Effective Hydrogen Diffusivity Research Articles

Understanding the correlation of aging treatments and stress corrosion crack growth of a secondary hardening ultra-high strength steel

The correlation of aging treatments and stress corrosion crack growth of a secondary hardening ultra-high strength steel was investigated using microstructural characterization, electrochemical hydrogen penetration experiment, thermal desorption spectroscopy analysis, and stress corrosion crack growth test. The results showed that increase of aging duration led to slight increase in the fraction of reversed austenite but decrease in dislocation density while no notable variation in grain boundary misorientation distribution and the corrosion behavior was observed. The shrinkage and fracture toughness continued to increase with aging duration while the yield strength reaching a maximum value after 5 hours of aging. Longer aging durations led to the decrease in effective hydrogen diffusion coefficient but improvement of stress corrosion cracking resistance, mainly due to the coarsening and nucleation of M2C carbides, as well as the higher fraction of reversed austenite. This work provided the theoretical and technical basis for improving the stress corrosion cracking resistance of this steel.

Hydrogen diffusion and trapping in a cryogenic processed high-Cr ferrous alloy

The effect of hydrogen diffusion and trapping was studied in a high-Cr ferrous alloy using an inverted scanning Kelvin probe and thermal desorption spectroscopy in correlation with microstructure and residual stress study. In addition, different processing of ferritic/martensitic 9Cr1WTaV alloy (EUROFER97) was tested in correlation with observed selected properties to observe induced changes in material degradation and surface. The activation energies for hydrogen traps were shown to have distinct peaks corresponding to different trapping mechanisms, including matrix dislocations and grain boundaries. For the cryogenically treated sample, an additional peak was also identified and correlated with increased carbide precipitation.

Hydrogen permeation in iron-chromium-aluminum (FeCrAl) alloys and the effects of microstructure and surface oxide

Iron–chromium–aluminum (FeCrAl) class alloys are candidates for use as cladding for accident-tolerant fuels and moderators. In this context, hydrogen isotope permeation in FeCrAl alloys is an important material property. In the present work, the apparent permeability, effective diffusivity, and apparent solubility of hydrogen in the FeCrAl alloys C26M and Kanthal D (KD) were measured with gas-driven hydrogen permeation. Permeation measurements were conducted at temperatures of 400 to 700 °C and at gas-driven pressures from 1 to 100 kPa. In particular, the effect of grain size on hydrogen transport was studied with KD samples with three different microstructures: nanocrystalline (NC), ultra-fine grained (UFG), and coarse-grained (CG). The UFG and NC specimens had higher apparent activation energies (73.4 kJ mol-1 and 65.2 kJ mol-l, respectively) for hydrogen permeability than the CG sample (46.9 kJ mol-1). An aluminum oxide layer formed on the primary- and secondary-side surfaces of all samples subjected to permeation experiments which demonstrated the propensity of FeCrAl alloys to form these innate oxide permeation barriers.

Study of Mass Transport in the Anode of a Proton Exchange Membrane Fuel Cell with a New Hydrogen Flow‐Rate Modulation Technique

AbstractHydrogen transport in the anode of a proton‐exchange membrane fuel cell (PEMFC) has been studied with a modulation technique relating the hydrogen flow‐rate ( ) and the faradaic current ( ), called Current‐modulated Hydrogen flow‐rate Spectroscopy (CH2S). A simple analytical expression for the transfer function, H(jω)=n F / , is provided, showing a skewed semicircle in Nyquist representation (−H'' vs. H'), extending from H’=0 to H’=1, and with the maximum frequency at ωmax=2.33(DH2 /Li2), where DH2 is the effective hydrogen diffusivity and Li the thickness of the anode gas diffusion layer (GDL). The expression for CH2S is also calculated with an existing reversible chemical reaction in the GDL. Experimental results under different operation conditions show two transport processes limiting the anode reaction, one attributed to molecular diffusion through the partially saturated GDL, and the other to the microporous layer (MPL), or its interfaces with GDL or with the catalyst layer (CL). CH2S provides the hydrogen diffusivities (DH2,i) associated to each process under the different conditions. Current density decreases slightly the diffusivity of the GDL, while it becomes activated in the MPL; using two GDLs in the anode improves both GDL and MPL diffusivities; humidification decreases the diffusivity in both, GDL and MPL; finally, a superhydrophobic anodic CL prepared by electrospray improves hydrogen diffusivity in GDL and MPL.

