Hydrogen embrittlement (HE) also known as hydrogen assisted cracking (HAC) and hydrogen-induced cracking (HIC), describes the embrittling of metal after being exposed to hydrogen. It is a complex process that is not completely understood because of the variety and complexity of mechanisms that can lead to embrittlement. Mechanisms that have been proposed to explain embrittlement include the formation of brittle hydrides, the creation of voids that can lead to bubbles and pressure build-up within a material and enhanced decohesion or localised plasticity that assist in the propagation of cracks.
For hydrogen embrittlement to occur, a combination of three conditions are required:
- the presence and diffusion of hydrogen
- a susceptible material
Hydrogen is often introduced during manufacture from operations such as forming, coating, plating or cleaning. Hydrogen may also be introduced over time (external embrittlement) through environmental exposure (soils and chemicals, including water), corrosion processes (especially galvanic corrosion) including corrosion of a coating and cathodic protection.
During hydrogen embrittlement, hydrogen is introduced to the surface of a metal and individual hydrogen atoms diffuse through the metal structure. Because the solubility of hydrogen increases at higher temperatures, raising the temperature can increase the diffusion of hydrogen. When assisted by a concentration gradient where there is significantly more hydrogen outside the metal than inside, hydrogen diffusion can occur even at lower temperatures.
Adsorbed hydrogen species recombine to form hydrogen molecules, creating pressure from within the metal. This pressure can increase to levels where the metal has reduced ductility, toughness, and tensile strength, up to the point where it cracks open (hydrogen-induced cracking, or HIC).
Metal hydride formation:
The formation of brittle hydrides with the parent material allows cracks to propagate in a brittle fashion.
Phase transformations occur for some materials when hydrogen is present.
Hydrogen enhanced decohesion:
Hydrogen enhanced decohesion (HEDE) where the strength of the atomic bonds of the parent material are reduced.
Hydrogen enhanced localised plasticity:
Hydrogen enhanced localised plasticity (HELP) is the process where the generation and movement of dislocations is enhanced and results in localised deformation such as at the tip of a crack increasing the propagation of the crack with less deformation in surrounding material giving a brittle appearance to the fracture. Experiments have shown that stationary dislocations begin to move when molecular hydrogen is dissociated and absorbed into pre-strained material.
Hydrogen enhanced vacancy formation:
Vacancy production can be increased in the presence of hydrogen but since vacancies cannot be readily eliminated this proposal is inconsistent with observations the removal of hydrogen reduces the embrittlement.
Hydrogen enhanced dislocation emission:
Hydrogen enhanced dislocation emission proposes that hydrogen is adsorbed onto to the surface and allows dislocations to be generated at lower stress levels thus increasing the level of localised plasticity at the tip of a crack allowing it to propagate more freely.
Hydrogen embrittles a variety of substances including steel, aluminium (at high temperatures only), and titanium. Austempered iron is also susceptible, though austempered steel (and possibly other austempered metals) display increased resistance to hydrogen embrittlement.
In tensile tests carried out on several structural metals under high-pressure molecular hydrogen environment, it has been shown that austenitic stainless steels, aluminium (including alloys), copper (including alloys, e.g. beryllium copper) are not susceptible to hydrogen embrittlement along with a few other metals.
If steel is exposed to hydrogen at high temperatures, hydrogen will diffuse into the alloy and combine with carbon to form tiny pockets of methane at internal surfaces like grain boundaries and voids. This methane does not diffuse out of the metal, and collects in the voids at high pressure and initiates cracks in the steel. This selective leaching process is known as hydrogen attack, or high temperature hydrogen attack, and leads to decarburization of the steel and loss of strength and ductility.
Steel with an ultimate tensile strength of less than 1000 MPa (~145,000 psi) or hardness of less than 32 HRC is not generally considered susceptible to hydrogen embrittlement. As an example of severe hydrogen embrittlement, the elongation at failure of 17-4PH precipitation hardened stainless steel was measured to drop from 17% to only 1.7% when smooth specimens were exposed to high-pressure hydrogen.
As the strength of steels increases, the susceptibility to hydrogen embrittlement increases. In high-strength steels, anything above a hardness of HRC 32 may be susceptible to early hydrogen cracking after plating processes that introduce hydrogen. They may also experience long-term failures anytime from weeks to decades after being placed in service due to accumulation of hydrogen over time from cathodic protection and other sources. Numerous failures have been reported in the hardness range from HRC 32-36 and more above; therefore, parts in this range should be checked during quality control to ensure they are not susceptible.
