氘在Incoloy800H合金材料中的扩散渗透行为

采用气相渗透技术研究了氘在Incoloy800H合金材料中的扩散渗透行为,利用高温气相渗透实验装置和四极质谱仪测定了450～600 ℃温度范围内、氘压110 kPa下氘的渗透实验曲线,计算得到了氘在Incoloy800H合金材料中的渗透率和扩散系数。结果表明,渗透扩散过程为扩散控制,得到的渗透率、扩散系数与温度的关系式均符合Arrhenius关系。     

First-principles energy and vibration spectrum simulations of Cr/V interacting with H in W-based alloy in a fusion reactor

We perform first-principles total energy and vibration spectrum calculations to study the effect of Cr/V on the H formation and diffusion at temperature range 300–2100 K in dilute W–Cr/W–V alloy. Temperature and H chemical potential are two important factors to affect the H formation energy and migrating energy. The H formation energy referring to the static/temperature-dependent H chemical potential decreases/increases with the temperature. At each given temperature, the presence of Cr in W reduces the H formation energy, while the existence of V in W has little effect on the H formation energy. The diffusion energy barrier and pre-exponential factor strongly depend on the temperature and increase with the temperature from 300 to 2100 K. Both Cr and V additions in W has a large consequences on H migrating energy. The energy barriers at any given temperature can be reduced by ～0.05 and 0.10 eV in W–Cr and W–V alloys, respectively. The current study reveals that vibration free energy plays a decisive role in the formation energy and migrating energy of H with the temperature, while the thermal expansion energy has little influence on the H formation energy and migrating energy with the temperature.     

Analysis of diffusion and dissolution of two-component hydrogen (H + D) in lead lithium

A lead–lithium eutectic alloy (Pb–Li) is one of the most promising candidate materials for the liquid blanket of an advanced fusion reactor. We have experimentally determined mass-transfer properties by an unsteady permeation method, which data are necessary to design a system to recover tritium (T) from a Pb–Li blanket. An experiment of simultaneous H and D permeation through Li₁₇Pb₈₃ is performed to clarify interactions between atoms in the two-component permeation process. The experimental results are analyzed by a model of one-dimensional or two-dimensional permeation through Li₁₇Pb₈₃. The major permeation proceeds in the longitudinal direction of the present system, and the ratio of hydrogen leak in the radial direction is evaluated using the simulation. As a result, it was found that H and D atoms permeate independently regardless of the H/D component ratio within the present experimental conditions. The permeability and diffusivity of H are 1.4 times higher than that of D. The solubility of H is close to that of D. The isotope effect in diffusivity is in proportion to the square root of the mass ratio of D to H. When these data can be extended to the case of T, T permeability and diffusivity is predicted as 1/1.7 times lower than that of H in the temperature range from 773 K to 973 K.     

Effect of surface oxide layer on deuterium permeation behaviors through a type 316 stainless steel

Effect of surface oxide layer on the hydrogen isotope permeation was studied. Iron oxide was uniformly formed in the oxide layer, although chromium was limited at the interface between the oxide layer and bulk SS-316. The permeation behavior of deuterium for oxidized SS-316 was compared with that for unoxidized SS-316 at temperature range of 333–673 K. The deuterium permeability for the oxidized SS-316 was reduced 1/10–1/20 times as high as that for unoxidized one. However, the activation energy of deuterium permeation as gas form for oxidized SS-316 was almost the same as that for unoxidized SS-316 and was 0.64 eV, which was almost consistent with the sum of activation energies for diffusion and solubility. This fact indicates that the deuterium permeation is diffusion limited. The permeability of deuterium as water form was almost constant even if heating temperature is high, showing that the deuterium was permeated through bulk SS-316 and react with oxygen at the oxide layer as water desorption, which is controlled by the permeation flux of deuterium and oxygen concentration on the surface of oxide layer in downstream side.     

CLAM钢中氕氘的渗透与去除

低活化铁素体/马氏体钢（RAFM钢）是聚变堆产氚包层的优选结构材料。氢同位素在结构材料中的扩散渗透特性关系到产氚回收率、燃料循环及运行安全。本工作对国内研发RAFM钢之一的CLAM钢进行了气体驱动的氘渗透实验，得到573～873 K温度范围内氘的宏观溶解度S（mol/(m³•Pa^0.5)）为0.264exp(-22 447/RT)，扩散系数D（m²/s）为1.38×10^-7exp(-17 271/RT)，渗透率Φ（mol/(m•s•Pa^0.5)）为3.64×10^-8exp(-39 718/RT)。还进行了氕氘气体混合物的渗透实验，确认了渗透同位素效应；探索了钢中溶解氘的真空热释放去除。     

