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

: Two important advances over the past 40 years enable the optimization and management of the structural integrity of components in high performance applications. First, the solid mechanics conununity established linear elastic fracture mechanics as the premier framework for modeling the damage tolerance of fracture critical components (Irwin and Wells, 1997; Paris, 1998). Second, materials scientists developed metals with outstanding balances of high tensile strength and high fracture toughness (Garrison, 1990; Wells, 1993; Boyer, 1993; Starke and Staley, 1995; Olson, 1997; Kolts, 1996). An example of achievable strength-toughness properties is provided in Fig. 1, a plot of plane strain fracture toughness vs. tensile yield strength (sigma-YS) for ultra-high strength steels (UHSS) and beta-Ti alloys precipitation hardened with a phase (Gangloff 2001). New nano-scale characterization and high performance computational methods provide for additional advances in the mechanical performance properties of structural metals. These modem alloys and analysis tools satisfy technological needs for optimization and management of component performance in demanding fatigue and fracture critical applications in the aerospace, marine, energy, transportation, and defense sectors.

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Hydrogen Assisted Cracking of High Strength Alloys

6.02 – Hydrogen-assisted Cracking

Stress corrosion cracking of Al-Zn-Mg-Cu (AA7xxx) aluminum alloys exposed to saline environments at temperatures ranging from 293 K to 353 K (20 °C to 80 °C) has been reviewed with particular attention to the influences of alloy composition and temper, and bulk and local environmental conditions. Stress corrosion crack (SCC) growth rates at room temperature for peak- and over-aged tempers in saline environments are minimized for Al-Zn-Mg-Cu alloys containing less than ~8 wt pct Zn when Zn/Mg ratios are ranging from 2 to 3, excess magnesium levels are less than 1 wt pct, and copper content is either less than ~0.2 wt pct or ranging from 1.3 to 2 wt pct. A minimum chloride ion concentration of ~0.01 M is required for crack growth rates to exceed those in distilled water, which insures that the local solution pH in crack-tip regions can be maintained at less than 4. Crack growth rates in saline solution without other additions gradually increase with bulk chloride ion concentrations up to around 0.6 M NaCl, whereas in solutions with sufficiently low dichromate (or chromate), inhibitor additions are insensitive to the bulk chloride concentration and are typically at least double those observed without the additions. DCB specimens, fatigue pre-cracked in air before immersion in a saline environment, show an initial period with no detectible crack growth, followed by crack growth at the distilled water rate, and then transition to a higher crack growth rate typical of region 2 crack growth in the saline environment. Time spent in each stage depends on the type of pre-crack (“pop-in” vs fatigue), applied stress intensity factor, alloy chemistry, bulk environment, and, if applied, the external polarization. Apparent activation energies (Ea) for SCC growth in Al-Zn-Mg-Cu alloys exposed to 0.6 M NaCl over the temperatures ranging from 293 K to 353 K (20 °C to 80 °C) for under-, peak-, and over-aged low-copper-containing alloys ( ~0.8 wt pct), they are typically ranging from 20 to 40 kJ/mol for under- and peak-aged alloys, and based on limited data, around 85 kJ/mol for over-aged tempers. This means that crack propagation in saline environments is most likely to occur by a hydrogen-related process for low-copper-containing Al-Zn-Mg-Cu alloys in under-, peak- and over-aged tempers, and for high-copper alloys in under- and peak-aged tempers. For over-aged high-copper-containing alloys, cracking is most probably under anodic dissolution control. Future stress corrosion studies should focus on understanding the factors that control crack initiation, and insuring that the next generation of higher performance Al-Zn-Mg-Cu alloys has similar longer crack initiation times and crack propagation rates to those of the incumbent alloys in an over-aged condition where crack rates are less than 1 mm/month at a high stress intensity factor.

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Stress Corrosion Cracking in Al-Zn-Mg-Cu Aluminum Alloys in Saline Environments

The coupled effect of corrosion and fatigue deteriorates the performance of reinforced concrete (RC) structures. This paper proposes a novel framework for the probabilistic life prediction ...

Probabilistic Life Prediction for Reinforced Concrete Structures Subjected to Seasonal Corrosion-Fatigue Damage

The state of the art in crack chemistry modeling is assessed. An overview of conceptual understanding of the processes occurring in a crack is given, and the foundations for establishing m...

A. Turnbull

Papers

Modeling of the chemistry and electrochemistry in cracks : A review