Micromechanical modelling of coupled crystal plasticity and hydrogen diffusion

Hydrogen transport behaviour in metals is greatly influenced by the mechanical stress and the underlying microstructural features. In this work, a micromechanical model based on coupled crystal plasticity and hydrogen diffusion is developed and applied to model hydrogen diffusion and storage in a polycrystalline microstructure. Particular emphasis is laid on mechanical influences on hydrogen transport, invoked by internal stresses and by trapping of dislocations generated by plastic strains. First, a study of a precharged material is carried out where hydrogen is allowed to redistribute under the influence of mechanical loading. These simulations demonstrate to which extent hydrogen migrates from regions with compressive strains to those with tensile strains. In the next step, the influence of plastic prestraining on hydrogen diffusion is analysed. This prestraining produces internal residual stresses in the microstructure, that mimic residual stresses introduced into components during cold working. Lastly, a series of permeation simulations is performed to characterise the influence of hydrogen trapping on effective diffusivity. It is shown that the effective diffusivity decreases with stronger traps and the effect is more prominent at a larger predeformation, because the trapped hydrogen concentration increases considerably. The reduction of effective diffusivity with plastic deformation agrees very well with experimental findings and offers a way to validate and parameterise our model. With this work, it is demonstrated how micromechanical modelling can support the understanding of hydrogen transport on the microstructural level.     

Surface characterization of Pd/Ag23 wt% membranes after different thermal treatments

Hydrogen permeation measurements of 1.5-10 μm thick Pd/Ag23 wt% membranes before and after thermal treatments at 300 °C in air (both sides) or in the temperature range 300-450 °C in N₂ (feed side) and Ar (permeate side) were performed. Accompanying changes in surface topography and chemical composition were subsequently investigated by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) depth profiling. For a 2 μm thick membrane, the surface roughness increased for all annealing temperatures applied, while a temperature of 450 °C was required for an increase in roughness of both membrane surfaces to occur for the 5 μm membrane. The thickest membrane, of 10 μm, showed changed surface roughness on one side of the membrane only and a slight decrease in hydrogen permeance after all heat treatments in N₂/Ar. X-ray photoelectron spectroscopy investigations performed after treatment and subsequent permeation measurements revealed segregation of silver to the membrane surfaces for all annealing temperatures applied. In comparison, heat treatment at 300 °C in air resulted in significantly increased hydrogen permeance accompanied by increasing surface roughness. Upon exposure to oxygen, Pd segregates to the surface to form a 2-3 nm thick oxide layer (PdO), with more complex segregation behavior after subsequent reduction and permeance measurements in pure hydrogen. The available permeance data for the Pd/Ag23 wt% membranes after heat treatment in air at 300 °C is found to depend linearly on the inverse membrane thickness, implying bulk limited hydrogen permeation for thicknesses down to 1.5-2.0 μm.     

Deuterium transport and isotope effects in type 316L stainless steel at high temperatures for nuclear fusion and nuclear hydrogen technology applications

We present the first complete data set for the permeability, diffusivity, and solubility of both deuterium and hydrogen in 316L stainless steel (316L SS) obtained over a wide temperature range of 350–850 °C that accommodates both nuclear fusion and nuclear hydrogen technology applications. The deuterium results were also compared with the hydrogen results to estimate the isotope effect. The isotope effect ratio for diffusivity was different from the classical prediction. Furthermore, some of our results were compared with the results previously reported for 316 SS. Results and discussion are presented with an emphasis on the deuterium permeation and isotope effects.     

Properties of passive nano films on zircaloy-4 affected by defects induced by hydrogen permeation

In this work, hydrogen absorption and the permeation behavior of the passive layer formed on zircaloy-4 are investigated. Potentiodynamic polarization, Mott–Schottky analysis, electrochemical impedance spectroscopy, and Raman scattering spectroscopy are employed to characterize the passive defects before and after hydrogen permeation. It is found that the nanoscale passive ZrO2 films play an important role in the resistance against corrosion; hydrogen impingement,however, reduces the passive impedance towards hydrothermal oxidation. The increase of defects(vacancies) in passive film is probably attributed to the degradation. We believe that this finding will provide valuable insight into the understanding of the corrosion mechanism of zircaloys used in light water reactors.     

