LaNi_(4.25)Al_(0.75)吸氕、氘、氚热力学同位素效应

采用自制的全金属氢化物吸放氢实验装置,恒温等容条件下测定LaNi_(4.25)Al_(0.75)材料吸氕、氘、氚单质气体的压力-组成等温线(P-C-T曲线),并根据Van’t Hoff(范特霍夫)方程得到LaNi_(4.25)Al_(0.75)吸氕、氘、氚形成氢化物相的热力学参数焓变ΔH分别为:-44.5、-45.0、-47.1kJ·mol-1,熵变ΔS分别为:-118.0、-121.8、-127.5J·mol~(-1)·K~(-1)。结果表明:LaNi_(4.25)Al_(0.75)材料吸收氕、氘、氚单质气体,在温度较低时,同位素效应不明显;温度高于100℃时,热力学同位素效应显著。相同温度、吸气容量条件下,吸气平衡压力从低到高依次是氕、氘和氚,其反应焓变和熵变从小到大依次是氚、氘和氕。结果表明,LaNiAl合金吸氢的热力学同位素效应依赖于温度的变化。     

铀吸、放氘/氚的热力学同位素效应

实验测定了铀吸收氘和氚单质气体的p-c-T曲线及解吸氘和氚气体的p-t曲线,获得了不同温度下吸气和解吸的平衡压,根据范德荷夫方程得到了铀吸收和解吸氘、氚的热力学参数ΔHΘ和ΔSΘ。数据显示,铀吸收氘和氚气体时,在相同温度相同原子比下,吸氘的平衡压比吸氚的平衡压低,解吸氘的平衡压也比解吸氚的平衡压低,且存在明显的滞后效应。从反应的焓变和熵变来看,铀吸、放氘/氚气体时存在较小的热力学同位素效应。     

钛吸氕氘混合气的同位素效应

本工作研究不同温度下钛吸收氕氘混合气体的特性，并计算其分离因子α。结果表明，在100～300℃温度范围内，ln α与温度T的倒数间存在线性关系ln α＝-0.13+107/T。在200 ℃下，当混合气中的氘浓度在10.0％～87.2％范围内变化时，钛吸收氕氘混合气的分离因子恒定不变。钛对氕氘混合气的吸收存在明显的同位素效应，钛更易于吸收氕气。     

氚老化对钯钇合金膜氢渗透性能的影响

在聚变堆燃料循环系统中,钯合金膜将被用于氢同位素与杂质气体间的渗透分离以及含氚杂质中氚的催化回收。长期连续的氚操作将使合金膜体内因氚衰变而累积3He,产生氚老化效应。本工作研究了贮氚老化对Pd8.5Y0.19Ru（原子百分数）合金膜的氕、氘渗透性能的影响。研究结果表明：对于膜内体氦浓度He/M为0.042的氚老化膜,在573～723K温度范围内,氕、氘渗透率被严重降低,膜的氕氘渗透分离系数则有所提高。     

氘氚燃料气体氕纯化系统设计及工艺初探

在惯性约束聚变氘氚冷冻靶制备中,对氘氚原料气中氕含量有严格限制。为控制少量燃料中氕含量,有必要开展相关氢同位素分离研究及工程研制。根据热循环吸附(Thermal Cycling Absorption Process,TCAP)原理及前期冷实验数据,研制了一套小型纯化热实验系统。系统内配置了一根长2 m、外径6.4 mm的钯/硅藻土填充柱用于对氕的过滤。按照纯化工艺设计,占总吸附量10%的原料气从填充柱一端输入,经过一次加热冷却循环后从柱另一端输出,氕在色谱柱内累积,进而实现原料气的纯化。经过纯化工艺初步探索,连续输入33次原料气后,柱内氕含量由12%累积到了52%,产品气中氕含量由12%降至3%,氘氚燃料回收率为82.5%,实现了柱内氕的有效富集,以及氘氚气体中氕的有效过滤。     

用氢同位素估算氚在熔盐堆结构材料中的渗透

熔盐堆产生的氚在高温下透过结构材料管壁进入大气环境。为降低此危害,研究氚在堆结构材料中的渗透过程十分必要。针对熔盐堆常用的结构材料Hastelloy N、GH3535、Hastelloy C230、Hastelloy C276,本研究采用压力差驱动法,在400-700 oC和5-40 k Pa的试验条件下,获得了氕、氘的渗透系数,并初步估算氚在该结构材料中的渗透。结果表明:氕、氘在镍基合金中的渗透通量与气体压力的平方根成正比,渗透系数随温度增大,与温度倒数的关系符合阿伦尼乌斯公式;氕、氘在成分相似的GH3535和Hastelloy N中渗透系数接近,与其它两种合金材料中渗透系数都在一个数量级内,在相同温度下两者渗透系数比值接近1.4,符合经典扩散理论;在400-700 oC内,氚在4种镍金合金中渗透过程的指前因子为1.1×10-7-1.6×10-7 mol·m-1·s-1·Pa-1/2,活化能为59-62 k J·mol-1。     

