Recovery of Hydrogen Isotopes by Pd-coated ZrNi from Inert Gas Atmosphere Containing Impurities

Effect of Pd coating on recovery of hydrogen isotopes from inert gas atmosphere was investigated for intermetallic compounds ZrNi. Powder of ZrNi was coated with Pd by electroless plating. Subsequent annealing at 1,073 K led to the formation of ZrPd at the powder surface. The durability in deuterium recovery from Ar gas was examined for the bare and the Pd-coated powders at temperatures from 373 to 573 K as well as the kinetics of deuterium absorption and desorption. The absorption and desorption of deuterium obeyed the first and the second order kinetics, respectively. The ZrPd layer on ZrNi did not alter the absorption and the desorption kinetics. The deuterium recovery by the bare powder was degraded with time owing to oxidation of powder surfaces by impurities contained in the Ar gas. The durability in deuterium recovery was markedly improved by Pd coating, and no significant degradation was observed for the Pd-coated specimen at 573 K. This difference in the durability was ascribed to the difference in the oxidation behavior between ZrNi and ZrPd. It was concluded that Pd coating significantly improves the applicability of ZrNi to tritium recovery in blanket systems.     

用于氢同位素分离的置换色谱分离材料的研究进展

置换色谱法是一种较有优势的氢同位素分离方法,而分离材料的性能是决定置换色谱法分离效果的一个关键因素。目前研究的置换色谱分离材料包括钯材料和很多非钯材料。钯虽然价格昂贵,但由于其出色的分离性能而难以用廉价金属或合金来替代。本文简要介绍了置换色谱法分离氢同位素的原理,重点介绍了几种置换色谱含钯分离材料(纯钯、载钯硅藻土、载钯氧化铝、钯铂合金等)的性能,初步分析了置换色谱分离材料的发展方向。     

Hydrogen cold plasma for synthesizing Pd/C catalysts: the effect of support-metal ion interaction

It has been found that cold plasma is a facile and environmentally benign method for synthesizing supported metal catalysts, and great efforts have been devoted to enlarging its applications. However, little work has been done to disclose the influence mechanism, which is significant for controllable synthesis. In this work, hydrogen cold plasma was adopted to synthesize a palladium catalyst supported on activated carbon(Pd/C-P) using H_2 PdCl_4 as a Pd precursor followed by calcination in hydrogen gas to remove the chlorine ions. The Pd/C-P catalyst was found to be made of larger Pd nanoparticles showing a decreased migration to the support outer surface than that prepared by the conventional thermal hydrogen reduction method(Pd/C-C). Meanwhile, the pore diameter of the activated carbon support is small(~4 nm).Therefore, Pd/C-P exhibits lower CO oxidation activity than Pd/C-C. It was proposed that the strong interaction between the activated carbon and PdCl_4~(2-)and the enhanced metal–support interaction caused by hydrogen cold plasma reduction made it difficult for Pd nanoparticles to migrate to the support outer surface. The larger-sized Pd nanoparticles for Pd/C-P may be due to the Coulomb interaction resulting in the disturbance of the metal–support interaction. This work has important guiding significance for the controllable synthesis of supported metal catalysts by hydrogen cold plasma.     

Preparation of Cr2O3 film by MOCVD as hydrogen permeation barrier

Cr₂O₃ film on structural material as hydrogen permeation barrier can be applied in many areas such as hydrogen storage devices, vacuum solar receivers and fusion reactors. In this study, the Cr₂O₃ film was prepared by MOCVD on 316L stainless steel using chromium(III) acetylacetonate as precursor. The film was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The hydrogen permeation inhibition performance of films was investigated by deuterium permeation experiment. The 366 nm thick Cr₂O₃ film on 316L could reduce the deuterium permeability by 24–117 times at 823–973 K, revealing efficient inhibition to hydrogen permeation. The Cr₂O₃ film is dense, crack-free and has a corundum structure which possesses a more stable structure than a metastable phase or an amorphous phase. Moreover, the crystalline Cr₂O₃ could be easily obtained by MOCVD at a low temperature, e.g. 773 K.     

