The Effect of Microstructural Characteristics on the Hydrogen Permeation Transient in Quenched and Tempered Martensitic Alloys

This work evaluates the permeation curve characteristics for four quenched and tempered generic, ternary alloys, each containing one specific carbide. The different carbides (W2C, Cr23C6, TiC, and V4C3, respectively) are induced by a quench and tempering treatment. The correlation is made between the different microstructural characteristics, including the carbides and the martensitic matrix, and the observed hydrogen diffusivity and thus the permeation transient. The permeation curves, obtained via the Devanathan and Stachurski method, are therefore compared with thermal desorption spectroscopy and hot extraction results. The delay of the permeation transient can be associated with the overall trap density, while the slope is related to the amount of reversible trapping sites. Generally, the obtained hydrogen permeation transient of the different ternary or Fe–C–X materials correlates with the hydrogen trapping ability. The following order of hydrogen diffusion is determined, i.e., Fe–C–V < Fe–C–Ti << Fe–C–Cr < Fe–C–W. The hydrogen trapping ability of the tempered induced carbides plays a decisive role in the value of the hydrogen diffusion coefficient.

Numerical Study of Hydrogen Trapping: Application to an API 5L X60 Steel

A numerical finite difference method is developed here to solve the diffusion equation for hydrogen in presence of trapping sites. A feature of our software is that an optimization of diffusion and trapping parameters is achieved via a non linear least squares fit. On the other hand, we have demonstrated that usual electrochemical hydrogen permeation tests are enough to assess hydrogen free energies of trapping in the range of −35 kJ/mol to −70 kJ/mol. These conclusions are obtained by assuming the presence of saturable traps in local equilibrium with hydrogen and are validated by means of simulated permeation and degassing transients. In addition, we check our model performing electrochemical hydrogen permeation tests at 30°C, 50°C, and 70°C, on an API 5L X60 as received steel state to study its trapping and diffusion properties considering only one type of trapping site. The binding energies (ΔG) and the trap densities (N) are determined by fitting the theoretical model to the experimental permeation data. The steel presents a high density of weak traps, |ΔG|<35 KJ/mol, namely, N=1.4×10−5 mol cm−3. Strong trapping sites which alter the shape of the permeation transient are also detected; their ΔG values ranged from 57 to 72 KJ/mol.

Thermo-Chemo-Mechanical Modelling of Mixed Conductors in Transient Stages

This study deals with the modelling of the mechanical behaviour accounting for the expansion induced by the oxygen diffusion in MIECs membrane during semi-permeation transient stage. A dedicated model of chemical expansion and its numerical implementation is used to study the relationship between the mechanical stress and the oxygen flux. The impact of the ratio between oxygen bulk diffusion and surface exchange kinetics on mechanical stress in transient stage is discussed. At last, the need of a compromise between the oxygen flux performance and the mechanical reliability is underlined.