Copper alloys which contain oxygen can be embrittled if exposed to hot hydrogen. The hydrogen diffuses through the copper and reacts with inclusions of Cu2O, forming H2O (water), which then forms pressurized bubbles at the grain boundaries. This process can cause the grains to literally be forced away from each other, and is known as steam embrittlement (because steam is produced, not because exposure to steam causes the problem).
Vanadium, nickel, and titanium
A large number of alloys of vanadium, nickel, and titanium absorb significant amounts of hydrogen. This can lead to large volume expansion and damage to the crystal structure leading to the alloys becoming very brittle. This is a particular issue when looking for non-palladium based alloys for use in hydrogen separation membranes.
Sources of hydrogen
There are many sources of Hydrogen Embrittlement, however they can be divided into two categories based on how the hydrogen is introduced into the metal; Internal Hydrogen Embrittlement (IHE) and Hydrogen Environmental Embrittlement (HEE). The first category is from the preexisting hydrogen already present within the metal from creation and the second category is hydrogen introduced from the environment the metal finds itself in. Examples of Internal Hydrogen Embrittlement include processes such as casting, carbonizing, surface cleaning, pickling, electroplating, electrochemical machining, welding, roll forming, and heat treatments. Examples of Hydrogen Environmental Embrittlement include generic corrosion from exposure to the environment or through misapplication of various protection measures.
Hydrogen embrittlement can occur during various manufacturing operations or operational use - anywhere that the metal comes into contact with atomic or molecular hydrogen. Processes that can lead to this include cathodic protection, phosphating, pickling, and electroplating. A special case is arc welding, in which the hydrogen is released from moisture, such as in the coating of welding electrodes. To minimize this, special low-hydrogen electrodes are used for welding high-strength steels. Other mechanisms of introduction of hydrogen into metal are galvanic corrosion, as well as chemical reactions with acids or other chemicals. One of these chemical reactions involves hydrogen sulfide in sulfide stress cracking (SSC), a significant problem for the oil and gas industries.
Hydrogen embrittlement can be prevented through several methods, all of which are centered on minimizing contact between the metal and hydrogen, particularly during fabrication and the electrolysis of water. Embrittling procedures such as acid pickling should be avoided, as should increased contact with elements such as sulfur and phosphate. The use of proper electroplating solution and procedures can also help to prevent hydrogen embrittlement.
If the metal has not yet started to crack, hydrogen embrittlement can be reversed by removing the hydrogen source and causing the hydrogen within the metal to diffuse out through heat treatment. This de-embrittlement process, known as "baking", is used to overcome the weaknesses of methods such as electroplating which introduce hydrogen to the metal, but is not always entirely effective because a sufficient time and temperature must be reached. Tests such as ASTM F1624 can be used to rapidly identify the minimum baking time (by testing using design of experiments, a relatively low number of samples can be used to pinpoint this value). Then the same test can be used as a quality control check to evaluate if baking was sufficient on a per-batch basis.
In the case of welding, often pre-heating and post-heating the metal is applied to allow the hydrogen to diffuse out before it can cause any damage. This is specifically done with high-strength steels and low alloy steels such as the chrome/molybdenum/vanadium alloys. Due to the time needed to re-combine hydrogen atoms into the hydrogen molecules, hydrogen cracking due to welding can occur over 24 hours after the welding operation is completed.
Another way of preventing this problem is through materials selection. This will build an inherent resistance to this process and reduce the need of post processing or constant monitoring for failure. Certain metals or alloys are highly susceptible to this issue so choosing a material that is minimally affected while retaining the desired properties would also provide an optimal solution. Much research has been done to catalog the compatibility of certain metals with hydrogen. Tests such as ASTM F1624 can also be used to rank alloys and coatings during materials selection to ensure (for instance) that the threshold of cracking is below the threshold for hydrogen-assisted stress corrosion cracking. Similar tests can also be used during quality control to more effectively qualify materials being produced in a rapid and comparable manner.
Most analytical methods for hydrogen embrittlement involve evaluating the effects of (1) internal hydrogen from production and/or (2) external sources of hydrogen such as cathodic protection. For steels, it is important to test specimens in the lab that are at least as hard (or harder) than the final parts will be. Ideally, specimens should be made of the final material or the nearest possible representative, as fabrication can have a profound impact on resistance to hydrogen-assisted cracking.
