LaNi5和LaNi4.7Al0.3氢化物柱内氢氘间的排代

进行了室温附近LaNi5和LaNi4.7Al0.3两种材料上气-固 间氢氘的排代实验。两种材料的排代效果都较好,相比之下,LaNi5的更优。可以推测, 在不要求得到高纯氚的情况下,都可以用作氚的冷卸载贮存床。初步的理论探讨揭示,气- 固界面的化学交换反应是产生排代效应的原因,宏观交换规律决定排代效果。理想化的塔板 理论模型对排代流出曲线的描述是有效和适用的,塔板高度是材料排代性能优劣的指标,在 确定的排代条件下,如果塔板高度小于1.0 cm,应该认为具有较好的排代效果。     

锆钴氢化物中氢氚的互排代研究

研究了一维排代条件下,ＺｒＣｏ－Ｈ体系上气－固间氢氚的互相排代特性,实验结果表明,氢氚间可以互相排代,影响排代效果的主要因素有：固相表面积、温度和气相流速。在粉化较好的ＺｒＣｏ颗粒（≥４８目）和较高的温度下（～８５℃）,气相流速提高到１．３ＮＬ／ｃｍ＾２ｍｉｎ还具有较理想的排代效果。氚丰度的流出曲线可以用塔板理论描述,且具有较小的塔板高度。     

锆钴氢化物中氢氘的互排代研究

研究了一维排代条件下,ZrCo-H体系上气固间氢氘的互相排代特性。实验结果表明,氢氘间可以互相排代,影响排代效果的主要因素有:固相表面积、温度和气相流速。在粉化较好的ZrCo颗粒(≥48目)和较高的温度下(～85℃),气相流速提高到1.3NL/cm2min还具有较理想的排代效果。氘丰度的流出曲线可以用塔板理论描述,且具有较小的塔板高度     

铝含量对LaNi_(5-x)Al_x 合金氘化与去氘化热力学函数的影响

测定了LaNi5-xAlx(x =0 .0、0 .1、0 .2、0 .3)的氘化与去氘化热力学参数 ,评价了LaNi5-xAlx 中铝含量对氘化与去氘化热力学函数的影响。研究结果表明 ,合金的坪台压力和吸氘容量随x的增加而降低 ;坪率随x的增加而增加 ;热力学焓变与熵变随x的增加而减少 ;滞后系数Hf 随x的增加而减少。     

氚老化对LaNi_(4.9)Al_(0.1)的动力学性能的影响

测定了不同材龄的LaNi4 .9Al0 .1氘化与去氘化动力学参数 ,评价了氚老化对LaNi4 .9Al0 .1动力学性能的影响。研究结果表明 ,氚老化不改变合金的氘化与去氘化的反应级数 ;反应速率随老化时间的增加而降低 ;活化能随老化时间的增加而增加     

Al2O3X(X=H,D,T)的电子振动近似理论方法研究

用密度泛函理论(DFT)方法在6-311 G(d,p)水平上对Al2O3X(X=H,D,T)分子较低能量的几何构型进行了优化.计算结果表明该分子有两个可能基态,即Al2O3X(X=H,D,T)(2A′)Cs和Al2O3X(X=H,D,T)(2B2)C2v.全电子计算了氢同位素分子及Al2O3X(X=H,D,T)的能量E、定容热容CV和熵S.应用电子振动近似理论,即用单个分子Al2O3X(X=H,D,T)中的电子和振动能量和熵近似代表它们处于固态时的能量和熵,计算得到固体Al2O3的氢化热力学函数ΔH0,ΔS0,ΔG0以及平衡压力与温度的关系.当Al2O3吸附氢(氘,氚)形成C2v对称性气态Al2O3X(X=H,D,T)对应的固体时,氢气可以排代氘气,氘气可以排代氚气.这种排代效应非常不明显;形成Cs对称性气态Al2O3X(X=H,D,T)对应的固体时,反应的氢氘氚排代效应的顺序为氚排代氘,氘排代氢,与钛等的氢氘氚排代效应的顺序相反.总体而言,这种排代效应都非常弱.随着温度的增加,这一系列反应的氢氘氚排代效应趋于消失.     

聚变堆氚系统设计中的一些重要问题研究(Ⅱ)

在文献[1]中,计算了FEB-E聚变堆PFC材料内的氚滞留量、堆系统总的氚投料量、启动运行开始阶段的氚坑深度和氚坑时间大小.这里将讨论在ITER的TBM氚增殖包层内固体氚增殖剂中的氚如何高效率地被载氚气体带出并且以高效率地提取回收.本部分将进行创新的探索性研究并且提出某些减少氚滞留量和改善氚提取回收效率的新方案,例如:基于氘饱和的海绵效应;第一壁表面建立氘和铍的伴同沉积层;基于在低频外电场作用下载氚气分子和硅酸锂颗粒电极化旋转催化同位素交换速率的增强载氚气提取氚效率“SPB方法”.     

