arXiv subjects

A. Zafra

Publications and source records attributed to A. Zafra.

7 recordsLinked to original sources

arXiv2026

High-sensitivity hydrogen gas permeation: system development, sample preparation, and influence of testing variables

There is a need to develop quantitative, high-resolution hydrogen gas (H2) permeation techniques to provide a better understanding of hydrogen-material interactions. This study aims to develop and validate a high-sensitivity H2 permeation system, which is then leveraged to systematically quantify the influence of surface condition and key testing variables (surface oxides, residual gas impurities, pressure, and temperature) on hydrogen permeation. A gas permeation system capable of operating at pressures up to 50 bar and temperatures up to 250 C was developed, incorporating high-sensitivity mass spectrometric detection and controlled surface preparation protocols. Permeation transients were analysed in a model material (annealed pure Fe) to determine hydrogen diffusivity and permeability under systematically varied surface states, oxygen contents, pressures and temperatures. Surface oxides are shown to play a dominant role in controlling hydrogen permeation at room temperature. The presence of oxide layers can severely hinder or completely suppress hydrogen uptake, with measurable permeation requiring oxide removal via pickling and Pd coating on both surfaces, or activation through hydrogen-assisted reduction at elevated temperature. Residual oxygen present prior to hydrogen exposure further reduces permeability by modifying surface boundary conditions, indicating strongly surface-controlled kinetics. Under optimised surface conditions, hydrogen transport follows bulk diffusion-controlled behaviour, with steady-state flux obeying Sieverts' law at 25 C (1-5 bar) and diffusivity and permeability exhibiting Arrhenius behaviour between 25 and 150 C at 5 bar, indicating bulk diffusion-controlled transport. The developed system resolves hydrogen fluxes as low as 1.98x10-9 mol(m2 s) and provides a robust platform for investigating surface, mechanical and environmental effects on H2 permeation.

physics.chem-ph↗

arXiv2026

Cryogenic hydrogen embrittlement of 316plus (EN 1.4420) stainless steel at 77 K and 20 K

This paper presents the first experimental characterisation of combined hydrogen-temperature effects in 316plus (EN 1.4420), a new austenitic stainless steel for liquid hydrogen (LH2) storage. Uniaxial tensile tests were conducted at room temperature (RT), 77 K and 20 K on uncharged and hydrogen-precharged specimens, complemented by fractography and EBSD-based quantification of strain-induced martensite (SIM). 316plus exhibited cryogenic strengthening at 77 K and 20 K by enhanced SIM formation. Hydrogen did not influence strength at RT or 77 K and caused a modest decrease (~10%) at 20 K, keeping 316plus at the upper bound of cryogenic strength for 316L. The presence of hydrogen resulted in significant reductions in ductility at all temperatures, being most severe at 77 and 20K (~40-50%). Hydrogen suppressed SIM at 20 K, but SIM fraction did not correlate with ductility reduction. Despite the combined effect of temperature and hydrogen, 316plus retained notable ductility (reduction in area ~30%).

physics.chem-ph↗

arXiv2025

New insights into hydrogen-assisted intergranular cracking in nickel

We characterize the grain boundary (GB) susceptibility to hydrogen-assisted intergranular cracking in pure nickel as a function of coincident site lattice value ($\Sigma$-n), over a wide range of hydrogen concentrations (4 to 14 wppm). Cracks on the surface and within the bulk material were identified across the entire gauge region of the specimens. The susceptibility of GBs to crack initiation and propagation was evaluated by separating cracks containing single GB or multiple GBs. A larger loss in fracture strain, a smaller reduction in area, and an increase in the percentage of intergranular fracture indicated a higher degree of embrittlement at elevated hydrogen concentrations. The number of cracks was significantly higher on the surface than in the bulk for the most severe hydrogen charging conditions ($\geq$ 8 wppm), while a similar number was observed for lower concentrations. The propensity for hydrogen-assisted intergranular cracking at different types of GBs on the surface and in the bulk material was consistent, indicating that while cathodic charging can promote surface cracks, it does not significantly impact the GBs relative susceptibility. The $\Sigma$-3 boundaries were the most resistant to cracking, as evidenced by the considerably lower fraction of these GBs exhibiting intergranular cracking at all hydrogen concentrations considered. This contrasts literature findings for Ni alloys and can be explained by the segregation energies and reductions in the cohesive strength with hydrogen, with less favorable trapping at the $\Sigma$-3 boundaries. No evidence of plasticity-mediated cracking initiation was observed.

cond-mat.mtrl-sci↗

arXiv2024

Helping university students to choose elective courses by using a hybrid multi-criteria recommendation system with genetic optimization