There are numerous ASTM standards for testing for hydrogen embrittlement:
- ASTM B577 is the Standard Test Methods for Detection of Cuprous Oxide (Hydrogen Embrittlement Susceptibility) in Copper. The test focuses on hydrogen embrittlement of copper alloys, including a metallographic evaluation (method A), testing in a hydrogen charged chamber followed by metallography (method B), and method C is the same as B but includes a bend test.
- ASTM B839 is the Standard Test Method for Residual Embrittlement in Metallic Coated, Externally Threaded Articles, Fasteners, and Rod-Inclined Wedge Method.
- ASTM F519 is the Standard Test Method for Mechanical Hydrogen Embrittlement Evaluation of Plating/Coating Processes and Service Environments. There are 7 different samples designs and the two most commons tests are (1) the rapid test, the Rising Step Load (RSL) test per ASTM F1624 and (2) the sustained load test, which takes 200 hours. The sustained load test is still included in many legacy standards, but the RSL method is increasingly being adopted due to speed, repeatability, and the quantitative nature of the test. The RSL method provides an accurate ranking of the effect of hydrogen from both internal and external sources.
- ASTM F1459 is the Standard Test Method for Determination of the Susceptibility of Metallic Materials to Hydrogen Gas Embrittlement (HGE) Test. The test uses a diaphragm loaded with a differential pressure.
- ASTM G142 is the Standard Test Method for Determination of Susceptibility of Metals to Embrittlement in Hydrogen Containing Environments at High Pressure, High Temperature, or Both. The test uses a cylindrical tensile specimen tested into an enclosure pressurized with hydrogen or helium.
- ASTM F1624 is the Standard Test Method for Measurement of Hydrogen Embrittlement Threshold in Steel by the Incremental Step Loading Technique. The test uses the incremental step loading (ISL) or rising step load (RSL) method for quantitatively testing for the Hydrogen Embrittlement threshold stress for the onset of Hydrogen-Induced Cracking due to platings and coatings from Internal Hydrogen Embrittlement (IHE) and Environmental Hydrogen Embrittlement (EHE). F1624 provides a rapid, quantitative measure of the effects of hydrogen both from internal sources and external sources (which is accomplished by applying a selected voltage in an electrochemical cell). The F1624 test is performed by comparing a standard fast-fracture tensile strength to the fracture strength from a rising step load test where the load is held for hour(s) at each step. In many cases it can be performed in 30 hours or less.
- ASTM F1940 is the Standard Test Method for Process Control Verification to Prevent Hydrogen Embrittlement in Plated or Coated Fasteners. While the title now explicitly includes the word fasteners, F1940 was not originally intended for these purposes. F1940 is based on the F1624 method and is similar to F519 but with different root radius and stress concentration factors. When specimens exhibit a threshold cracking of 75% of the net fracture strength, the plating bath is considered to be 'non-embrittling'.
There are many other related standards for hydrogen embrittlement:
- NACE TM0284-2003 (NACE International) Resistance to Hydrogen-Induced Cracking
- ISO 11114-4:2005 (ISO)Test methods for selecting metallic materials resistant to hydrogen embrittlement.
- Standard Test Method for Mechanical Hydrogen Embrittlement Evaluation of Plating/Coating Processes and Service Environments
Notable failures from hydrogen embrittlement
- In 2013, six months prior to opening, the East Span of the Oakland Bay Bridge failed during testing. Catastrophic failures occurred in shear bolts in the span, after only two weeks of service, with the failure attributed to embrittlement, possibly from the environment.
- In the City of London, 122 Leadenhall Street, generally known as 'the Cheesegrater', suffered from hydrogen embrittlement in numerous steel bolts, with three bolts failing in 2014 and 2015. Extensive remediation works were initiated.
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- "Study reveals clues to cause of hydrogen embrittlement" (Press release). McGill University. November 19, 2012. Retrieved November 20, 2012.
- Vergani, Laura; Colombo, Chiara; et al. (2014). "Hydrogen effect on fatigue behavior of a quenched and tempered steel". Procedia Engineering. 74 (XVII International Colloquium on Mechanical Fatigue of Metals (ICMFM17)): 468–71. doi:10.1016/j.proeng.2014.06.299.
- Djukic, M.B.; et al. (2014). "Hydrogen embrittlement of low carbon structural steel". Procedia Materials Science. 3 (20th European Conference on Fracture): 1167–1172. doi:10.1016/j.mspro.2014.06.190.
