NH4HF2氟化制备UF4工艺及热力学研究

采用自制氟化反应器,以NH₄HF₂为氟化剂,开展了不同反应温度、氟化剂过量比条件下NH₄HF₂氟化制备UF₄工艺研究,实验获得了反应温度、NH₄HF₂过量比对氟化效率的影响规律,采用化学分析结合X射线粉晶衍射法对反应产物进行鉴定。研究结果表明：温度为573、673、823 K时,氟化产物中UF₄含量随NH₄HF₂过量比的增加而逐渐增大,当温度为723、773 K时,氟化率随NH₄HF₂过量比的增加呈先增大后减小的趋势。温度为723 K、NH₄HF₂过量比为300%时,该反应氟化率最大,为92.53%。反应温度为573～823 K时,该氟化反应氟化产物中包括4NH₄F·UF₄、NH₄F·3UF₄、3...     

La2/3Ca1/3Mn1-xCrxO3（x=0.0，0.1）晶体结构的中子衍射研究

采用传统高温固相反应法合成钙钛矿型多晶样品。在室温下分别测量了La_2/3Ca_1/3Mn_1-xCr_xO₃(x=0.0,0.1)的中子粉末衍射谱,采用Rietveld峰形精修方法对衍射数据进行拟合,得到样品晶胞参数和原子坐标,根据原子坐标计算了与稀土锰氧化物宏观磁性能密切相关的锰氧键的键长和键角。     

模拟核素固化体ZrxCe1-xSiO4的制备和表征

为研究锆英石对放射性核素Pu(Ⅳ)的固化能力,选用Ce(Ⅳ)作为Pu(Ⅳ)的模拟替代物质,以ZrO₂、SiO₂和CeO₂粉体为原料,在1500 ℃条件下通过保温72 h进行Zr_xCe_1-xSiO₄（0≤x≤0.5）系列样品的制备。利用XRD对所获样品的物相和结构进行分析,并采用Rietveld结构精修方法对样品的晶胞参数进行精细化计算。结果表明：当0≤x≤0.05时,样品保持为锆英石相;当x>0.05时,有CeO₂物相出现。在锆英石相范围内,晶胞参数a、c、V与x之间符合线性关系。     

Fe-Al/Al2O3涂层表面氧化膜的掠入射X射线衍射研究

本文采用掠入射X射线衍射（GXRD）α-2θ扫描模式,进行了掠入射角α为0.1°～5°范围内Fe-Al/Al₂O₃阻氚涂层表面氧化膜的X射线衍射实验。结果表明,随α的增加,表面氧化膜中Al₂O₃相与Fe₃Al相对应的衍射峰强度绝对值增强;α的增加加深了分析区域的深度,引起Al₂O₃相的相对含量下降,导致Al₂O₃相对衍射峰强度降低。对Fe-Al/ Al₂O₃涂层表面氧化膜的掠入射X射线衍射而言,较佳的掠入射角是0.25°,此时对应Al₂O₃相的衍射峰相对强度最高。经比对PDF卡片,表面氧化膜相结构为暂态γ-Al₂O₃（200）。在此基础上建立了GXRD分析Fe-Al/ Al₂O₃涂层表面亚微米氧化膜的相结构组成的快速无损检测方法。     

基于二维X射线衍射技术的TiH2薄膜残余应力分析

氢化钛（TiH₂）的多数X射线衍射(XRD)峰与Mo的衍射峰峰位很接近,采用传统θ-2θ扫描X射线衍射方法很难获得Mo基底上TiH₂薄膜的较好的衍射峰形。本文采用XRD分析了Mo基底上TiH₂薄膜的残余应力,为获得足够的薄膜衍射信息,通过掠入射二维X射线衍射法消除了薄膜基底衍射信号对薄膜衍射峰的干扰影响。采用纳米压痕仪测得的TiH₂薄膜样品的弹性模量及TiH₂薄膜的（311）衍射晶面,利用掠入射二维X射线衍射法和侧倾法测定了TiH₂薄膜样品中不同深度范围的残余应力。测试结果表明,在TiH₂薄膜样品中,随着深度的增加,薄膜样品中的残余应力由张应力逐渐转变为压应力,且张应力和压应力均表现为呈椭圆形分布的正向应力。     

各向同性和各向异性BaFe_(12)O_(19)的磁性和穆斯堡尔效应的研究

样品采用工业生产的各向同性和各向异性BaFe_(12)O_(19)材料。先进行室温和77K的磁性研究。材料性能如下表所示。其中,σ_s(77K)为77K时的饱和磁矩,其余为室温数据。     

