Hydrogen embrittlement contributions to fatigue crack growth in a structural steel

The detrimental effects of a hydrogen atmosphere on the fatigue resistance of BS 4360 steel have been assessed by a comparison of crack growth rates in air and hydrogen at a low cycling frequency (0.1Hz), and at a number of temperature (25, 50 and 80 °C). The crack propagation rates in air are almost independent of temperature over this range, but those measured in hydrogen differ by more than an order of magnitude between 25 and 80 °C. The greatest enhancement is seen at 25 °C and at high values of ΔK, the maximum occurring between 40–45 MPa √m at each temperature. There is little hydrogen contribution to crack growth at values of ΔK below 20 MPa √m for R = 0.1. The enhancement of crack growth rates is reflected by the presence of ‘quasi-cleavage’ facets on the fatigue fracture surfaces of specimens tested in hydrogen. These are most apparent where the greatest increases in growth rate are recorded. The facets show linear markings, which run both parallel and perpendicular to the direction of crack growth. The former are analogous to the ‘river’ lines noted on brittle cleavage facets, and reflect the propagation direction. The latter are more unusual, and indicate that facet formation by hydrogen embrittlement during fatigue is a step-wise process.

Significant quantum effects in hydrogen activation

Dissociation of molecular hydrogen is an important step in a wide variety of chemical, biological, and physical processes. Due to the light mass of hydrogen, it is recognized that quantum effects are often important to its reactivity. However, understanding how quantum effects impact the reactivity of hydrogen is still in its infancy. Here, we examine this issue using a well-defined Pd/Cu(111) alloy that allows the activation of hydrogen and deuterium molecules to be examined at individual Pd atom surface sites over a wide range of temperatures. Experiments comparing the uptake of hydrogen and deuterium as a function of temperature reveal completely different behavior of the two species. The rate of hydrogen activation increases at lower sample temperature, whereas deuterium activation slows as the temperature is lowered. Density functional theory simulations in which quantum nuclear effects are accounted for reveal that tunneling through the dissociation barrier is prevalent for H2 up to ∼190 K and for D2 up to ∼140 K. Kinetic Monte Carlo simulations indicate that the effective barrier to H2 dissociation is so low that hydrogen uptake on the surface is limited merely by thermodynamics, whereas the D2 dissociation process is controlled by kinetics. These data illustrate the complexity and inherent quantum nature of this ubiquitous and seemingly simple chemical process. Examining these effects in other systems with a similar range of approaches may uncover temperature regimes where quantum effects can be harnessed, yielding greater control of bond-breaking processes at surfaces and uncovering useful chemistries such as selective bond activation or isotope separation.