Hydrogen diffusion and precipitation influenced by non-uniformly distributed stress in zirconium alloy with different textures

Hydrogen embrittlement is a crucial factor for the performance and life of zirconium alloys in nuclear industry. During service, the residual stress in the materials induces re-distribution of hydrogen, which further affects the fracture behavior. This study is dedicated to investigating the hydrogen diffusion and precipitation under the meso‑scale non-uniform deformation field. The texture effect of hydrogen behavior was examined by considering three different texture scenarios: grains with c-axis deviating from the tensile direction of random angle, 0°and 90° The cases were termed Random, T000, and T0900 respectively. The crystal plasticity finite element method (CPFEM) was employed to simulate the stress-assisted diffusion of hydrogen atoms in the polycrystalline zirconium alloy. It is determined that the T0900 case gets fewer regions with higher hydrostatic stress gradient, which helps relieve the hydrogen concentration. Compared to the T0900 texture, the interaction between soft and hard grains in the Random and T000 texture conditions results in higher stress gradient and severe hydrogen concentration. Statistical analysis was conducted and the hydrogen concentration in the three textures presents a normal distribution. T0900 gets a relatively lower overall hydrogen concentration while the T000 texture gets severe hydrogen concentration larger than 120 wt.ppm. In Random and T000 textures, hydrogen tends to accumulate at grain interior and boundaries, and continuous hydrogen concentration band forms along adjacent GBs. The T0900 scenario is free of large continuous hydrogen concentration zones, which helps reduces the adverse effects of hydrogen diffusion and precipitation. The findings of the work advance the understanding of the hydrogen behavior affected by stress heterogeneity and texture, which is the basis for the exploration of hydrogen embrittlement.

Hydrogen and deuterium permeation in Hastelloy N

Hastelloy N was chosen as the fluoride salt-contacting structural material for the Molten Salt Reactor Experiment due to its excellent compatibility with the fuel salt FLiBe. FLiBe is currently investigated for several advanced fusion and fission reactor concepts where tritium generation in the FLiBe is anticipated. Knowledge of hydrogen transport properties through Hastelloy N is important to understand how tritium would permeate through this material and result in an unintentional release. In this study, the hydrogen and deuterium permeability, diffusivity, and solubility were measured from 500 to 700 °C at a primary-side pressure of 10 kPa in a well-characterized sample of Hastelloy N. The prepared polycrystalline Hastelloy N had C and O impurities present on the surface. These impurities were investigated using Auger Emission Spectroscopy and Ar depth profiling. The adventitious C was removed upon the first Ar sputter cycle whereas O persisted deeper into the sample. For permeation experiments, applied deuterium pressures ranged from 13 Pa to 100 kPa and deuterium transport remained in the diffusion-limited regime (J ∝ P0.5) throughout the pressure range examined. Two methods are employed to measure the effective hydrogen and deuterium diffusivity: rise and decline. The decline method produced improved statistical model fits for calculating the effective diffusion coefficient compared to the rise method. The resultant transport properties compared well to published values for other nickel alloys.

First principles study on strain effect of hydrogen diffusion and dissolution behavior in Ruthenium

In this work, the role of three kinds of strain, such as volumetric, biaxial and shear strain, in the dissolution and diffusion of Hydrogen (H) in Ruthenium (Ru) were studied by using first-principles simulation method. It was found that under volumetric or biaxial strains, the dissolution energy of H in Ru increases with the increase of compressive strain and decreases with the increase of tensile strain. For shear strain, the effect of strain on the dissolution energy of H in Ru relies on the crystal plane to which the strain is applied. The diffusion coefficients of H in Ru are different along the c and a direction and strongly dependent on the type and value of strain. All above results indicate that, in comparison to strain-free Ru film, H aggregation and even H bubbles are more difficult to form in Ru film under compressive strain.