Effect of water vapor on tritium permeation behavior in the blanket system

It is found that most hydrogen supplied to the purge gas changed to water vapor due to the water formation reaction in the early stage of the blanket operation and that physical or chemical adsorbed water is released in the high concentration into the blanket purge gas when the blanket temperature becomes higher than several hundreds of degrees K if the pre-treatment is not applied to the solid breeder materials. Effect of coexistence of water vapor in the purge gas on permeation behavior of hydrogen through F82H ferritic steel in the breeding part and palladium–silver (Pd–Ag) in the recovery part is discussed because use of them is generally considered for recovery of bred tritium from the solid blanket. Almost no decrease in permeation rate of F82H is observed in this study when water vapor exists in the blanket purge gas. The permeability of hydrogen isotopes through the Pd–Ag pipe gradually decreases when water vapor exists in the blanket purge gas. Properties required in estimation of the hydrogen permeated to the purge gas are experimentally obtained in this study.     

反应堆非能动氢气复合器严重事故下消氢性能研究

非能动氢气复合器（PAR）是核电厂主要的消氢措施。在严重事故下，某些裂变反应产生的特殊杂质(如I₂、CsI、CO等)可能对催化剂产生有害的影响，为保证PAR消氢性能的可靠性，中毒机理研究十分必要。本文根据相关试验研究结果，从铂、钯金属原子分布结构、催化反应性面积两个方面对催化剂中毒效应进行机理分析，研究得出催化剂中金属原子的分布结构、进入PAR的实际毒物浓度等均是影响催化剂中毒效应的关键因素。     

Measurement of deuterium and helium by glow-discharge optical emission spectroscopy for plasma–surface interaction studies

To examine the resolution of isotope analysis of hydrogen with glow-discharge optical emission spectroscopy (GDOES), depth profiles of hydrogen and deuterium in a H-containing Ta/D-containing Ti/Ni layered structure were measured. The depth profiles of deuterium could be measured with sufficient resolution in the presence of relatively large amounts of hydrogen and vice versa. In addition, measurements of depth profiles of He implanted in W at room temperature were also performed with Ne plasma. The intensity of the He emissions was sufficiently high at a fluence of 10²⁰ He m^?2 or higher. The depth profiles of He measured in this manner were in good agreement with the results of cross-sectional observations using a transmission electron microscope. Therefore, it was concluded that GDOES with Ne plasma is a promising technique for the depth profile analysis of plasma-facing materials and deposited layers formed on them.     

Deuterium Retention and Physical Sputtering of Low Activation Ferritic Steel

Low activation materials have to be developed toward fusion demonstration reactors. Ferritic steel, vanadium alloy and SiC/SiC composite are candidate materials of the first wall, vacuum vessel and blanket components, respectively. Although changes of mechanical-thermal properties owing to neutron irradiation have been investigated so far, there is little data for the plasma material interactions, such as fuel hydrogen retention and erosion. In the present study, deuterium retention and physical sputtering of low activation ferritic steel, F82H, were investigated by using deuterium ion irradiation apparatus. After a ferritic steel sample was irradiated by 1.7 keV D^ ions, the weight loss was measured to obtain the physical sputtering yield. The sputtering yield was 0.04, comparable to that of stainless steel. In order to obtain the retained amount of deuterium, technique of thermal desorption spectroscopy (TDS) was employed to the irradiated sample. The retained deuterium desorbed at temperature ranging from 450 K to 700 K, in the forms of DHO, D2, D2O and hydrocarbons. Hence, the deuterium retained can be reduced by baking with a relatively low temperature. The fiuence dependence of retained amount of deuterium was measured by changing the ion fiuence. In the ferritic steel without mechanical polish, the retained amount was large even when the fluence was low. In such a case, a large amount of deuterium was trapped in the surface oxide layer containing O and C. When the fluence was large, the thickness of surface oxide layer was reduced by the ion sputtering, and then the retained amount in the oxide layer decreased. In the case of a high fluence, the retained amount of deuterium became comparable to that of ferritic steel with mechanical polish or SS 316 L, and one order of magnitude smaller than that of graphite. When the ferritic steel is used, it is required to remove the surface oxide layer for reduction of fuel hydrogen retention. Ferritic steel sample was exposed to the environment of JFT-2M tokamak in JAERI and after that the deuterium retention was examined. The result was roughly the same as the case of deuterium ion irradiation experiment.     

