Hydrogen embrittlement is the process by which various metals, most importantly high-strength steel, become brittle and fracture following exposure to hydrogen. Hydrogen embrittlement is often the result of unintentional introduction of hydrogen into susceptible metals during forming or finishing operations and increases cracking in the material. This phenomenon was first described in 1875.
Hydrogen embrittlement is also used to describe the formation of zirconium hydride and delayed hydride cracking. Use of the term in this context is common in the nuclear industry.
The mechanism starts with lone hydrogen atoms diffusing through the metal. At elevated temperatures, see activation energy, the elevated solubility of hydrogen allows hydrogen atoms to enter the metal by means of diffusion. The hydrogen can also diffuse in at a low temperature, assisted by a concentration gradient, see Fick's laws of diffusion. When these hydrogen atoms re-combine in minuscule voids of the metal matrix to form hydrogen molecules, they create pressure from inside the cavity where they are located. This pressure can increase to levels where the metal has reduced ductility and tensile strength, up to the point where it cracks open (hydrogen induced cracking, or HIC). High-strength and low-alloy steels, nickel and titanium alloys are most susceptible. Austempered iron is also susceptible. Steel with an ultimate tensile strength of less than 1000 MPa (~145,000 psi) or hardness of less than 30 HRC are not generally considered susceptible to hydrogen embrittlement. Jewett et al. reports the results of tensile tests carried out on several structural metals under high-pressure molecular hydrogen environment. These tests have shown that austenitic stainless steels, aluminum (including alloys), copper (including alloys, e.g. beryllium copper) are not susceptible to hydrogen embrittlement along with few other metals. For example of a severe embrittlement measured by Jewett, 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.
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, chemical reactions of metal with acids, or with other chemicals (notably hydrogen sulfide in sulfide stress cracking, or SSC, a process of importance for the oil and gas industries).
|This section requires expansion with: reviews and additional citations. (January 2013)|
If the metal has not yet started to crack, the condition can be reversed by removing the hydrogen source and causing the hydrogen within the metal to diffuse out, possibly at elevated temperatures. Susceptible alloys, after chemical or electrochemical treatments where hydrogen is produced, are often subjected to heat treatment to remove absorbed hydrogen. There is a 4-hour time limit for baking out entrapped hydrogen after acid treating the parts. This is the time between the end of acid exposure and the beginning of the heating cycle in the baking furnace. This per SAE AMS 2759/9 Section 188.8.131.52 which calls out the correct procedure for eliminating entrapped hydrogen.
In the case of welding, often pre- 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 steel such as the chrome/molybdenum/vanadium alloys. Due to the time needed to re-combine hydrogen atoms into the harmful hydrogen molecules, hydrogen cracking due to welding can occur over 24 hours after the welding operation is completed.
Products such as ferrosilicates can be used to treat surfaces normally subject to hydrogen embrittlement in order to prevent it from taking place.
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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.
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).
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.
There are two ASTM standards for testing embrittlement due to hydrogen gas. The Standard Test Method for Determination of the Susceptibility of Metallic Materials to Hydrogen Gas Embrittlement (HGE) Test, uses a diaphragm loaded with a differential pressure. The Standard Test Method for Determination of Susceptibility of Metals to Embrittlement in Hydrogen Containing Environments at High Pressure, High Temperature, or Both uses a cylindrical tensile specimen tested into an enclosure pressurized with hydrogen or helium.
Another ASTM standard exists 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) - F1624-06 Standard Test Method for Measurement of Hydrogen Embrittlement Threshold in Steel by the Incremental Step Loading Technique. and ASTM STP 962,"Hydrogen Embrittlement: Prevention and Control."
- 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 Process Control Verification to Prevent Hydrogen Embrittlement in Plated or Coated Fasteners
- Standard Test Method for Mechanical Hydrogen Embrittlement Evaluation of Plating/Coating Processes and Service Environments
- Hydrogen analyzer
- Hydrogen damage
- Hydrogen piping
- Hydrogen safety
- Low hydrogen annealing
- Nascent hydrogen
- Oxygen-free copper
- "Study reveals clues to cause of hydrogen embrittlement" (Press release). McGill University. November 19, 2012. Retrieved November 20, 2012.
- Jewett, R.P. (1973). Hydrogen Environment Embrittlement of Metals. NASA CR-2163.
- "Overview of interstate hydrogen pipeline systems" (PDF). Retrieved 2013-12-16.
- Bartlam, Peter (November 19, 2009). "WP6 - Decision Support Tool" (PDF). NATURALHY. Archived from the original on December 18, 2013.
- "Using the existing natural gas system for hydrogen" (PDF). NATURALHY. October 2009. Archived from the original on October 31, 2013.
- 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.
- "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.
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- ASM international, ASM Handbook #13: Corrosion, ASM International, 1998
- Resources on hydrogen embrittlement, Cambridge University
- Zinc Plating and Hydrogen Embrittlement
- Hydrogen embrittlement
- Corrosion-Doctors.org Hydrogen embrittlement
- Hydrogen purity plays a critical role
- A Sandia National Lab technical reference manual.
- Hydrogen Embrittlement group
- The Network of Excellence (NoE) in Hydrogen Embrittlement