The wide availability of specific courses together with the flexibility of academic plans in university studies reveal the importance of Recommendation Systems (RSs) in this area. These systems appear as tools that help students to choose courses that suit to their personal interests and their academic performance. This paper presents a hybrid RS that combines Collaborative Filtering (CF) and Content-based Filtering (CBF) using multiple criteria related both to student and course information to recommend the most suitable courses to the students. A Genetic Algorithm (GA) has been developed to automatically discover the optimal RS configuration which include both the most relevant criteria and the configuration of the rest of parameters. The experimental study has used real information of Computer Science Degree of University of Cordoba (Spain) including information gathered from students during three academic years, counting on 2500 entries of 95 students and 63 courses. Experimental results show a study of the most relevant criteria for the course recommendation, the importance of using a hybrid model that combines both student information and course information to increase the reliability of the recommendations as well as an excellent performance compared to previous models.

cs.LG↗

arXiv2022

On the relative efficacy of electropermeation and isothermal desorption approaches for measuring hydrogen diffusivity

The relative efficacy of electrochemical permeation (EP) and isothermal desorption spectroscopy (ITDS) methods for determining the hydrogen diffusivity is investigated using cold-rolled pure iron. The diffusivities determined from 13 first transient and 8 second transient EP experiments, evaluated using the conventional lag and breakthrough time methods, are compared to the results of 10 ITDS experiments. Results demonstrate that the average diffusivity is similar between the second EP transient and ITDS, which are distinctly increased relative to the first EP transient. However, the coefficient of variation for the ITDS experiments is reduced by 2 and 3-fold relative to the first and second EP transients, confirming the improved repeatability of ITDS diffusivity measurements. The source of the increased error in EP measurements is systematically evaluated, revealing an important influence of assumed electrochemical boundary conditions on the analysis and interpretation of EP experiments.

physics.chem-ph↗

arXiv2021

Comparison of hydrogen diffusivities measured by electrochemical permeation and temperature-programmed desorption in cold-rolled pure iron

The diffusivity of hydrogen in cold-rolled pure iron is investigated using permeation and desorption methods. Electrochemical charging, electro-permeation and thermal desorption spectroscopy (TDS) experiments are conducted. Firstly, the relation between the charging current and the hydrogen concentration is established. Secondly, permeation experiments are conducted at 22, 40 and 67°C to quantify the diffusivity dependence on temperature. Finally, the diffusivity is estimated by using two types of desorption experiments and Fick's law: (i) a `rest time' method, by which we measure the hydrogen content of samples held at room temperature for different times, and (ii) isothermal desorption experiments at temperatures ranging from 22 to 80°C, fitting the resulting desorption rate versus time curves. Good agreement is obtained between the isothermal desorption and permeation approaches, with observed differences discussed and rationalised. Moreover, measured diffusivity values for cold-rolled pure iron are also found to be comparable to those reported in the literature. This work demonstrates that isothermal desorption experiments are a convenient approach to determine hydrogen diffusivity over a wide range of temperatures, as facilitated by new TDS systems with fast heating rates.

cond-mat.mtrl-sci↗

arXiv2020

Simulation of hydrogen permeation through pure iron for trapping and surface phenomena characterisation

There is a need for numerical models capable of predicting local accumulation of hydrogen near stress concentrators and crack tips to prevent and mitigate hydrogen assisted fracture in steels. The experimental characterisation of trapping parameters in metals, which is required for an accurate simulation of hydrogen transport, is usually performed through the electropermeation test. In order to study grain size influence and grain boundary trapping during permeation, two modelling approaches are explored; a 1D Finite Element model including trap density and binding energy as input parameters and a polycrystalline model based on the assignment of a lower diffusivity and solubility to the grain boundaries. Samples of pure iron after two different heat treatments - 950C for 40 minutes and 1100C for 5 minutes - are tested applying three consecutive rising permeation steps and three decaying steps. Experimental results show that the finer grain microstructure promotes a diffusion delay due to grain boundary trapping. The usual methodology for the determination of trap densities and binding energies is revisited in which the limiting diluted and saturated cases are considered. To this purpose, apparent diffusivities are fitted including also the influence of boundary conditions and comparing results provided by the constant concentration with the constant flux assumption. Grain boundaries are characterised for pure iron with a binding energy between 37.8 and 39.9 kJ/mol and a low trap density but it is numerically demonstrated that saturated or diluted assumptions are not always verified, and a univocal determination of trapping parameters requires a broader range of charging conditions for permeation. The relationship between surface parameters, i.e. charging current, recombination current and surface concentrations, is also studied.

physics.app-ph↗