A novel strategy for estimating the diffusion behavior of hydrogen in metallic materials with the combined effect of stress corrosion and hydrogenation: Case study of 2.25Cr-1Mo-0.25V high-strength steel

Hydrogen equipment for long-term service in complex hydrogen environment is threatened by the phenomenon of hydrogen-induced damage, and the combined effect of stress corrosion and hydrogen attack can intensify the formation and development of hydrogen damage. In this study, a new strategy to indirectly estimate the hydrogen diffusivity of metallic materials under tensile stress was proposed by combining the electrochemical hydrogen permeation test (EHPT), the hydrogen diffusion descriptive equation based on Fick's law, and hydrogen pre-charged tensile test. The results revealed that the hydrogen permeation curve obtained after considering the effect of the residual hydrogen extraction stage was highly approximate to the theoretical trend. The hydrogen embrittlement (HE) susceptibility of the pre-tensioned tensile and hydrogen-charged specimens increased with increasing stress. At tensile stress (0–400 MPa) the effective hydrogen diffusivity of 2.25Cr-1Mo-0.25 V steel was: Deff=1.1686+0.4842×exp(σ/277.869). The micrograph from the fracture surfaces also reflected the aggravated brittle fracture characteristics of the steel.

On the Change in Hydrogen Diffusion and Trapping Behaviour of Pearlitic Rail Steel at Different Stages of Production.

To avoid hydrogen flaking in rail production, it is of crucial importance to understand the differences in hydrogen diffusion and trapping between different production steps. Therefore, as-cast unfinished material was compared with two finished rails, hot-rolled and head-hardened, using electron backscattered diffraction (EBSD), electrochemical permeation, and thermal desorption spectroscopy (TDS). A significant increase in dislocation density was in the head-hardened rail compared with the other material states. This leads to an effective hydrogen diffusion coefficient of 5.8 × 10-7 cm2/s which is lower by a factor of four than the diffusion coefficients examined in the other states. Thermal desorption spectroscopy analyses show a clear difference between unfinished and finished rail materials. While a peak in activation energy between 32 and 38 kJ/mol is present at all states, only as-cast unfinished material shows a second peak with an activation energy of 47 kJ/mol, which is related to microvoids. The results show that in the investigated material, the effect of increasing dislocation density has a stronger influence on the effective diffusion coefficient than the presence of a second active trapping site.

Hydrogen accumulation and diffusion in cylindrical-shaped pipeline steels with coating defects

The effective diffusion of hydrogen in a cylindrical geometry, mimicking a pipe with a coating defect, was investigated by modelling and verified experimentally. Analytical solutions for the extreme cases of no hydrogen uptake and constant hydrogen uptake were developed. Simulations showed less than 5% error, when compared to two well-documented reference cases for diffusion. The intermediate case of modelling kinetic controlled hydrogen uptake was investigated and the effects of time, position, effective diffusion coefficient, corrosion protection current density and their binary interactions, were reported. Modelling results show, that certain parameter combinations such as effective hydrogen diffusion coefficients between 10−11 - 10−9.5 m2 s−1, particularly in combination with a hydrogen uptake jH of more than 0.1 A m−2, may lead to locally increased hydrogen concentrations in the material.

Numerical Simulations Reproduce Field Observations Showing Transient Weakening During Shear Zone Formation by Diffusional Hydrogen Influx and H2O Inflow

AbstractExposures on Holsnøy island (Bergen Arcs, Norway) indicate fluid infiltration through fractures into a dry, metastable granulite, which triggered a kinetically delayed eclogitization, a transient weakening during fluid‐rock interaction, and formation of shear zones that widened during shearing. It remains unclear whether the effects of grain boundary‐assisted aqueous fluid inflow on the duration of granulite hydration were influenced by a diffusional hydrogen influx accompanying the fluid inflow. To better estimate the fluid infiltration efficiencies and the parameter interdependencies, a 1D numerical model of a viscous shear zone is utilized and validated using measured mineral phase abundance distributions and H2O‐contents in nominally anhydrous minerals of the original granulite assemblage to constrain the hydration by aqueous fluid inflow and diffusional hydrogen influx, respectively. Both hydrations are described with a diffusion equation and affect the effective viscosity. Shear zone kinematics are constrained by the observed shear strain and thickness. The model fits the phase abundance and H2O‐content profiles if the effective hydrogen diffusivity is approximately one order of magnitude higher than the diffusivity for aqueous fluid inflow. The observed shear zone thickness is reproduced if the viscosity ratio between dry granulite and deforming, reequilibrating eclogite is ∼104 and that between dry granulite and hydrated granulite is ∼102. The results suggest shear velocities <10−2 cm/a, hydrogen diffusivities of ∼10−13±1 m2/s, and a shearing duration of <10 years. This study successfully links and validates field data to a shear zone model and highlights the importance of hydrogen diffusion for shear zone widening and eclogitization.