PdY合金管束的氢渗透性能

PdY合金膜因其具有良好的透氢性能与机械性能,有望应用于聚变堆氢同位素纯化工艺。基于PdY合金膜的服役参数及氚安全要求,有必要研究在低氢压下PdY合金膜的氢同位素渗透特性,为后续设计氢同位素纯化组件提供数据支撑。本工作基于直管外压式PdY扩散器,研究了低氢压（<50 kPa）、工作温度为350~450 ℃条件下,厚度为80 μm的PdY合金薄膜管的氢渗透速率与膜两侧压力、工作温度的关系。结果表明,低氢压下,PdY合金膜的氢渗透规律符合J=Φpⁿ_H-pⁿ_Ld,且压力指数n等于0.9,渗透速率控制机制主要表现为表面过程控速;提高工作温度使得合金膜的渗透通量增大,且温度对扩散过程的影响更大,使渗透过程更加趋于表面控速。此外,计算了该工作温度范围下的渗透系数,并通过阿伦尼乌斯公式推导求得渗透活化能约为24.54 kJ/mol,渗透常数Φ₀为5.86×10^-6 mol/(m·s·kPa^0.9)。低氢压下,该厚度膜的渗透系数可由5.86×10^-6e^-24.54/^(RT) mol/(m·s·kPa^0.9)进行计算。     

氚在一些弹性材料和聚合材料中渗透率的测量

在制造氚容器、氚操作系统(如手套箱)的材料中,弹性材料和聚合材料是十分重要,而且几乎是不可缺少的材料。例如,各种橡胶、塑料和密封用的粘接材料都广泛应用于制造手套、垫圈、维修用帐篷以及氚防护服等。氚在这些材料中的渗透率一般都比在金属中     

氚在RAFM钢中的渗透

采用气相渗透方法，开展了国产低活化铁素体/马氏体钢（RAFM钢?）之一的CLAM钢的氚渗透实验，研究了影响渗透的关键因素，建立了可靠的实验方法。在573~823?K温度范围内，得出氚的渗透率F_T为2.57×10-8exp(-38639/RT)，氚溶解度S_T为2.2×10-1exp(-38639/RT)，扩散系数D_T?为1.17×10-7exp(-22011/RT)。另外，氘氚混合渗透时存在明显的正同位素效应，在实验温度范围内，推导得出的氘氚渗透分离系数α_DT为1.42，氕氚渗透分离系数α_HT为3.76。      

Mo含量对Ti-Mo合金氢同位素效应的影响

采用磁悬浮熔炼法制备了固溶体合金TiMox（x=0．03、0．13、0．25、0．50、1．00，x为Mo与Ti原子数之比），经活化后与H—D混合气（D原子占50％）反应，反应平衡后用质谱分析气相中H和D的含量。根据反应前气相中H和D的含量，由质量守恒定律求得固相中H和D的含量。根据气、固两相中的氕氘原子数之比（D／H），由公式α（H-D]=（ED3／[H]）（目目）／（ED3／[H]）（气相）计算得到H-D分离因子α（H-D）。结果表明：20℃下，x0．03～1．00时，α（H-D）〉1．00，合金氢化物表现为正同位素效应。随着Mo含量的增加，α（H—D）由1．04增加到1．27；x〉0．50时，α（H-D）基本保持不变。2／7—0．03时α（H-D）≈1．00，合金表现为零同位素效应。根据以前热分析实验结果，TiMo0.03吸氢后析出大量负同位素效应的TiH2，并有少量正同位素效应的Ti—Mo合金氢化物，零同位素效应是两者共同作用的结果。根据Mo含量和分离因子的关系，室温下H原子倾向于占据4Ti四面体间隙位置，而D原子倾向于占据能量较高的3TilMo四面体间隙位置。     

Transport of hydrogen and deuterium in the reduced activation martensitic steel ARAA

Advanced reduced activation alloy (ARAA) is a reduced activation ferritic/martensitic (RAFM) steel under development at the Korea Atomic Energy Research Institute. The transport of hydrogen and deuterium in ARAA was investigated in an elevated temperature range of 250–600 °C. A continuous-flow method, a time-dependent gas-phase technique, was used for the measurements. Complete sets of transport parameters (permeability, diffusivity, solubility, trap site density, and trapping energy) of hydrogen and deuterium in ARAA were successfully obtained. We show that appreciable trapping effects are observed only at low temperatures (250–350 °C) and that the isotope effect ratio for the diffusivity differs from the classical prediction. However, the measured values of permeability, effective diffusivity, and effective solubility of ARRA were within the range of results reported for other RAFM steels.     