整体式除氚催化剂的制备及催化氧化性能

针对大型核设施产生的大流量废气的处理,发展低气阻的整体式催化剂尤为必要。本工作在整体式堇青石载体上生长分子筛涂层,以离子交换法负载活性组分Pt,获得的整体式催化剂具有高的金属分散度,达到了60%。使用该催化剂,在15 ℃、体积空速为10 000～40 000 h^-1、1.0%（体积分数）H₂的条件下实现大于99.9%的H₂转化率;在25 ℃、体积空速为50 000 h^-1 、1.0% H₂的条件下实现H2的完全转化。在更低的H₂浓度下（0.1% H₂和0.5% H₂）,该催化剂在湿条件下的H₂转化率低于干条件下的H₂转化率,表明水蒸气会抑制室温催化活性。由于分子筛涂层较Al₂O₃涂层具有更低的吸水性,整体式Pt/sil-cord催化剂在湿条件下具有比Pt/Al₂O₃高得多的室温催化活性（0.1% H₂下,转化率为80%,而在Pt/Al₂O₃ 上的转化率为13%）,表现出较好的抗湿性。     

硝酸体系中Tc(Ⅶ)与乙异羟肟酸的反应动力学研究

采用溶剂萃取法研究了HNO₃溶液中乙异羟肟酸（AHA）与Tc(Ⅶ)的相互作用。结果表明,有AHA存在时,Tc在30%TBP/煤油HNO₃体系中的分配比随反应时间下降,在实验条件下反应50 h后Tc在两相中的分配基本达到平衡,分配比D_Tc降至0.03,这表明Tc(Ⅶ)能被AHA还原为亲水性的低价Tc配合物［Tc^Ⅱ(NO)(AHA)₂H₂O］⁺;溶液吸收光谱显示,反应产物在428 nm（ε＝2 559 L·mol^-1·cm^-1）和565 nm处有吸收峰。通过溶剂萃取法得到Tc(Ⅶ)还原反应的表观反应速率方程式为r＝-dc(Tc(Ⅶ))/dt＝k′c(Tc(Ⅶ))c^1.6(AHA),在18 ℃下,c(AHA)＝1.0 mol/L,c(HNO₃)＝0.50 mol/L时半反应时间t_1/2＝16.5 h。进一步研究了溶液中有Pu(Ⅳ)存在时AHA与Tc(Ⅶ)的作用以及Tc分配比的变化。结果表明：Pu(Ⅳ)的存在会加快Tc(Ⅶ)转化为低价态亲水性配合物,而Pu的分配比在过程中基本不变。     

稀土氧化物Gd2O3、Nd2O3、Sm2O3和Dy2O3在KCl-LiCl-Li2O熔盐中的电解

采用循环伏安法和计时电位法研究了Li₂O在KCl-LiCl熔盐中的电化学行为,并利用卷积伏安法计算了923 K下O₂^-在KCl-LiCl熔盐中的扩散系数（D),得到D=0.5×10^-5 cm²/s。以Gd₂O₃、Nd₂O₃、Sm₂O₃和Dy₂O₃为阴极,在KCl-LiCl-Li₂O(w=1%)熔盐中进行电解（恒电压3.40 V、电解温度923 K、电解时间25 h）。通过X射线衍射分析(XRD),证实稀土氧化物被部分还原为金属,并分析了电解过程中可能发生的反应。同时利用PRS模型（该模型可将固态阴极内离子的极限扩散速率与固态氧化物孔隙P、金属/氧化物摩尔体积R、阴极还原后的体积收缩率S等参数关联）分析了这些稀土氧化物的电解还原模型,得到Gd₂O₃、Nd₂O₃、Sm₂O₃和Dy₂O₃的最优孔隙率分别为18.7%、24.2%、30.6%、16.7%,最短电解时间分别为133、157、143、119 h,将这些结果与电解实验结果进行对比,发现阴极的孔隙率和电解时间均不满足金属氧化物完全被还原的要求,并给出了相应的解释。     