碳涂覆光纤的最新进展

本文首先介绍了气密性光纤的发展过程，接着重点分析了碳涂覆光纤的两个重要参数：长期可靠性和抗氢渗透性。引入了新的衡量碳涂覆光纤抗氢渗参量－缺氢渗因子，最后介绍了西安应用光学研究所碳涂覆光纤“八．五”末的进展情况，以及国内外现状比较。     

Characterization of nuclear tracks by positron annihilation and gas permeation

The application of polymeric membrane in combination with metallic films can be used for gas purification in particular for hydrogen where the molecular size is very small. The affinity of hydrogen to certain metals assists the flow of hydrogen, although it restricts the permeation of other gases. However, the flow rate is very small in dense membranes. Attempts have been made to generate nuclear tracks in polymeric membranes to control the gas flow. These tracks can be characterized by positron lifetime spectroscopy and gas permeation measurements. The long lifetime of ortho-positronium gives the estimate of size of the track-free volume of the order of 0.25 nm. The nuclear tracks can be modified by a chemical etching process. The chemical etching normally takes place from both sides of the membrane. When the etched pits from both sides meet, a rapid increase in gas permeation is observed. The size of the nano opening of the track has been observed for two different gases hydrogen and carbon dioxide, which have a molecular size of 0.2 and 0.4 nm, respectively.     

Accumulation and transport of hydrogen in RUSFER-EK-181 ferritic-martensitic steel

The influence of heat treatment on interaction between hydrogen and RUSFER-EK-181 Russian ferritic-martensitic steel is studied by the method of thermodesorption mass spectrometry. Based on our experimental data combined with published data for the structure of ferritic-martensitic steels, it can be supposed that the precipitation of fine carbides considerably facilitates the hydrogen sorption. Numerical simulation of hydrogen transport in the steel is conducted.     

Structure–phase transformations and physical properties of ferritic–martensitic 12% chromium steels EK-181 and ChS-139

The thermophysical properties (specific heat, thermal diffusivity, thermal conductivity, linear thermal expansion coefficient, density) of 12% chromium ferritic–martensitic steels EK-181 (RUSFER-EK-181) and ChS-139 and the structure–phase transformations that occur in them upon heating and cooling in the temperature range 20–1100°C are studied. The temperatures of the start and finish of the α → γ and γ → α transformations in these steels and the Curie temperature are determined by differential scanning calorimetry. Peaks in the temperature dependence of the specific heat and jumplike changes in the linear thermal expansion coefficient and the density and the minimum of thermal diffusivity are detected in the α → γ transformation range. Specific heat peaks, thermal conductivity minima, and inflection points in thermal diffusivity curves are also observed near the Curie temperature.     

Hydrogen degradation of steels and its related parameters,a review

Many steel structures can absorb varying amounts of hydrogen during manufacturing, processing such as electroplating or acid pickling and during service life by corrosion reactions or cathodic protection. Hydrogen is known to have a devastating effect on strength and ductility of iron and steel components. Many studies have been done on the detrimental effects of hydrogen on iron and different steel structures but there is a need for comprehensive research to cover all related parameters which can control the extent of hydrogen interaction and degradation in steels. In this review, at first hydrogen uptake and different damages associated with absorbed hydrogen in steels are discussed. Then, the effective parameters in the extent of hydrogen interaction and degradation, especially hydrogen embrittlement which is more common in steel components are reviewed.     

Simultaneous three-channel measurements of hydrogen diffusion with light intensity analysis of images by employing webcam

After exposure to high-pressure hydrogen and subsequent decompression, a three-channel technique for simultaneous measurement of hydrogen sorption content emitted from polymers and diffusivity and plastics was developed. The technique is based on the volumetric measurement of released H₂ gas combined with light intensity analysis of bright water level images by employing webcams and Lab view software. By measuring the released hydrogen corresponding to the change in water level against elapsed time in three parallel channels in real time, the total hydrogen uptake and diffusivity as a function of exposed pressure were determined with the developed diffusion analysis program. The technique was applied to three kinds of sealing rubber materials and two polyethylene liner materials. The pressure-dependent transport behaviors obtained by the developed technique are discussed and compared with those obtained by different techniques. Diffusion parameters versus variation in volume and shape for high-density polyethylene are presented together with an uncertainty evaluation for this method.     