Cesium solubility,diffusion and permeation in zirconium carbide

To compare the relative effectiveness of ZrC vis-a-vis SiC as a fission product barrier in fuel structures for high temperature gas cooled reactor (HTGR) applications, a series of cesium infusion experiments on various ZrC powders, and ZrC coated graphite structures was performed to study the cesium solubility, diffusivity, and permeability of this coating material. The ZrC powder results yield a solubility of Cs in ZrC, S(ppm wt) = (1.7 × 10^?6) exp[229 kJ/RT], over the temperature range 1485–1896 K. The diffusion coefficient of Cs in ZrC is 10^?18–10^?16 m²/s over a similar temperature interval. The activation energy of diffusion is estimated to be ≈ 50 kJ/mole.The results of experiments in which both SiC and ZrC coated graphite samples were exposed to cesium are more difficult to interpret. The results support the conclusions of the ZrC powder experiments that ZrC is comparable to SiC as a diffusion barrier to cesium.     

低活化铁素体/马氏体钢CLF-1氢氘的渗透行为

低活化铁素体/马氏体钢（RAFM钢）作为聚变堆结构材料中最有前景的候选材料,其氢同位素渗透行为备受关注。采用氢同位素气相驱动渗透的方法,对中国低活化铁素体/马氏体钢CLF-1的氢同位素渗透行为进行了研究,研究了温度、气体压强、样品表面状态等因素对其渗透行为的影响。结果表明：氢、氘在RAFM CLF-1钢中渗透扩散过程为体扩散控制,渗透率与温度的关系式均遵循Arrhenius关系;在实验测试过程中,由于样品表面发生氧化现象和缺陷捕获造成H₂和D₂渗透实验中渗透通量出现下降的现象。     

高温下GH3535合金中的氢同位素扩散渗透效应分析

Flibe具有熔点低、中子性能好、沸点高等特点,是未来大型氟盐冷却高温堆的主要候选氟盐冷却剂之一,在堆芯中与中子相互作用后会导致一定量的副产物氚产生。根据哈氏N合金的成分,钍基熔盐堆核能系统(TMSR)发展了GH3535合金,作为未来大型熔盐堆的主要候选结构材料。本实验中采用GH3535合金为试样,通过使用压力差驱动原理搭建的氢同位素扩散渗透装置,试验测得了400~800℃的温度下氢气、氘气在该合金中的渗透系数、扩散系数、Sieverts常数等主要参数。实验结果表明,氢气与氘气在GH3535合金中的扩散渗透机理均属于基体扩散控制过程,扩散渗透过程中氢气、氘气的主要参数与相应温度关系均符合阿累尼乌斯公式。对于不同质量数的氢同位素原子,拟合后渗透系数和扩散系数的指前因子之比分别为1.4:1和1.2:1,扩散和渗透过程中的激活能也非常接近,符合经典扩散理论的同位素效应,可以估算得到氚在GH3535合金中扩散渗透时的主要参数大约为氢的1/3(1/2),并可能用于氚在熔盐堆中的分布计算。     

Ti-Mo合金的吸放氢动力学

采用磁悬浮熔炼法制备了5种不同组成的TiMo_x（x=0.03, 0.12, 0.25, 0.50, 1.00，原子比）固溶体合金，用定容变压法测试了其在不同温度范围内的吸放氢动力学性能。研究结果表明，合金的吸放氢动力学可以按一级反应来描述，决速步骤为氢原子在合金晶格中的扩散。相同温度下，不同组成样品的吸氢容量随Mo含量的增加而降低。合金的吸氢活性随Mo含量增加先增强后减弱，氢化物的稳定性随Mo含量的增加而降低。     

Effect of Argon Ion Sputtering of Surface on Hydrogen Permeation through Vanadium

In order to measure the hydrogen permeation rate through V with atomically cleaned surface, an Ar ion sputtering apparatus has been installed in the hydrogen permeability measuring system. The permeation rate of the initial specimen was found to be increased by about one order of magnitude after Ar ion sputtering of its upstream side surface. Repeating of such a sputter-cleaning was not so much effective in increasing the steady state permeation rate as the initial sputtering was, but it accelerated the transient response rate by a factor of 2 or 3. The transient response rate was also accelerated by the increase of hydrogen pressure, but this effect tended to be diminished by the sputter-cleaning of specimen surface. The surface impurity layer on the downstream side of specimen was also inferred to act as a diffusion barrier affecting the steady state permeation rate. The present value of activation energy for hydrogen permeation through V at temperatures below 873 K was the smallest one ever obtained, showing that the surface effect was minimized in the present study on account of the surface sputter-cleaning in addition to the ultra high vacuum system.     