Ti-Mo合金氢化物放氢动力学同位素效应研究

在高真空金属系统中,采用非零初压热解析方法研究了钛钼合金TiMox（x=0.03, 0.13, 0.25, 0.50, 1.00, 原子比）氘化物的热解析动力学,测试了氘解析量c随时间t的变化关系,应用反应速率分析方法得到了热解析速率常数kd和热解析表观活化能Ed ,合金氘化物Ed依次为46.6, 22.4, 13.7, 17.1, 10.4kJ.mol-1。比较氕化物的热解析动力学行为,Mo含量小于0.03时,合金氕化物Ed小于氘合金化物Ed,与钛放氢动力学同位素效应保持一致。Mo含量在0.13 ~ 0.25时,氕化物Ed大于氘化物Ed,Mo含量大于0.50时,氕,氘化物Ed 差别不大。通过初始解析时合金中氕,氘含量的比较,结合室温下合金吸氕,氘量,对合金放氢动力学同位素效应的本质进行了探讨。     

序言

<正>“氚科学与技术“专栏氚(T)是氢的一种同位素,质量数为3,其核外电子结构与氕(H)和氘(D)相同,因而它们具有一些非常相似的物理、化学性质。在所有具有同位素的元素中,氢同位素之间的相对原子质量差异最大,因而其具有最为显著的同位素效应。氚具有β放射性,在衰变过程中发射低能β射线,生成³He,这使得氚在许多方面的性质与氕、氘相比又有很大差异。由于氚在未来聚变能源应用中发挥着不可或缺的重要作用,世界各国均非常重视氚科学技术的发展。     

热导检测技术在线分析氢同位素气体

以高纯氕作载气,对热导检测技术(TCD)在线分析氢同位素气体进行了实验研究,考察了进样压力、氘丰度以及样品中HD含量对测量结果的影响.实验结果表明,TCD对氘的响应与氘的压力呈良好的线性关系;对已知氘丰度为1%～90%的氕氘混合物样品进行了测定,测量结果的误差与氕氘混合气体中的HD丰度成正比,绝对误差范围在0.000～0.025.     

氚纯化装置的研制及性能验证研究

铀是一种传统的贮氚材料,在铀粉瓶中贮存的氚会不断衰变产生氦气,导致使用时氚的纯度下降,影响标记化合物产率。本研究设计了氚纯化装置,对装置进行安装调试,并对该装置中的铀床进行活化,利用该装置测定铀吸收氘单质气体的p-t曲线及在400~550 ℃范围的解吸氘气体的p-t曲线。应用调试好的系统对长期存放贮氚铀粉瓶中的氚进行纯化。结果表明,设计的氚纯化装置系统密封性好,经氦质谱检漏测定值为7.8×10^-13 Pa•m³/s;利用该装置测定氘的吸附饱和曲线,氘完全解吸时铀对氘的吸附量为240 mL/g。验证实验回收了久置铀粉瓶中的氚为1.44×10¹³ Bq,利用氦气体积推算出久置铀粉瓶中含氚质量百分率为53.1%。实验结果证实了系统纯化氚的可行性,可为氚标记化合物制备提供可靠的氚源。     

Investigation of fusion reactions in palladium and titanium tritide using galvanostatic,coulometric, and hydrogen permeation techniques

We describe several electrochemical methods used to investigate the possibility of cold fusion phenomena in palladium and titanium tritide cathodes. We performed long-term (up to 77 days) electrolysis experiments with electrochemical cells of the University of Utah type at current densities as high as 1 A/cm², while monitoring neutron and tritium levels. With some cells, we pulsed the current to determine if neutron bursts would result. In another cell, we used titanium tritide as the cathode to determine if D-T reactions yielding neutrons would occur. In no instance were levels of neutrons or tritium significantly above background except in the titanium tritide cell where isotopic exchange, occcurring between the electrode and the electrolyte, resulted in significant tritium levels. We also combined x-ray photoelectron spectroscopy (XPS) and electrochemical hydrogen permeation experiments to determine the effectiveness of various Pd surface treatment procedures on the resultant electrochemical hydrogen absorption efficiency. Electroanalytical and thermal desorption/gas analysis techniques indicated the maximum loading of H in Pd was to a ratio of HPd=0.8.     

Isotopic Effects of Hydrogen During the Decomposition of Water in Electrolysis with a Solid Polymer Electrolyte

The partition coefficients of hydrogen isotopes in the decomposition of water in electrolyzers with a solid polymer electrolyte are measured in a wide range of deuterium content in the initial water (from the natural content up to close to 100%), including for water containing trace concentrations of tritium. Equations describing the temperature dependence of the partition coefficients (temperature range 298–333 K) and the deuterium content dependence of the tritium partition coefficient are obtained. Partition coefficients are presented for binary isotopic mixtures protium–deuterium, protium–tritium, deuterium–tritium. 1 figure, 3 tables, 17 references.     