Impact of Variant Gate Insulator Fabrication Process on Reliability of Dual-Gate InGaZnO Thin-Film Transistors

The effect of hydrogen diffusion in the bilayer bottom gate insulator (BGI) in dual-gate InGaZnO (IGZO) thin-film transistors (TFT) is investigated. It is discovered that hydrogen diffuses from the first deposited GI, migrates toward the second one, and forms a weak chemical bond with a dangling bond at the interface between the GI and the active layer. The stress condition with a positive gate bias at various temperatures makes the weakly bonded hydrogen break, thereby forming defects that can induce electron trapping in the interface and bulk, causing the threshold voltage to increase. With the rising temperature of positive bias temperature stress (PBTS), more broken bonds appear at the interface, which results in more trapped electrons. Through a charge trapping model and data fitting, the parameter that indicates the quality of the film can be extracted and compared. The trend of degradation between threshold voltage, bond breaking, and defect generation is examined.

Experimental comparison of gaseous and electrochemical hydrogen charging in X65 pipeline steel using the permeation technique

Herein, hydrogen uptake and diffusivity in X65 pipeline steel were investigated using the permeation technique under different hydrogen charging conditions. Hydrogen charging was performed using hydrogen gas at different pressures, and electrochemical charging was performed at different cathodic current densities. The results revealed that both the sub-surface hydrogen concentration in lattice and reversible trap sites and the effective hydrogen diffusivity were dependent on the charging conditions. Moreover, the relationship between equivalent hydrogen fugacity and overpotential was determined.

Effect of Cold Deformation on the Hydrogen Permeation Behavior of X65 Pipeline Steel

In this study, an electrochemical hydrogen permeation experiment was used to determine the diffusion parameters, and a hydrogen microprint test was used to visualize the distribution of hydrogen in X65 pipeline steel with different levels of cold deformation. The hydrogen permeation curves show that both hydrogen permeation current density and effective hydrogen diffusion coefficient decrease with increasing cold deformation. The density of reversible and irreversible hydrogen traps is calculated from the permeation parameters, and it is found that the amount of both traps increases with increasing deformation, especially a significant increase in reversible hydrogen traps, which is in agreement with the results measured by thermal desorption spectroscopy. Hydrogen microprint test results indicate that the degree of hydrogen aggregation on the specimen surface increases with increasing cold deformation, especially at phase and grain boundaries. In addition, the dislocation configuration after cold deformation was further investigated by transmission electron microscopy.

Hydrogen Embrittlement Susceptibility of Corrosion-Resistant Spring Rod Used in High-Speed Railway

The corrosion of spring steel is very important for vehicle safety. In this work, we conducted an experiment on multi-element micro-alloy composition design; the corrosion resistance of a 60Si2Mn spring was improved by adding Cr, Ni, Cu and other corrosion-resistant elements, and the corrosion resistance index (I) was increased from 3.21 to 8.62. Hydrogen embrittlement resistance was studied using a hydrogen permeation experiment and a slow strain rate tensile experiment. For this study, the following steps were performed: Firstly, the material composition was designed, and the experimental materials that met the experimental design were prepared according to the corresponding deformation and heat treatment process; secondly, the experimental materials were charged with hydrogen; and finally, conventional tensile testing, slow tensile testing and fracture morphology testing were carried out. A hydrogen permeation experiment was carried out for the materials. The result showed that, with the increase of hydrogen charging time, the hydrogen content of two steel samples increased, and the plasticity indexes such as elongation and reduction of the area appeared in three different stages which rapidly decreased, slowly declined, and then tended to balance. The uniform NbC nano precipitated phase can double the number of irreversible hydrogen traps (Nir) per unit volume, and decreased the effective hydrogen diffusion coefficient (Deff) from 1.135 × 10−10 to 6.036 × 10−11. It limited the free diffusion of hydrogen and made the immersed hydrogen harmless, thus improving the hydrogen embrittlement resistance of corrosion-resistant spring steel 60Si2Mn.