LaNi5氚老化效应的实验研究

测定了老化LaNi5料的解吸等温线及去氘化热力学参数.评价了氚老化对LaNi5贮氢性能的影响.结果表明,氚老化使LaNi5解吸等温线形貌发生重大改变.与新鲜材料相比,老化2140天后,在373 K下,坪台压力降低了约50%,坪斜由0.033到0.130,可逆吸氢容量减少了约1.3 mmol.g-1.老化LaNi5料去氘化反应热力学焓变ΔH和熵变ΔS分别由30.1 kJ.mol-1和105 J.mol-1.K-1增加到44.5 kJ.mol-1和128 J.mol-1.K-1.     

钛（锆、铀）-氢体系氢同位素效应

钛和锆是两种性能优良的贮氢材料，在氚工艺中常作为膜材料贮存氚气或氘氚混合气，而铀通常作为氘氚原料气的气源材料使用，因此，这几种金属材料与氢作用时的同位素效应对产品性能将有很大的影响，有必要进行深入研究。     

A12O3X2（X=H，D，T）的电子振动近似方法

用密度泛函理论在B3LYP／6．311＋＋g（d,P）基组水平上对A12O3X2（X=H,D,T）分子的可能较低能量构型进行了几何优化．结果表明该分子的基态电子态和对称性为A12O3X2（X=H,D,T）（1A’）G,计算了氢同位素分子及A12O3X2（X=H,D,T）的电子能量E、定容热容Cv和熵S．用电子振动近似方法计算了固体A12O3的氢化热力学函数△H0,△S0,△G0,以及平衡压力与温度的关系．当A1203吸附氢（氘,氚）形成固体时,反应的氢氘氚排代效应的顺序为氚排代氘,氘排代氢,与钛等金属与氢及其同位素反应的氢氘氚排代效应的顺序相反．总体来说,这种排代效应都非常弱．随着温度的增加,这系列反应的氢氘氚排代效应趋于消失．     

Theoretical study of aging effects on LaNi_5 tritium storage

1 Introduction LaNi5 intermetallic compounds, used in storage, separation and purification of hydro- gen and hydrogen isotopes, are known for a high-density storage, easy activation, low pressure, and rapid and reversible absorption and desorption[1-15]. Tritium as an impor- tant material in the nuclear industry is radioactively decaying into 3He with a half-life of 12.3 years. With time, there are many changes in the electronic and physical properties of the tritide for the deposition of 3He…     

活化LaNi5衍射峰各向异性应力展宽模型在LHPM程序中的实现

在活化LaNi5的粉末衍射轮廓中会出现较明显的各向异性展宽现象,这给衍射数据的Rietveld分析带来相当的难度.Rodriguez-Carvajal提出了一个唯像模型,只需精修少量的参数就能对于各向异性展宽的衍射峰获得较好的拟合.基于这个模型的原理,本文描述了活化laNi5衍射峰各向异性应力展宽模型在LHPM 6.5中的实现过程,并将所得结果与FullProf 2000的结果进行了比较.     

锂铅合金释氚实验研究

由于锂铅合金因具有高增殖比、低活泼性和可能作为冷却剂的特点,被认为是最有潜力的能源堆包层氚增殖材料。在理论模型描述熔融锂铅合金氚释放行为的基础上,开展了中子辐照后Li₁₇Pb₈₃合金的离线氚释放实验。结果表明: 释放氚的化学形式99％以上为难溶于水的成分（HT或T2）; 氚滞留时间随载气中氢分压的增加而减小,氢分压达到1000 Pa后变为常数,且与实体积无关;氚释放速率对温度的依赖性符合Arrhenius定律。以此为基础得到的氚在熔融锂铅中的动力学参数结果,虽与文献值有差异,但同样证明了在633—973 K的范围内, 氚从液态锂铅到气相的整个释放过程中起决定作用的是氚在合金内的扩散和气\|液界面的多相反应重组。Lithium\|lead alloy is considered to be one of the most prominent tritium breeding materials for the fusion reactor blanket because of its high breeding ratio, and low reactivity and possible use as coolant. An out\|of\|pile experiment of tritium release from Li₁₇Pb₈₃ alloy was performed after neutron irradiation on the base of mathematical model to describe tritium release behavior from an eutectic lithium\|lead alloy. The results suggest that the dominant chemical form of the released tritium (>99%) was the water\| insoluble component (HT or T2). Tritium residence time decreased with increasing H₂pressure in carrier gas up to 1000 Pa, and above this concentration limit it became constant and not influenced by the plenum volume. The temperature dependence of the tritium release rate can be described by an Arrhenius law. Consequently, the present results on the kinetic parameters of tritium in molten Li₁₇Pb₈₃alloy are considered to be different from the values in literature, but it is the same that the overall release process is governed by the diffusion of tritium atoms in the Li₁₇Pb₈₃and by the heterogeneous reaction at the gas\|eutectic interface of the tritium atom recombination at temperatures from 633 to 973 K.     

