0.7Ce_0.3)₂O₇、Nd₂(Zr_0.7Ce_0.3)₂O₇和Sm₂(Zr_0.7Ce_0.3)₂O₇均为烧绿石结构,而Gd₂(Zr_0.7Ce_0.3)₂O₇为萤石结构。结合SEM观察、体积收缩以及相对密度,分析了块...     

First-principles study on electronic structure, phase stability, and optical properties of In2X2O7 (X═C, Si, Ge or Sn)

In₂Ge₂O₇ and In₂Si₂O₇ are commonly used as scintillation materials. More studies on In₂X₂O₇ (X═C, Si, Ge, or Sn) are important to explore the possibility of using these materials for optoelectronic devices. This work presents results dealing with structural properties, electronic structure, chemical bonding, carrier effective masses, and optical spectra of polymorphs of In₂X₂O₇ obtained from first-principles calculations. The monoclinic phase of In₂Ge₂O₇, cubic and monoclinic phases of In₂Si₂O₇, as well as cubic phase of In₂Sn₂O₇ are known in scientific literature. From the total energy calculations at high pressure/strain we have found that the monoclinic phase of In₂Si₂O₇, In₂Ge₂O₇, and In₂Sn₂O₇ can be transformed into the cubic phase. The cubic phase of In₂Ge₂O₇ and In₂Sn₂O₇ is found to be more stable than the monoclinic phase. However, the monoclinic phase of In₂C₂O₇ and In₂Si₂O₇ is more stable than the cubic phase. The phase stability study suggests that In₂C₂O₇ is not stable, and that it might dissociate into corresponding binary oxides. Effective masses of electrons and holes have been estimated. Analysis of optical properties shows that in Si solar cells In₂Si₂O₇ and In₂Sn₂O₇ can be used as antireflection coating layer.     

Crystal structure of a double Np(V) and Co(NH3)63+ maleate, Co(NH3)6[NpO2(HL)2(H2O)3](HL)2?H2O [L = OOC(HC)2COO]

Crystal structure of a double Np(V) and Co(NH₃) ₆ ³⁺ maleate Co(NH₃)₆[NpO₂(HL)₂(H₂O)₃](HL)₂H₂O [L = OOC(HC)₂COO] was studied. The crystal structure consists of complex anions [NpO₂(HL)₂(H₂O)₃]^–, HL^– anions, [Co(NH₃)₆]³⁺ cations, and water molecules of crystallization. Hydrogen bonds in which proton donors are water molecules and hexaamminecobalt cations link structural fragments to form a 3D network. The coordination polyhedra of the Np(V) atoms are pentagonal bipyramids whose equatorial planes are formed by oxygen atoms of two HL^– anions and three water molecules. Four crystallographically independent maleate anions were identified in the structure. Two of these anions enter into the Np(V) surrounding, and their coordination capacity is 1.Translated from Radiokhimiya, Vol. 46, No. 6, 2004, pp. 521–523.Original Russian Text Copyright © 2004 by Charushnikova, Krot, Starikova.     

Interaction of methanesulfonic acid with actinide ions. The new complexes HImid[Np(C2O4)(CH3SO3)3(H2O)2], [NpO2(Terpy)(CH3SO3)(H2O)]·2H2O, and [UO2(CH3SO3)2(H2O)]

Complexation of methanesulfonic acid with Np(IV), Np(V), and U(VI) ions in aqueous solutions was studied. New crystalline compounds HImid[Np(C₂O₄)(CH₃SO₃)₃(H₂O)₂] (I), [NpO₂(Terpy)(CH₃SO₃)·(H₂O)]·2H₂O (II), and [UO₂(CH₃SO₃)₂(H₂O)] (III) were isolated. The absorption spectra of all the compounds in the IR, visible, and UV ranges were examined. The relationship between the composition, crystal structure, and IR and electronic absorption spectra of the complexes is discussed. Original Russian Text ? G.B. Andreev, N.A. Budantseva, I.G. Tananaev, B.F. Myasoedov, 2009, published in Radiokhimiya, 2009, vol. 51, no. 3, pp. 197–201.     

Preparation of nano-sized ABi2Nb2O9 (A?=?Ca2+, Sr2+, Ba2+) ferroelectric ceramics by soluble Nb(V) tartarate precursor and their dielectric characteristics after sintering

ABi₂Nb₂O₉ (A = Ca²⁺, Sr²⁺, Ba²⁺) were prepared by using an aqueous solution method from the mixture of water-soluble M-EDTA (M = Ca²⁺, Sr²⁺, Ba²⁺), Bi-EDTA, Nb-tartarate and TEA as the starting materials. A black fluffy mass resulted on heating the solution mixture at ∼200 °C. X-ray powder diffraction (XRD) showed that a single phase with the layered perovskite structure was formed after calcining the black fluffy mass at 600 °C. No intermediate phase was found during heat treatment at and above 600 °C. The particle size obtained from TEM lay between 20 and 30 nm. Structural electron microscopy (SEM) revealed that the average grain size after sintering at 900 °C for 4 h ranges from 1.2 to 1.67 μm with a relative compact density of ≥90%. A comparative study on dielectric constant and corresponding tangent loss were carried out at 1 kHz, 100 kHz, 1 MHz, and 5 MHz from which the Curie temperature (T _c) was found to be at 935, 450, and 170 °C with peak dielectric constants at 930, 595, and 545, respectively, for CBN (CaBi₂Nb₂O₉), SBN (SrBi₂Nb₂O₉), and BBN (BaBi₂Nb₂O₉) measured at frequency 100 kHz with very low tangent loss.     

