The effects of hydrogen on the physical and mechanical properties of iron and steel are reviewed. A new mechanism for the cold work peak for hydrogen in iron is considered. Together, internal friction and mechanical properties indicate that hydrogen softens iron by enhancing screw dislocation mobility at room temperature but hardens iron by core interactions at low temperatures. No single mechanism exists for the degradation of the properties of steel by hydrogen. Instead a complex process involving many of the proposed mechanisms as contributing factors is shown to account for most degradation phenomena.

Effects of hydrogen on the properties of iron and steel

A simple method for evaluating stress intensity factor, crack velocity (K, V) diagrams is described. The method is evaluated for the glass/water system and is shown to generate data that are entirely consistent with data obtained on the same system using other techniques. The method is applied to the alumina/water system and the K, V diagrams are used to predict times to failure (Ψ) and effects of strain-rate on strength (σf). The calculated Ψ and σf, are in excellent agreement with available data.

A method for evaluating the time-dependent failure characteristics of brittle materials — and its application to polycrystalline alumina

A kinetic model is presented for the transport of hydrogen, as Cottrell atmospheres on dislocation, at a rate appreciably in excess of that for lattice diffusion. The particular destinations for the hydrogen which are modeled here are ductile fracture initiation sites such as inclusions and microvoids. The functional predictions of the mechanism are shown to be consistent with available experimental evidence on ductile fracture behavior in the presence of hydrogen.

Hydrogen transport by dislocations

A simple, inexpensive method for studying slow crack growth is described. The method entails measurements of load relaxation at constant displacement using a double torsion specimen. It is demonstrated that the data generated using this technique are in excellent agreement with data obtained using the more complex conventional techniques, for a range of materials - steel, titanium, glass, aluminum oxide, PMMA. These encouraging initial results suggest that additional and more detailed studies using this test procedure are merited.

A simple method for studying slow crack growth.

We present a model of hydrogen embrittlement based upon: (i) a cohesive law dependent on impurity coverage that is calculated from first principles; (ii) a stress-assisted diffusion equation with appropriate boundary conditions accounting for the environment; (iii) a static continuum analysis of crack growth including plasticity; and (iv) the Langmuir relation determining the impurity coverage from its bulk concentration. We consider the effect of the following parameters: yield strength, stress intensity factor, hydrogen concentration in the environment, and temperature. The calculations reproduce the following experimental trends: (i) time to initiation and its dependence on yield strength and stress intensity factor; (ii) finite crack jump at initiation; (iii) intermittent crack growth; (iv) stages I and II of crack growth and their dependence on yield strength; (v) the effect of the environmental impurity concentration on the threshold stress intensity factor; and (vi) the effect of temperature on stage II crack velocity in the low-temperature range. In addition, the theoretically and experimentally observed intermittent cracking may be understood as being due to a time lag in the diffusion of hydrogen towards the cohesive zone, since a buildup of hydrogen is necessary in order for the crack to advance. The predictions of the model are in good quantitative agreement with available measurements, suggesting that hydrogen-induced degradation of cohesion is a likely mechanism for hydrogen-assisted cracking.

A quantum-mechanically informed continuum model of hydrogen embrittlement

Quenched and tempered steel, investigating embrittlement as function of temperature in partially dissociated atomic hydrogen environment

Embrittlement of a ferrous alloy in a partially dissociated hydrogen environment

Study of environmental hydrogen embrittlement of a Ti-6 Al-4 alloy as a function of test displacement rate and of variations in alpha-beta microstructure Embrittlement in low-pressure (about 1 atm) gaseous hydrogen was inversely dependent on test displacement rate and strongly dependent on microstructure At a given displacement rate, microstructures having a continuous alpha-phase matrix were less severely embrittled than those having a continuous beta-phase matrix Further, brittle fracture occurred in the former microstructures by transgranular cleavage and in the latter microstructures by intergranular separation These observations are consistent with previous studies made on slow strain-rate embrittlement of hydrogen-charged titanium alloys and are explained in terms of relative hydrogen transport rates within the alpha-phase and beta-phase titanium

Environmental hydrogen embrittlement of an α-β titanium alloy: Effect of microstructure

The kinetics of hydrogen-induced cracking have been studied in the Ti-5Al-2.5Sn titanium alloy having a structure of acicular α platelets in a β matrix. It was observed that the relationship between hydrogen-induced crack growth rate and applied stress intensity can be described by three separable regions of behavior. The crack-growth rate at low stress-intensity levels was found to be exponentially dependent on stress intensity but essentially independent of temperature. The crack-growth rate at intermediate stress-intensity levels was found to be independent of stress intensity but dependent on temperature in such a way that crack-growth rate was controlled by a thermally activated mechanism having an activation energy of 5500 cal per mole and varied as the square root of the hydrogen pressure. The crack-growth rate at stress-intensity levels very near the fracture toughness is presumed to be independent of environment. The results are interpreted to suggest that crack growth at high stress intensities is controlled by normal, bulk failure mechanisms such as void coalescence and the like. At intermediate stress-intensity levels the transport of hydrogen to some interaction site along the α-β boundary is the rate-controlling mechanism. The crack-growth behavior at low stress intensities suggests that the hydrogen interacts at this site to produce a strain-induced hydride which, in turn, induces crack growth by restricting plastic flow at the crack tip.

Gaseous hydrogen-induced cracking of Ti-5Al-2.5Sn

A study has been conducted of the terrace-like fracture morphology of gaseous hydrogen-induced crack growth in acicular alpha-beta titanium alloys in terms of specimen configuration, magnitude of applied stress intensity, test temperature, and hydrogen pressure. Although the overall appearance of the terrace structure remained essentially unchanged, a distinguishable variation is found in the size of the individual terrace steps, and step size is found to be inversely dependent upon the rate of hydrogen-induced slow crack growth. Additionally, this inverse relationship is independent of all the variables investigated. These observations are quantitatively discussed in terms of the formation and growth of a thin hydride film along the alpha-beta boundaries and a qualitative model for hydrogen-induced slow crack growth is presented, based on the film-rupture model of stress corrosion cracking.

A film-rupture model of hydrogen-induced, slow crack growth in acicular alpha-beta titanium

The stability fields of various sulfide phases that form on Fe-Cr, Fe-Ni, Ni-Cr, and Fe-Cr-Ni alloys have been developed as a function of temperature and the partial pressure of sulfur. The calculated stability fields in the ternary A-B-S system are displayed on plots of log \textpS2 pS2 vs. the conjugate extensive variable (nA/nA–nB), which provides a better framework for following the sulfidation of Fe-Cr-Ni alloys at high temperatures. Experimental and estimated thermodynamic data were used in developing the sulfur potential diagrams. Current models and correlations were employed to estimate the unknown thermodynamic behavior of solid solutions of sulfides and to supplement the incomplete phase-diagram data of geophysical literature. These constructed stability field diagrams are in excellent agreement with the sulfide phases and compositions determined experimentally during the sulfidation of SAE 310 stainless steel. The sulfur potential plots appear to be very useful in predicting and correlating the sulfidation of commercial alloys.

Howard G. Nelson

Papers

Embrittlement of a ferrous alloy in a partially dissociated hydrogen environment

Environmental hydrogen embrittlement of an α-β titanium alloy: Effect of microstructure

Gaseous hydrogen-induced cracking of Ti-5Al-2.5Sn

A film-rupture model of hydrogen-induced, slow crack growth in acicular alpha-beta titanium

Phase relations in the Fe-Ni-Cr-S system and the sulfidation of an austenitic stainless steel