Pressure-dependent EXAFS mean-square relative displacements of germanium and silicon crystals

In this paper, the statistical moment method (SMM) has been developed to study the pressure dependence of thermodynamic quantities of germanium and silicon crystals. We have derived the analytical expressions of the pressure-dependent parallel mean-square relative displacement (MSRD) or extended X-ray absorption fine structure (EXAFS) Debye–Waller factor, mean-square displacement (MSD) as well as lattice constant and volume change of diamond-type crystals. Numerical calculations performed for these semiconductors up to 11 GPa are found to be in good and reasonable agreement with available experimental data as well as with previous theoretical studies. Our results indicate that the SMM can be efficiently used for determining the relative change of the pressure-dependent MSRDs of germanium and silicon semiconductors. The research also shows the advantage of SMM on studying other thermodynamic properties of materials under high pressures.     

一般边界条件下球形压力容器钢壁中氚和氦-3的浓度变化规律研究

为了认识储氚高压容器壁材料的力学性能变化及其导致的容器承载能力变化, 必须研究储氚期间, 容器壁中氚和氦-3浓度的空间分布和随时间的变化. 针对容器外表面为一般传质边界条件和容器内部氚为范德瓦尔斯气体的情况, 同时考虑容器腔内和容器壁中氚的衰变和扩散, 建立求解储氚高压容器壁中氚和氦-3浓度的解析理论模型, 导出了氚和氦-3浓度的理论公式. 通过解析计算给出了器壁中氚和氦-3浓度随外表面传质系数的变化曲线和浓度的时空变化曲线, 提出了氦-3浓度的2β ₁ + β ₂ / 2倍定律, 即处于开放空间的储氚球形高压容器, 器壁中氦-3的浓度呈内高外低的分布, 时间越长, 浓度沿径向的梯度越大, 在时间足够长时, 各处浓度逼近时间无限长时的最终值, 也就是各处的最大值, 内表面处的最大值是该处氚初始时刻浓度的2β ₁ + β ₂ / 2倍, 这里β ₁ 和β ₂ 为与氚的范德瓦尔斯常数相关的参数. 研究结果为储氚高压容器的强度安全性评估提供了前提.     

Pressure effects on EXAFS Debye-Waller factor and melting curve of solid krypton

The pressure effects on atomic mean-square displacement, extended X-ray absorption fine structure (EXAFS) Debye-Waller factor and melting temperature of solid krypton have been investigated in within the statistical moment method scheme in quantum statistical mechanics. By assuming the interaction between atoms can be described by Buckingham potential, we performed the numerical calculations for krypton up to pressure 120?GPa. Our calculations show that the atomic mean-square displacement and EXAFS Debye-Waller factor of krypton crystal depend strongly on pressure. They make the robust reduction of the EXAFS peak height. Our results are in good and reasonable agreements with available experimental data. This approach gives us a relatively simple method for qualitatively calculating high-pressure thermo-physical properties of materials. Moreover, it can be used to verify future high-pressure experimental and theoretical works.     

Pd-Ag膜电解浓缩氚的动力学模型及理论计算

建立了模拟Pd-Ag合金膜电解浓缩氚的过程和诸多电解参数的动力学模型。采用求解数学扩散方程的方法得到理论值，并与文献报道的实验数据进行比较。计算结果表明：氚在Pd-Ag膜上的吸附、解吸、浓缩等行为受到诸多条件的制约。在保证密封性能的前提下，对Pd-Ag膜电解槽体的要求是至少应包括有含氚水路循环、阳极气体消除和阴极扩散后氚再生3个组成部分，采取相匹配的级联技术可以提高分离效果；对电解参数的要求是采取尽可能高的电解液温度和稳定的OH-浓度，合适的电流密度，合理的膜厚度、表面特征和Pd黑结合紧密。     

Z箍缩驱动聚变-裂变混合堆氚燃料循环系统氚盘存量与氚自持初步分析

为研究氚自持条件，建立了Z-FFR氚分析模型，基于理论方程和氚平均滞留时间方法进行计算，得到稳态运行时排灰气处理系统、氚增殖提取系统、同位素分离系统、水去氚化系统的氚质量流分别为52.30，25.40，81.30，3.60 g/day，对应的氚盘存量为52.30，25.40，8.13，1.80 g。同时以氚质量流推导出氚自持判断条件，分析了设计参数能够满足氚自持要求，同时获得了燃烧效率、氚增殖率、提取效率与氚自持的互补关系，三者作为关键参数相互依存，于临界值、设计值、理想值之间分析了氚的自持情况。     

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In part one published in the last issue, the tritium retention and the total tritium inventory in PFC materials of FEB-E fusion reactor had been calculated. The tritium well depth, tritium well time during the FEB-E fusion reactor start-up and initial operation phase had been obtained. In this part, how to improve tritium recovery efficiency in the ITER TBM solid breeder blanket with using purge gas has been discussed. Some new innovative schemes for reducing tritium retention and improving tritium recovery efficiency are proposed. Such as, sponge mechanism based on deuterium saturated PFC materials; deuterium and beryllium co-deposition layer created on first wall surface; SPB scheme for enhancing tritium recovery efficiency of purge gas in ceramic breeder blanket based on the electrical polarization rotations catalyzing isotope exchange rate enhancement resulted from applied low frequency electric-field, of Li4SiO4 grain and purge gas molecular particles and so on, are explored.