氢在不锈钢及氧化铬膜复合体中的稳态渗透实验

本文介绍氢在ＨＲ－１不锈钢基体及镀有氧化铬膜的复合材料中的行为研究，包括基体的准备；膜的制备；用不同手段从不同角度对膜进行的分析测试；膜与基体之间的平均结合力测定；用不锈钢材料构成的高温低压渗透回路的建造、调试、密封性能校准；纯ＨＲ－１基体材料中的氢渗透规律研究；有膜复合材料中氢的稳态迁移过程的表现规律实验结果。它们与国外类似的实验符合得较好；膜的分析测试结果反过来对制膜工艺提供了很有用的反馈信息，氢渗透回路的性能通过了有关专家鉴定，主要技术指标已达到国际同类设备的先进水平。为下阶段更广泛深入的研究奠定了良好的基础。     

Role of hydrogen in stress corrosion cracking of austenitic stainless steels

Effects of hydrogen charging on the stress corrosion cracking (SCC) behavior of 304 and 310 stainless steels under sustained load were investigated in boiling 42% MgCl₂ solution. The cracking was accelerated by the incorporation of hydrogen into the steel without altering the crack growth mechanism. The fact that the active dissolution is almost unaffected by the hydrogen charging and tensile stress indicates that the phenomenon of hydrogen-promoted SCC is unlikely a result of hydrogen-facilitated active dissolution. In contrast, hydrogen significantly promotes anodic dissolution in the potential range where the active-to-passive transition occurs. The electrochemical noise detected in the SCC process implies that the crack propagation process is discontinuous and hydrogen charging can raise the frequency of film breakdown at the crack tip. These observations suggest that the hydrogen-promoted SCC may result from the hydrogen-induced passivity degradation.     

碳化钛及其复合涂层材料抗氚渗透层的稳定性

研究了３１６Ｌ不锈钢表面镀ＴｉＣ和ＴｉＮ＋ＴｉＣ复合涂层材料的抗氚透层在聚变环境中的稳定性。研究结果表明,ＴｉＣ和ＴｉＮ＋ＴｉＣ复合涂层材料经化学热处理后在其表面层生成的抗氚渗透层能抗Ｈ＾＋离子辐照,能抗很大的温度梯度和热循环,经长时间实验证明这些涂层材料的抗氚渗透层性能稳定。     

Heat diffusivity and heat conductivity of Ni near the Curie point

The heat diffusivity of Ni near the Curie point was measured by an a.c. oscillating method. The period of self-oscillation is related to the heat diffusivity. The principle and some technical details of the experimental method is given. The critical behavior of heat diffusivity near the Curie temperature is analysed. Using known specific heat data the heat conductivity for Ni can be calculated. A conclusion is made that the Wiedemann-Franz law is not valid near the ferromagnetic phase transition.     

Hydrogen diffusion in crystalline semiconductors

The diffusion of hydrogen in semiconductors is complicated by the existence of several charge states (notably H⁺ in p-type material and H^- or H⁰ in n-type material, at least for Si) and also that hydrogen is present in a number of different forms, namely atomic, molecular or bound to a defect or impurity. Since the probability of formation of these different states is dependent on the defect or impurity type and concentration in the material and on the hydrogen concentration itself, then the apparent hydrogen diffusivity is a function of the sample conductivity and type and of the method of hydrogen insertion. Under conditions of low H⁺ concentration in p-type Si, for example, the diffusivity is of the order of 10^-10 cm² · s^-1 at 300 K and is consistent with the value expected from an extrapolation of the Van Wieringen and Warmoltz expression D_H = 9.4 × 10^-3 exp[-0.48 eV/kT] cm² · s^-1. The characteristics of hydrogen diffusion in n- and p-type Si and GaAs are reviewed in this paper, and the retardation of hydrogen permeation by molecular formation and impurity trapping is discussed. The measurement of several key parameters, including the energy levels for the hydrogen donor and acceptor in Si and the diffusivity of the H⁰ and H^- species, would allow a more quantitative treatment of hydrogen diffusion in semiconductors.     