热循环吸附法分离氕、氘的研究

对热循环吸附法(TCAP)全回流模式和生产模式下的氕 氘分离实验进行了研究。全回流模式下，主要考核了初始进料比、冷/热循环温度、进料位置对分离效果的影响。结果表明，原料气体从分离柱中部进料时，初始进料比相对越大，冷/热循环温差越大，分离效果越好；而从回流柱进料时，分离效果相对更好。在几组实验中，回流柱初始进料为90%、冷/热循环温度分别为56 ℃/290 ℃的一组效果最好。生产模式下，由于分离柱中气阻较大，有可能影响氕、氘的分离效果，这部分实验还有待继续进行。     

金属氢化物的正电子湮没研究

采用正电子湮没方法在７７－３００Ｋ温区和ｘ为０－０．８６氢浓度范围研究了Ｐｄ０．７５Ａｇ０．２５Ｈｘ和ＮｂＨｘ两种金属氢化物，叙述了获得的实验结果。     

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。     

Ni掺杂对金属V抗毒化性能的影响

采用磁悬浮感应熔炼法制备VNi_0.01合金,完全活化后,在含0.5%CO₂的1.0 MPa毒化气氛中进行吸氘反应。在反应初期VNi_0.01合金与纯V相比,仍保持较快的吸氘速率,随后合金吸氘速率迅速下降直至为零。样品毒化后经加热除气处理,样品室内再次充入1.0 MPa高纯氘气,VNi_0.01合金吸氘速率已恢复至完全活化时的水平,而纯V的吸氘速率则低于初次活化时的吸氘速率。合金经活化后测得其增压性能在300～400 K范围内均优于纯V,因而合金有望用于增压化学床。这些研究结果将为该材料的应用提供直接依据。     

载钯硅藻土的制备及其吸放氢性能研究

采用PdCl2溶液以浸渍还原法制备了载钯硅藻土复合材料(Pd/K),并对Pd/K复合材料中钯的分布状态,以及Pd/K复合材料的p-C-T曲线、热力学、动力学及循环吸放氢性能进行了研究。结果表明:与纯钯相比,载钯硅藻土样品吸氢量有所降低,吸放氢平台压稍有升高,平台斜率增大,其吸氢速率比纯钯的高1倍以上;吸放氢焓变值降低,熵变值升高。经2000次吸放氢循环后,载钯硅藻土的样品饱和吸氢量和吸氢速率未改变,粉化率为3.6%(质量分数)。     

Interaction of hydrogen plasma with carbon-tungsten composite layer

Interaction of neutral hydrogen atoms with the layer of hydrogenated carbon-tungsten composite was studied. A 1 μm thick layer was prepared by sputter deposition from C and WC-targets in Ar/C₂-H₂ gas mixture. After deposition the samples were treated in weakly ionized highly dissociated hydrogen plasma created in a microwave discharge at a power of 1 kW. The gas flow was 13 l/h and pressure was 90 Pa. Temperature of the samples during treatment was about 850 K. After plasma treatment the samples were analyzed by AES (Auger electron spectroscopy) depth profiling, XPS (X-ray photoelectron spectroscopy) and SEM (scanning electron microscopy). It was found that during hydrogen plasma treatment selective etching of the C-W layer occurred. Carbon was preferentially removed from the C-W layer, and after about 10 min of treatment practically only tungsten with a huge porosity was detected.     

电子束高剂量辐照新鲜贻贝肉制品的试验研究

研究了即食鲜贻贝肉制品经电子束高剂量辐照带来的影响和杀菌保存效果.使用NFZ-10/4.0-1000电子直线加速器对密闭罐装鲜贻贝实施15 kGy和25 kGy两种剂量的双向辐照,并作微生物培养试验.主观评价和剂量测试.结果表明,高剂量辐照密闭的罐装鲜贻贝肉,对其食用性和风味没产生明显的影响,但可有效杀灭各类微生物,使...     

载钯硅藻土吸氕/氘动力学同位素效应

恒温等容条件下,通过p-t曲线测量,研究在223~393K范围内载钯硅藻土(Pd/K)吸氕、氘动力学特性。应用反应速率分析方法计算了反应速率常数,得到了Pd/K吸氕、氘反应活化能。动力学计算结果显示:在整个温度范围内,载钯硅藻土与氕、氘反应明显分为两个温度段。低温段(223~313K),载钯硅藻土吸氕、氘反应速率常数随温度升高而增大且吸氕反应速率大于吸氘反应速率,吸氕、氘反应活化能分别为19.5、19.2kJ/mol;高温段(313~393K),载钯硅藻土吸氕、氘反应速率则随温度升高而减小,氕、氘反应活化能分别为:-18.6、-12.1kJ/mol。测试结果表明,载钯硅藻土吸氕、氘反应存在显著的动力学同位素效应且同位素效应依赖于温度的变化。     