溶解硫酸盐硫同位素测试预处理方法优化

为分析水体中硫酸盐硫同位素组成,常将SO^2-₄转化为固体BaSO₄,进行预处理,但是该方法对体积少且低浓度硫酸盐样品（0～20 mg·L^-1）存在耗时长、回收率低等问题,对硫同位素测试结果的影响仍不明确。本文通过对不同Ba²⁺添加量、反应温度、pH和沉淀时间等条件对SO^2-₄回收率及δ³⁴S BaSO₄测试影响进行研究,优化由SO^2-₄转化BaSO₄的方法,并选取四种不同类型水体（雨水、湖水、污水、海水）进行验证。结果表明：1） SO^2-₄的回收率受沉淀生成速率和反应时间控制,在相同反应时间内,沉淀生成速率与过饱和度比、温度成正比,与H⁺浓度成反比,并且搅拌可以加速BaSO₄晶体的生长;2） 改进的预处理流程为：在水样中添加适量盐酸和氯化钡（pH=2.6,过饱和度比≥55）,用玻璃棒匀速搅拌1 min,90 ℃水浴加热1 h,冷却至室温后用滤膜收集BaSO₄;3） 优化后的预处理方法测试天然样品时,SO^2-₄可以在1 h内完全转化为BaSO₄固体,并且不发生硫同位素分馏,低SO^2-₄浓度（3.24 mg·L^-1）的雨水样品,其转化率从0提高至98.7%,δ³⁴S约为15.7‰±0.1‰;中等SO^2-₄浓度（30.34 mg·L^-1）的湖水样品,其转化率从26%提高至100%,δ³⁴S为5.8‰±0.2‰;高SO^2-₄浓度（140.4～2 516.4 mg·L^-1）的污水和海水样品,硫酸盐的回收率和δ³⁴S与传统方法得到的结果相近。改进的预处理方法有效提高了低浓度水溶硫酸盐样品的回收率,避免转化过程中的同位素分馏。该方法对于中高浓度的样品同样适用。     

Neutron irradiation effects in uranium monosulfide

Uranium monosulfide (US) was irradiated to investigate the effects of fission damage. Post-irradiation examinations were done by measuring the electrical resistivity, and partly the magnetic properties, at low temperature. The lattice parameter and the electrical resistivity measured at room temperature just after the irradiations showed an increase starting at a fission dose of 1 × 10¹⁶ fissions/cm³ and attaining a maximum at 3 × 10¹⁶ fissions/cm³. After that, a saturation of both increases persiste until 3 × 10¹⁷ fissions/cm³. The low-temperature electrical resistivity in the magnetic ordered state (ferromagnetic transition, T_c, at about 180 K) increased remarkably, while decreasing drastically in the magnetization, with increasing fission dose, apparently corresponding to the lattice expansion. In addition, the Curie point (T_c) shifted to lower temperatures with accumulating fission damage.     

Thermal expansion studies on Inconel-600 by high temperature X-ray diffraction

The lattice thermal expansion characteristics of Inconel-600^® have been studied by high temperature X-ray diffraction (HT-XRD) technique in the temperature range 298-1200 K. Altogether four experimental runs were conducted on thin foils of about 75-100 μm thickness. The diffraction profiles have been accurately calibrated to offset the shift in 2θ values introduced by sample buckling at elevated temperatures. The corrected lattice parameter data have been used to estimate the instantaneous and mean linear thermal expansion coefficients as a function of temperature. The thermal expansion values estimated in the present study show a fair degree of agreement with other existing dilatometer based bulk thermal expansion estimates. The lattice parameter for this alloy at 300 K is found to be 0.3549(1) nm. The mean linear thermal expansivity is found to be 11.4 × 10⁻⁶ K⁻¹.     

Lattice thermal expansions of NpN, PuN and AmN

Lattice parameters of NpN, PuN and AmN were measured by a high temperature X-ray diffraction method from room temperature up to 1478 K. Linear thermal expansions of these TRU nitrides were determined as a function of temperature. The average coefficients of linear thermal expansion from 293 to 1273 K were 8.8, 11.1 and 11.2 × 10⁻⁶ K⁻¹ for NpN, PuN and AmN, respectively. The instantaneous coefficient of thermal expansion either at 293 or at 1273 K against the reciprocal decomposition temperature under 1 atm of nitrogen showed a linear relationship for TiN, ZrN, HfN, UN, NpN and PuN. Based on this relationship, the decomposition temperature of AmN was roughly predicted to be 2700 K.     

新型稀土永磁材料Nd_2Fe_(17-x-y)Nb_xAl_y的中子衍射分析及磁性能研究

通过X射线衍射、中子衍射及磁测量等研究了Nb、Al双取代对Nd2Fe17-x-yNbxAly化合物结构和磁性能的协同影响。X射线衍射结果表明,Nd2Fe17-x-yNbxAly的晶胞体积几乎随Al含量的增加而线性增加,当Al含量相同时,Nb的加入引起晶胞体积的增大。中子衍射分析结果表明,Nb优先占据6c晶位,Al优先占据18h晶位。磁测量结果表明,0.0≤y≤3.0时,单取代的Nd2Fe17-yAly化合物的居里温度随Al含量的增加先升高后降低,但双取代的Nd2Fe16.5-yNb0.5Aly化合物的居里温度却随Al含量的增加而线性升高,这表明Nb、Al双取代对磁性能的改善会产生协同效应。     

Thermal expansion characteristics of a titanium modified austenitic stainless steel: measurement by high-temperature X-ray diffraction and modelling using Grüneisen formalism