Bubble-loop complexes induced by helium irradiation and effect of pre-irradiation and post-irradiation of hydrogen in reduced-activation ferritic/martensitic steel

In the present work, the synergistic effect of high concentration hydrogen and helium on the dislocation loops and bubbles as well as their correlations in reduced-activation ferritic/martensitic (RAFM) steels is investigated. Such an effect was transmuted from 14?MeV neutron irradiation and has been one of the most challenging issues for RAFM steels for future fusion reactors. After low dose (0.18?dpa) high concentration (5000 appm) single-ion helium irradiation at 723?K, very large dislocation loops were observed, and the majority of bubbles were inside dislocation loops, forming bubble-loop complexes. These bubble-loop complexes defects were also present in hydrogen/helium and helium/hydrogen sequential-ion irradiated steels. Pre-irradiated hydrogen ion effectively inhibited the later growth of loops induced by helium post-irradiation, and the higher the ratio of hydrogen to helium fluence, the greater the effect of inhibition. At high fluence of hydrogen pre-irradiation, the structure of bubble-loop complexes disappeared. On the other hand, hydrogen post-irradiation promoted the growth of loops induced by helium pre-irradiation, and the higher the ratio of hydrogen to helium fluence, the greater the effect of promotion. The mechanisms for hydrogen/helium synergistic effects are discussed.     

Effect of hydrogen on interatomic bonds in austenitic steels

Mössbauer spectroscopy was used to investigate the influence of dissolved hydrogen on the interatomic bonds in austenitic steels. It was carried out to prove the decohesion mechanism of hydrogen embrittlement (HE). It is shown that hydrogen increases Debye temperature, i.e., the interatomic bonds in hydrogenated austenitic steel becomes stronger.     

蓄热式催化重整氢发生器的研究

本文提出了一种可用于内燃机的新的制氢方案。以往的研究者只关心一方面,主要研究催化重整制氢,或者是蓄热式换热等。蓄热式催化重整氢发生器是将这两点结合,即蜂窝状蓄热体与重整反应结合起来所设计的。它既有催化重整反应器的优势,又有蓄热体的优势,可以利用蓄热体的快速换热性质,快速地产生氢气,是一种新型氢发生器。     

氢在HR－1不锈钢中迁移特性的热动力方法研究

本文研究了氢在ＨＲ－１不锈钢中热动力驱动的宏观迁移特性。用不同的方法（电化学方法和１０５ｐａ氢压强下高温气相法）使试样充氢，然后研究加热升温放气规律，得到了在有意义的温度范围内出气峰的位置以及氢在ＨＲ－１材料中扩散、溶解、渗透系数与温度的关系，并与渗透法测得的结果和国外类似实验结果符合得较好。这些数据对估计未来聚变堆中氚的投料量和氚的渗透漏失有实际意义。     

Constant-load delayed fracture test of atmospherically corroded high strength steels

Constant load tests of circumferentially notched round bar specimens of high strength steels after cyclic corrosion test and outdoor exposure have been performed to demonstrate that delayed fracture occurs when the hydrogen content from the environment, H_E, exceeds the critical hydrogen content for delayed fracture, H_C. During the constant load tests the humidity around the specimen was increased in stepwise manner to increase hydrogen entry. After fracture the specimen was kept at the humidity long enough to homogenize hydrogen in the specimen and to obtain more quantitative hydrogen content by thermal desorption analysis. H_E of the fractured specimens was higher than H_C, and H_E of the specimens not fractured was lower than H_C. This result confirms that the balance between H_C and H_E determines the occurrence of delayed fracture and that hydrogen-content-based evaluation of susceptibility to delayed fracture is reasonable. To certify the increase of H_E with increase in humidity, electrochemical hydrogen permeation test was carried out. The hydrogen permeation current density was increased especially at 98%RH. Enhancement of hydrogen entry with increase in CCT number was also shown by the test.