Influence of oxide layer morphology on hydrogen concentration in tin and niobium containing zirconium alloys after high temperature steam oxidation

The influence of the oxide layer morphology on the hydrogen uptake during steam oxidation of (Zr,Sn) and Zr-Nb nuclear fuel rod cladding alloys was investigated in isothermal separate-effect tests and large-scale fuel rod bundle simulation experiments. From both it can be concluded that the concentration of hydrogen in the remaining metal strongly depends on the existence of tangential cracks in the oxide layers formed by the tetragonal - monoclinic phase transition in the oxide, known as breakaway effect. In these cracks hydrogen is strongly enriched. It results in very local high hydrogen partial pressure at the oxide/metal interface and in an increase of the hydrogen concentration in the metal at local regions where such cracks in the oxide layer exist. Due to this effect the hydrogen uptake of the remaining zirconium alloy does not depend monotonically on temperature. Differences between (Zr,Sn) and Zr-Nb alloys are caused by differences in the hydrogen production due to different oxidation kinetics and in the crack forming phase transformation in the oxides as well as in the mechanical stability of the oxides.     

Air exposure and sample storage time influence on hydrogen release from tungsten

In investigations of hydrogen retention in first wall components the influence of the conditions of the implanted target storage prior to analysis and the storage time is often neglected. Therefore we have performed a dedicated set of experiments. The release of hydrogen from samples exposed to ambient air after irradiation was compared to samples kept in vacuum. For air exposed samples significant amounts of HDO and D₂O are detected during TDS. Additional experiments have shown that heavy water is formed by recombination of releasing D and H atoms with O on the W surface. This water formation can alter hydrogen retention results significantly, in particular - for low retention cases. In addition to the influence of ambient air exposure also the influence of storage time in vacuum was investigated. After implantation at 300 K the samples were stored in vacuum for up to 1 week during which the retained amount decreased significantly. The subsequently measured TDS spectra showed that D was lost from both the high and low energy peaks during storage at ambient temperature of ∼300 K. An attempt to simulate this release from both peaks during room temperature storage by TMAP 7 calculations showed that this effect cannot be explained by conventional diffusion/trapping models.     

三氧化二铝PLOT柱气相色谱法分离氢同位素自旋异构体

氢同位素核自旋异构体正-仲态比例影响氢同位素的低温物性,有必要对其比例进行测定。本文利用活性三氧化二铝多孔层开管(Porous Layer Open Tubular,PLOT)柱实现了正-仲氢同位素(氕、氘)的基线分离,发展了一种可在液氮温度下测定同核分子正-仲态比例的色谱分析技术。研究结果表明,与传统三氧化二铝填充柱相比,高效PLOT柱实现了正、仲氕(o-H_2、p-H_2)以及正、仲氘(o-D2、p-D2)的基线分离(分离度R_s大于1.5),当流量为5 m L·min-1时,分离度R_s(p-H_2,o-H_2)=6.9,R_s(o-D2,p-D2)=1.8。正仲态分离度与进样量、流量均有关系。根据峰面积的积分结果,常温(298 K)下正、仲氕比例为2.77:1,正、仲氘比例为1.78:1,与理论测算值基本符合。HD与o-H_2实现了部分分离,R_s(o-H_2,HD)=0.5,根据理论预测,实现HD与o-H_2的基线分离(R_s达到1.5),理论塔板数需要达到3.9×105。     

Hydrogen absorption by zirconium alloys at high temperatures

At high temperatures, e.g. during a hypothetical severe accident, zirconium and its alloys are not stable to other materials and to oxidising atmospheres. Exothermic reactions with steam cause the production of hydrogen which will be released to the atmosphere and, thus, endanger the containment or may be absorbed by the remaining metal. The hydrogen solubility in Zircaloy-4 and Zr-1Nb was measured in the temperature range of 1230-1730 K and at hydrogen partial pressures between 10 and 100 kPa. The parameters of the Sieverts constant were determined. No significant differences between the two alloys were observed. The hydrogen solubility of oxygen containing Zircaloy-4 decreases with increasing oxygen content.