铒二氢化物的氘、氚热力学同位素效应

在真空系统中对金属铒的氘活化特性进行了测试,测定了铒与氘、氚反应生成二氢化物及其可逆反应的压强-组成-温度（PCT）曲线。结果显示,铒的氘、氚化物α+β相平台区较宽且十分平坦,其二氘化物和二氚化物分解反应均未见明显滞后效应。基于PCT曲线获得了H/Er原子比在0.6～1.6区间的标准焓（ΔH°）和标准熵（ΔS°）,其数值均随H/Er比的增大而减小,相同原子比下氚化物的ΔH°和ΔS°较氘化物的小,具有轻微的同位素效应。其中,ErD₁的ΔH°和ΔS°分别为（-199.7±7.3）kJ/mol和（-143.4±7.2） J/(mol•K),ErT₁的ΔH°和ΔS°分别为（-209.3±3.3） kJ/mol和（-152.9±3.2）J/(mol•K)。     

Depth profiles of deuterium in titanium from gas emission during sputtering

A simple technique for the determination of the depth distributions of deuterium and tritium in the near-surface region (0–1 μm) of materials has been demonstrated. In particular, the depth distribution of deuterium in a layered, deuterided titanium film has been determined by monitoring the HD and D₂ gas emissions during sputtering by 2 keV argon ions. For the nonoptimized conditions employed the detection sensitivity was $\text{D/Ti}\text{\$}\text{?}\text{0.02}$ and the fractional depth resolution was ~0.24 (i.e., ~240Å for a 1000Å film). Even for these conditions, this technique has a near-surface depth resolution superior, or equal, to that of other techniques for profiling hydrogen and a more than adequate sensitivity for the detection of deuterium and tritium in CTR-related studies, hydride studies and studies of tritided targets for neutron production.     

Spectroscopic quantitative analysis of the isotopic composition of gas mixtures containing hydrogen, deuterium, and tritium

A detailed experiment is carried through to construct a calibrating curve in the concentration interval from 0.7 to 97% H₂ in D₂. The results obtained are in good agreement with theory. It is shown that it is possible to perform an isotopic analysis of tritium in mixtures with hydrogen and deuterium. An investigation is performed of the relative intensity of the isotope lines as a function of the pressure in a discharge tube.     

Spectroscopic quantitative analysis of the isotopic composition of gas mixtures containing hydrogen,deuterium, and tritium

A detailed experiment is carried through to construct a calibrating curve in the concentration interval from 0.7 to 97% H₂ in D₂. The results obtained are in good agreement with theory. It is shown that it is possible to perform an isotopic analysis of tritium in mixtures with hydrogen and deuterium. An investigation is performed of the relative intensity of the isotope lines as a function of the pressure in a discharge tube.     

Fuel hydrogen retention of tungsten and the reduction by inert gas glow discharges

Polycrystalline tungsten was exposed to deuterium glow discharge followed by He, Ne or Ar glow discharge. The amount of retained deuterium in the tungsten was measured using residual gas analysis. The amount of desorbed deuterium during the inert gas glow discharge was also measured. The amount of retained deuterium was 2–3 times larger compared with a case of stainless steel. The ratios of desorbed amount of deuterium by He, Ne and Ar glow discharges were 4.6, 3.1 and 2.9%, respectively. These values were one order of magnitude smaller compared with the case of stainless steel. The inert gas glow discharge is not suitable to reduce the fuel hydrogen retention for tungsten walls. However, the wall baking with a temperature higher than 700 K is suitable to reduce the fuel hydrogen retention. It is also shown that the use of deuterium glow discharge is effective to reduce the in-vessel tritium inventory in fusion reactors through the hydrogen isotope exchange.     

LaNi_(4.7)Al_(0.3)合金贮氘氚后的老化效应

将氘氚装载到LaNi4.7Al0.3合金样品中并在室温下贮存480d或1120d，发现LaNi4.7Al0.3合金贮合金几乎能保留所有的衰变子体氦－3。通过氘氚化物的解吸等温线，观察到该合金存在显著的氚老化效应；坪压降低，坪斜增加，可逆容量减少及被称为“渣”（heel）的深捕陷氢同位素形成。实验还发现623K下除气可以部分消除这些老化效应。     

Tritium permeation experiments using reduced activation ferritic/martensitic steel tube and erbium oxide coating

Low concentration tritium permeation experiments have been performed on uncoated F82H and Er₂O₃-coated tubular samples in the framework of the Japan-US TITAN collaborative program. Tritium permeability of the uncoated sample with 1.2 ppm tritium showed one order of magnitude lower than that with 100% deuterium. The permeability of the sample with 40 ppm tritium was more than twice higher than that of 1.2 ppm, indicating a surface contribution at the lower tritium concentration. The Er₂O₃-coated sample showed two orders of magnitude lower permeability than the uncoated sample, and lower permeability than that of the coated plate sample with 100% deuterium. It was also indicated that the memory effect of ion chambers in the primary and secondary circuits was caused by absorption of tritiated water vapor that was generated by isotope exchange reactions between tritium and surface water on the coating.