MgO,CaO,Y2O3掺杂ZrO2相组成的定量分析

以共沉淀法制备了掺杂８ｍｏｌ％ＭｇＯ，ＣａＯ，Ｙ２Ｏ３的ＺｒＯ２粉料，在１５５０℃烧结得到致密的稳定或稳定ＺｒＯ２试样，应用Ｘ射线步长扫描衍射数据和Ｒｉｅｔｖｅｌｄ方法对试样进行了相含量的定量分析，结果表明，相同组份不同金属氧化物稳定的ＺｒＯ２试样在烧结后得到不同的相组成，ＭｇＯ部分稳定ＺｒＯ２为立方、四方和单斜三相混合物（１７：５７：２６：ｗｔ％），ＣａＯ的部分稳定ＺｒＯ２仅包含立方和单斜相（６     

锂离子电池富锂正极材料xLi2MnO3·（1-x）LiMO2(M=Co,Fe,Ni1/2Mn1/2…)的研究进展

新一代固溶体富锂正极材料xLi2MnO3.(1-x)LiMO2(M=Co,Fe,Ni1/2Mn1/2…)具有高比容量、优秀的循环能力以及新的电化学充放电机制,可能被用做新型高比能量锂离子电池正极材料.本文介绍了富锂正极材料的结构、合成方法、电化学性能研究,探讨了影响其电化学性能的若干因素.并对其进行的各种改性研究进行了概述,分析总结了不同富锂正极材料所具有的特性和发展趋势.     

MgO-Al2O3-SiO2-TiO2-Y2O3玻璃的弹性模量

根据硬盘基板用材料的要求，制备了MgO-Al2O3-SiO2-TiO2-Y2O3高弹性模量玻璃（120GPa)，玻璃的弹性模量随组成的变化服从Makishima-Mackenzie理论，MgO,Al2O3,TiO2,Y2O3等具有较高单位体积离解能的氧化物有利于提高玻璃的弹性模量，但玻璃弹性模量的理论计算值低于测试值，这是因为Makishima-Mackenzie理论没有考虑玻璃内阳离子的具体配位，对MgO,Y2O3堆积密度因子的堆导存在误差，因此利用Makishima-Mackenzie理论发展高弹性模量玻璃时应对MgO,Y2O3等氧化物的计算进行修正。     

(Ca,Sr,Ba)3V2O8的制备和发光性能研究

采用微波辅助溶胶-凝胶法制备了自激发钒酸盐A3(VO4)2(A:Ca,Sr,Ba)。采用X射线衍射仪、傅里叶变换红外光谱仪、扫描电镜、透射电子显微镜、荧光谱仪对样品各项参数进行了表征,研究了A3(VO4)2的光致发光特性,探讨了不同制备工艺条件对其发光性质的影响。实验结果表明,Sr3V2O8样品发光强度随退火温度而变化,在680～900℃时,其发射光谱强度随温度上升而单调下降,达到1000℃时开始上升;pH值为4时,样品的发射光谱强度最大。     

低温燃烧法制备(W,Mo)C/Al2O3/La2O3复合粉末及性能

为了开发出一种无黏结相硬质合金来减少传统硬质合金中钴元素的应用,采用化学法制备(W,Mo)C/Al₂O₃/La₂O₃。以偏钨酸铵、钼酸铵、硝酸铝、硝酸镧、尿素和葡萄糖为原料,通过低温燃烧法探究硝酸盐和尿素、葡萄糖的不同配比,得出最优配比后还原炭化制备(W,Mo)C/Al₂O₃/La₂O₃粉末。在1500~1800℃经离子烧结制备(W,Mo)C/Al₂O₃/La₂O₃无黏结相材料,研究其力学性能并分析强韧化机制。结果表明:硝酸盐和尿素的最佳摩尔配比为1∶2,硝酸盐和葡萄糖的最佳摩尔配比为1∶0.5,加入葡萄糖后颗粒尺寸减小了0.28μm,比表面积提高了75.64%。致密度、维氏硬度和抗弯强度在1600℃时达到最大值分别为:98.45%,2202HV和1203 MPa,断裂韧度在1500℃时达到最大值为7.52 MPa·m^1/2。由于晶粒的细化及第二相颗粒的增韧的影响,(W,Mo)C/Al₂O₃/La₂O₃在1500~1600℃时以沿晶断裂和穿晶断裂为主;晶粒长大以及孔隙的出现导致(W,Mo)C/Al₂O₃/La₂O₃在1700~1800℃时以沿晶断裂为主。     