Publisher Correction: Alleviation of Hydrogen Embrittlement to Delay Effective Hydrogen Diffusion Against MA Constituent Formation Due to Mo Solutes for 420 MPa Grade Offshore Steels

Publisher Correction: Alleviation of Hydrogen Embrittlement to Delay Effective Hydrogen Diffusion Against MA Constituent Formation Due to Mo Solutes for 420 MPa Grade Offshore Steels

Hydrogen embrittlement behavior in the nugget zone of friction stir welded X100 pipeline steel

Hydrogen-induced damage is an inevitable challenge in pipeline safety applications, especially, the fusion welded joints owing to microstructure heterogeneity caused by welding process. In this work, X100 pipeline steel was subjected to friction stir welding (FSW) at rotation rates of 300–600 rpm under water cooling, and the relationship among the microstructure, hydrogen diffusivity, and hydrogen embrittlement (HE) behavior of the nugget zone (NZ) were studied. The NZ at 600 rpm had the highest effective hydrogen diffusion coefficient (Deff) of 2.1 × 10−10 m2/s because of the highest dislocation density and lowest ratio of effective grain boundary. The Deff decreased with decreasing rotation rate due to the decrease of dislocation density and the increase of ratio of effective grain boundary, and the lowest Deff of 1.32 × 10−10 m2/s was obtained at 300 rpm. After hydrogen charging, the tensile strength of all specimens decreased slightly, while the elongation decreased significantly. As the rotation rate decreased, the elongation loss was obviously inhibited, and ultimately a lowest elongation loss of 31.8% was obtained at 300 rpm. The abovementioned excellent mechanical properties were attributed to the fine ferrite/martensite structure, low Deff, and strong {111}//ND texture dramatically inhibiting hydrogen-induced cracking initiation and propagation.

Alleviation of Hydrogen Embrittlement to Delay Effective Hydrogen Diffusion Against MA Constituent Formation Due to Mo Solutes for 420 MPa Grade Offshore Steels

Alleviation of Hydrogen Embrittlement to Delay Effective Hydrogen Diffusion Against MA Constituent Formation Due to Mo Solutes for 420 MPa Grade Offshore Steels

Accelerating off-lattice kinetic Monte Carlo simulations to predict hydrogen vacancy-cluster interactions in [formula omitted]-Fe

We present an enhanced off-lattice kinetic Monte Carlo (OLKMC) model, based on a new method for tolerant classification of atomistic local-environments that is invariant under Euclidean-transformations and permutations of atoms. Our method ensures that environments within a norm-based tolerance are classified as equivalent. During OLKMC simulations, our method guarantees to elide the maximum number of redundant saddle-point searches in symmetrically equivalent local-environments. Hence, we are able to study the trapping/detrapping of hydrogen from up to five-vacancy clusters and simultaneously the effect hydrogen has on the diffusivity of these clusters. These processes occur at vastly different timescales at room temperature in body-centred cubic iron. We predict the diffusion pathways of clusters/complexes without a priori assumptions of their mechanisms, not only reproducing previously reported mechanisms but also discovering new ones for larger complexes. We detail the hydrogen-induced changes in the clusters’ diffusion mechanisms and find evidence that, in contrast to mono-vacancies, the introduction of hydrogen to larger clusters can increase their diffusivity. We compare the effective hydrogen diffusivity to Oriani’s classical theory of trapping, finding general agreement and some evidence that hydrogen may not always be in equilibrium with traps, when the traps are mobile. Finally, we compute the trapping atmosphere of meta-stable states surrounding non-point traps, opening new avenues to better understand and predict hydrogen embrittlement in complex alloys.

AC interference on hydrogen absorption in low carbon steel under cathodic protection

The effect of AC and cathodic protection (CP) potentials on hydrogen evolution and absorption in carbon steel 1010 is investigated by hydrogen permeation tests, using a Devanathan-Stachurski electrochemical cell. Hydrogen evolution reaction occurs via the coupled discharge-recombination mechanism under CP and AC. Hydrogen permeation is controlled by bulk diffusion and less than 1% of the total hydrogen permeates through the steel membrane. A significant increase in the hydrogen uptake occurs as the AC voltage increases with more negative CP potentials. More negative CP potentials increase the hydrogen flux and absorption under AC imposition. The highest effective hydrogen diffusivity (∼5 × 10−8 cm2/s) and subsurface hydrogen concentration (∼3.5 × 10−5 mol/cm3) are found at −1.5 VSCE with AC imposition. These results demonstrate a synergy between the CP potential and AC voltage on the hydrogen evolution and absorption behavior in steel and provide insights into the implications of AC interference with CP on hydrogen embrittlement.