Studies on hydrogen permeability of 2.25% Cr–1% Mo ferritic steel: correlation with microstructure

The influence of microstructure on the hydrogen permeability, diffusivity and solubility in 2.25% Cr–1% Mo ferritic steel was investigated using electrochemical permeation technique. Varieties of microstructures ranging from martensite in water-quenched (WQ) steel to a predominant ferrite structure in annealed steel were characterised using analytical transmission electron microscopy. In the tempered structures, continuous precipitation of a variety of carbides of different morphologies and sizes was also characterised. The hydrogen diffusivity showed a continuous increase as the structure changed from martensite to ferrite and also with increasing extent of tempering. Solubility showed a corresponding decrease. The trends have been understood in terms of the number of reversible traps available for hydrogen in these different structures. Accordingly, martensite structure offered the maximum resistance to hydrogen diffusivity and tempered structure the least resistance due to the annihilation of defects during tempering and reduction in the solute content of the matrix due to precipitation.     

Neutron Irradiation Effect on Magnetic Properties of Cr-, Mo- and Si-Doped FeNi-Alloys

Sample of FeNi, FeNi: Cr, FeNi: Mo, and FeNi: Si alloys were irradiated by neutron beams in the vicinity of a 2 MW reactor core and their magnetic hysteresis curves, magnetic after effects as well as variations of magnetic permeability with temperature were determined. From these curves Curie temperature shift, spectrum widthk, and activation energy for self-diffusion of Fe and Ni atoms were obtained.

The presence of Si impurities in the FeNi alloy produces a considerable attenuation in the vacancy supersaturation and the analysis of the spectrum width in this sample indicates that the defect structure due to neutron irradiations is more complex than that due to thermal effect.     

Evaluating the hydrogen isotope absorption/diffusion coefficient of CVD-SiC at high temperature

Deuterium diffusion coefficient measurements of CVD-SiC were carried out using a solubility and diffusivity measurement apparatus to investigate the permeation mechanism of the hydrogen isotope through CVD-SiC. Experiments were conducted with thin-sheet-type samples with thicknesses of 0.1 mm, 1 mm, and 2 mm at 1073–1183 K. Total amount of occluded gas into or released gas from different thickness but same weight sample were expected to be the same, but unexpectedly differed by more than 50%. As the release rates after sufficient time had passed were almost the same, and the 1-mm-thick sample had twice the surface area of the 2-mm-thick sample, the measurements were probably affected by adsorbed gas on the surface. The value of D/L² (the diffusion coefficient divided by the square of the thickness), obtained by fitting to the theoretical formula but ignoring the early phase of discharge, was in good agreement for samples of different thickness at the same temperature, and was more than 5 orders of magnitude smaller than that obtained from the permeability measurement experiments. Therefore, we believe that the deuterium permeation through CVD-SiC is primarily dependent on the permeation rate through the grain boundaries.     

Ti-Mo合金吸氢动力学的同位素效应

为寻找一种价格低廉、分离性能优良的氢同位素分离材料来替代金属Pd,对Ti-Mo合金的氢同位素效应进行研究。采用磁悬浮熔炼方法制备5种不同组成的TiMox（x=0.03、0.13、0.25、0.50、1.00,Mo/Ti原子比）固溶体合金,用定容变压法测试了250～650℃范围内的吸氘动力学性能。结合前期吸氕动力学的研究结果可知,在250～650℃范围内,合金的平衡吸氕量略大于合金的平衡吸氘量。Mo含量小于1.00,在低温（250～450℃）下,合金的吸氘表观活化能均为负值。高温（450～650℃）下,合金的吸氘表观活化能大于吸氕表观活化能,与钛吸氢同位素动力学效应保持一致。     

Hydrogen and Deuterium Transport through Type 304 Stainless Steel at Elevated Temperatures

The permeation time-lag method have been used to determine the permeabilities, diffusion coefficients and solubilities of hydrogen and deuterium in type 304 stainless steel of three kinds of surface treated specimens; with oxide film, reduced by H₂ gas and Pd coated. For the specimen with a thin oxide film the permeability increased abruptly at the temperature higher than 1,050 K owing to reduction of the oxide film by H₂ gas introduced. The permeability and diffusion coefficient for hydrogen-reduced specimens agreed with those for Pd-coated specimens showing the data of bulk diffusion limited. The isotope effects for permeability Φ_H/Φ_D, diffusion coefficient D _H/D _D and solubility were about 1.4, 1.2 and 1.1, respectively. From these values θ(=hν/k)=1,530±50K and θ′(=hν/k)=2,740±20K were obtained by the quantum effect of a harmonic approximation.