Er2O3掺杂Gd2(Zr0.8Ti0.2)2O7陶瓷的物理性能

用固相反应法制备(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇(摩尔分数x=0,0.2,0.4)陶瓷并测试其晶体结构、显微形貌和物理性能,研究了Er₂O₃掺杂的影响。结果表明,(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇陶瓷具有立方烧绿石结构,显微结构致密,在室温至1200℃高温相的稳定性良好;Er³⁺掺杂降低了陶瓷材料的热导率和平均热膨胀系数,当x=0.2时,其1000℃的热导率最低(为1.26 W·m^-1·k^-1)。同时,Er³⁺掺杂还提高了这种材料的硬度和断裂韧性。     

Rare earth titanates ceramics Na2La2Ti3O10: Pr3+ and RE2Ti2O7: Pr3+ (R?=?Gd, Y): sol–gel synthesis, characterization and luminescence

In this work, rare earth (La, Gd, Y) titanate ceramics have been synthesized with a sol–gel process of Ti(OC₄H₉)₄ precursor. It is found that these titanates of the three rare earth ions present two different typical phase composition and crystal structure in spite of the same reaction ratio of the precursors and synthesis conditions, which is taken in the formula Na₂La₂Ti₃O₁₀, and RE₂Ti₂O₇ (RE = Gd, Y), respectively. Besides, the microstructure (particle size and morphology) also show different features for different titanates by SEM. Subsequently, the optical properties (such as ultraviolet–visible diffuse reflectance absorption and photoluminescence) of these titanates activated with Pr³⁺ Na₂La₂Ti₃O₁₀: x mol % Pr³⁺ (x = 0, 0.2, 2, 5, 10, 15), and RE₂Ti₂O₇: x mol % Pr³⁺ (RE = Gd and Y) (both x = 0, 0.2) are compared to study. Especially Na₂La₂Ti₃O₁₀: Pr³⁺ is selected as an example to check that the concentration effect on the luminescence of Pr³⁺, revealing that Na₂La₂Ti₃O₁₀: 0.2 mol % Pr³⁺ possesses the strongest emission.     

Li2O/K2O物质的量比对P2O5-Al2O3-BaO-Li2O-K2O磷酸盐玻璃热光性能的影响

通过高温熔融法制备了不同Li_2O/K_2O物质的量比的磷酸盐玻璃,研究了其热学性能和热光性能。采用干涉仪法测试了玻璃的折射率温度系数dn/dT,并进一步计算获得了热光系数。结果表明:随着Li_2O/K_2O物质的量比的增大,玻璃的转变温度Tg、软化温度Tf、热膨胀系数α皆出现极值点,呈现明显的混合碱效应;而玻璃的热光系数dS/dT随着Li_2O含量增加而增大,当Li_2O/K_2O物质的量比为9∶6时,玻璃的dS/dT为0.08×10~(-6)/K;在磷酸盐体系中可获得具有零热畸变的光学玻璃。     

Single step synthesis of nanosized CeO2–MxOy mixed oxides (MxOy?=?SiO2, TiO2, ZrO2, and Al2O3) by microwave induced solution combustion synthesis: characterization and CO oxidation

Various CeO₂ –M _x O _y (M _x O _y  = SiO₂, TiO₂, ZrO₂, and Al₂O₃) mixed oxides were prepared by microwave induced solution combustion method and analyzed by different complimentary techniques, namely, X-ray diffraction (XRD), Raman spectroscopic (RS), UV–Vis diffuse reflectance spectroscopy (UV-DRS), X-ray photoelectron spectroscopy (XPS), thermogravimetry (TG-DTA), and BET surface area. XRD analyses revealed that CeO₂ –SiO₂ and CeO₂ –TiO₂ mixed oxides are in slightly amorphous form and exhibit only broad diffraction lines due to cubic fluorite structure of ceria. XRD lines due to the formation of cubic Ce_0.5Zr_0.5O₂ were observed in the case of CeO₂ –ZrO₂ sample. RS results suggested defective structure of the mixed oxides resulting in the formation of oxygen vacancies. The UV-DRS measurements provided valid information about Ce⁴⁺ ← O²⁻ and Ce³⁺ ← O²⁻ charge transfer transitions. XPS studies revealed the presence of cerium in both Ce³⁺ and Ce⁴⁺ oxidation states. The ceria–zirconia combination exhibited better oxygen storage capacity (OSC) and CO oxidation activity when compared to other samples. The significance of present synthesis method lays mostly on its simplicity, flexibility, and the easy control of different experimental factors.