- Djukic, M.B.; et al. (2015). "Hydrogen damage of steels: A case study and hydrogen embrittlement model". Engineering Failure Analysis. 58 (Recent case studies in Engineering Failure Analysis): 485–498. doi:10.1016/j.engfailanal.2015.05.017.
- Djukic, Milos B.; et al. (2016). "Hydrogen Embrittlement of Industrial Components: Prediction, Prevention, and Models". Corrosion. 72 (7, Environment Assisted Cracking): 943–961. doi:10.5006/1958.
- Ambat, Rajan; Dwarakadasa (February 1996). "Effect of Hydrogen in aluminium and aluminium alloys: A review". Bulletin of Materials Science. 19 (1): 103–114. doi:10.1007/BF02744792.
- Eberhart, Mark (2003). Why Things Break. New York: Harmony Books. p. 65. ISBN 978-1-4000-4760-4.
- Tartaglia, John; Lazzari, Kristen; et al. (March 2008). "A Comparison of Mechanical Properties and Hydrogen Embrittlement Resistance of Austempered vs Quenched and Tempered 4340 Steel". Metallurgical and Materials Transactions A. 39 (3): 559–76. Bibcode:2008MMTA...39..559T. doi:10.1007/s11661-007-9451-8. ISSN 1073-5623.
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- Gillette, J.L.; Kolpa, R.L. (November 2007). "Overview of interstate hydrogen pipeline systems" (PDF). Retrieved 2013-12-16.
- Dolan, Michael D.; Kochanek, Mark A.; Munnings, Christopher N.; McLennan, Keith G.; Viano, David M. (February 2015). "Hydride phase equilibria in V–Ti–Ni alloy membranes". Journal of Alloys and Compounds. 622: 276–281. doi:10.1016/j.jallcom.2014.10.081.
- Branko, Popov (2018). Handbook of Environmental Degradation of Materials (3rd ed.). ISBN 978-0-323-52472-8.
- Weman, Klas (2011). Welding Processes Handbook. Elsevier. p. 115. ISBN 978-0-85709-518-3.
- "Standard Test Method for Process Control Verification to Prevent Hydrogen Embrittlement in Plated or Coated Fasteners". Astm.org. Retrieved 24 February 2015.
- Main contributor: Clive D. Pearce (2006). "Hydrogen Embrittlement: An Overview from a Mechanical Fastenings Aspect" (PDF). The Fastener Engineering and Research Association. Confederation of British Metalforming. Retrieved 9 May 2015.
- Chalaftris, George (December 2003). "Abstract". Evaluation of Aluminium–Based Coatings for Cadmium Replacement (PhD thesis). Cranfield University School of Industrial and Manufacturing Science. hdl:1826/103.
- Federal Engineering and Design Support. "Embrittlement" (PDF). Fastenal. Fastenal Company Engineering Department. Retrieved 9 May 2015.
- Marchi, C. San (2012). "Technical Reference for Hydrogen Compatiblity of Materials" (PDF).
- "ASTM F1459 - 06(2012): Standard Test Method for Determination of the Susceptibility of Metallic Materials to Hydrogen Gas Embrittlement (HGE)". Astm.org. Retrieved 2015-02-24.
- "ASTM G142 - 98(2011) Standard Test Method for Determination of Susceptibility of Metals to Embrittlement in Hydrogen Containing Environments at High Pressure, High Temperature, or Both". Astm.org. Retrieved 2015-02-24.
- ASTM STP 543, "Hydrogen Embrittlement Testing"
- Raymond L (1974). Hydrogen Embrittlement Testing. ASTM International. ISBN 978-0-8031-0373-3.
- "ASTM F1940 - 07a(2014) Standard Test Method for Process Control Verification to Prevent Hydrogen Embrittlement in Plated or Coated Fasteners". Astm.org. Retrieved 2015-02-24.
- "ASTM F519 - 17a Standard Test Method for Mechanical Hydrogen Embrittlement Evaluation of Plating/Coating Processes and Service Environments". www.astm.org. Retrieved 21 April 2018.
- Yun Chung (2 December 2014). "Validity of Caltrans' Environmental Hydrogen Embrittlement Test on Grade BD Anchor Rods in the SAS Span" (PDF).
- "British Land to replace 'a number of bolts' on Leadenhall Building". constructionnews.co.uk. Retrieved 21 April 2018.