The thermal expansion of a titanium modified, swelling resistant austenitic stainless steel designated as D9 is studied by measuring the lattice parameter as a function of temperature in the range 300-1300 K by high-temperature X-ray diffraction technique. The thermal expansion data thus obtained is in reasonable agreement with the typical thermal expansion values reported for similar nuclear grade austenitic stainless steels. However, at temperatures exceeding 900 K, the measured thermal expansivity exhibits a pronounced non-linear increase due partly to the precipitation of complex carbide and intermetallic phases. The high-temperature thermal expansion data obtained in the present study are augmented by modelling the low-temperature thermal expansion behaviour by Grüneisen formalism.     

The elastic properties of lithium oxide and their variation with temperature

The energies of the acoustic phonon modes in a single crystal of ⁷Li₂O have been measured in the temperature range 293–1603 K using the technique of inelastic neutron scattering. The slopes of the phonon energy dispersion curves as they approach the Brillouin zone centre give values for the cubic elastic stiffness constants, C_ij. C₁₁ is found to undergo a sharp decrease above ˜ 1350 K similar to that observed in structurally related compounds, such as CaF₂ and SrCl₂, as they undergo a transition to a fast-ion phase. The Reuss and Voigt averaging methods have been used to calculate the temperature dependence of the adiabatic Young's modulus, shear modulus, bulk modulus and Poisson's ratio of polycrystalline Li₂O. Estimates of the corresponding isothermal values are obtained using an expression for the linear thermal expansion coefficient of Li₂O obtained in this work, together with thermodynamic data available from specific heat measurements. These results represent the first experimental data describing the elastic properties of Li₂O at elevated temperatures and are important in predicting the behaviour of this material in its potential role as a tritium breeding blanket material for future fusion reactors.     

Room temperature ferromagnetism of Co doped TiO2 using ion implantation and defect engineering

Ferromagnetic (FM) semiconductors obtained by doping ferromagnetic elements into a nonmagnetic semiconductor matrix are essential for the second generation of spintronics devices. In this study, we investigate Co doping behavior and subsequent magnetic properties in Co implanted and thermally annealed TiO₂. In TiO₂ single crystals, a decrease in the oxygen partial pressure during thermal annealing is found to enhance the Co substitutional fraction by increasing the concentration of oxygen vacancies. Magnetic properties determined from superconducting quantum interference device magnetometer (SQUID) measurements show that TiO₂ crystals with a large fraction of substitutional Co are ferromagnetic at room temperature. In addition to single crystals, the feasibility of Co doping via ion implantation is studied in sol–gel synthesized TiO₂ thin films. Results from grazing incidence X-ray diffraction (GIXRD) show that the implantation can produce Co doped TiO₂ thin films and that the Co incorporation into Ti lattice site accompanies the transition from rutile to anatase phase. These results show that ion beam synthesis is a useful tool for producing ferromagnetic TiO₂ with a high Curie temperature (T_C).     

含钆中子屏蔽材料的设计及其力学性能分析

设计了一种具有良好中子屏蔽能力、高强度及高韧性的新型中子屏蔽材料，用于吸收核电站乏燃料储存格架和乏燃料运输过程中的热中子辐射。材料通过蒙特卡罗粒子传输(输运）软件MCNP进行设计，并通过放电等离子烧结设备及热轧的方式制成了板材。MCNP模拟结果及材料热中子屏蔽测试结果表明：铝基Gd₂O₃复合材料的热中子屏蔽性能与铝基碳化硼相当。Gd₂O₃颗粒球磨后呈现μm、亚μm级甚至有些颗粒达到了nm级。随球磨时间的增加，材料的力学性能逐渐增强。X射线衍射检测发现了钆-铝合金相的生成。经TEM分析表明：材料的强化机制主要是位错强化和nm级Gd₂O₃颗粒的弥散强化，拉伸强度和伸长率分别达到了240 MPa和16%，其断口主要为韧性断裂。     

Thermal conductivity of neptunium dioxide

The thermal diffusivity of neptunium dioxide was measured in the temperature range from 473 to 1473 K by using a laser flash method. The thermal diffusivity slightly decreased with increasing temperature in the temperature range investigated. The heat capacity of NpO₂ was measured in the temperature range from 334 to 1071 K by using a drop calorimetry method. The heat capacity of NpO₂ determined in this study was slightly larger than that of UO₂ and about 7% smaller than that of PuO₂. The thermal conductivity of NpO₂ was determined from the thermal diffusivity, the heat capacity and the bulk density. It was found that the thermal conductivity of NpO₂ from 873 to 1473 K lay between those of UO₂ and PuO₂.