Hydrogen embrittlement

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.
Hydrogen embrittlement can occur during various man-
ufacturing operations or operational use - anywhere that
the metal comes into contact with atomic or molecular hy-
drogen. Processes that can lead to this include cathodic
Hydrogen Induced Cracks (HIC) protection, phosphating, pickling, and electroplating. A
special case is arc welding, in which the hydrogen is re-
Hydrogen embrittlement is the process by which met- leased from moisture, such as in the coating of welding
als such as steel become brittle and fracture due to the in- electrodes.[7][11] To minimize this, special low-hydrogen
troduction and subsequent diffusion of hydrogen into the electrodes are used for welding high-strength steels.
metal. This is often a result of accidental introduction of Other mechanisms of introduction of hydrogen into metal
hydrogen during forming and finishing operations. This are galvanic corrosion, as well as chemical reactions with
phenomenon was first described in 1875.[1] acids or other chemicals. One of these chemical reactions
involves hydrogen sulfide in sulfide stress cracking (SSC),
an important process for the oil and gas industries.[12]
1 Process
During hydrogen embrittlement, hydrogen is introduced 1.1 Counteractions
to the surface of a metal and individual hydrogen atoms
diffuse through the metal. Because the solubility of hy- Hydrogen embrittlement can be prevented through sev-
drogen increases at higher temperatures, raising the tem- eral methods, all of which are centered on minimiz-
perature can increase the diffusion of hydrogen. When ing contact between the metal and hydrogen, particularly
assisted by a concentration gradient where there is signif- during fabrication. Embrittling procedures such as acid
icantly more hydrogen outside the metal than inside, hy- pickling should be avoided, as should increased contact
drogen diffusion can occur even at lower temperatures. with elements such as sulfur and phosphate. The use
These individual hydrogen atoms within the metal grad- of proper electroplating solution and procedures can also
ually recombine to form hydrogen molecules, creating help to prevent hydrogen embrittlement.[13] Furthermore,
pressure from within the metal. This pressure can in- metal substrates (generally ferrous sulfide or other sul-
crease to levels where the metal has reduced ductility, fides) can be applied to metal in order to prevent hydrogen
toughness, and tensile strength, up to the point where embrittlement.[14][15]
it cracks open (hydrogen-induced cracking, or HIC).[2]
Though hydrogen atoms embrittle a variety of substances, If the metal has not yet started to crack, embrittlement
including steel,[3][4][5] aluminium(at high temperatures can be reversed by removing the hydrogen source and
only[6] ), and titanium,[7] hydrogen embrittlement of high- causing the hydrogen within the metal to diffuse out
strength steel is of the most importance. Austempered through heat treatment.[16] This de-embrittlement pro-
iron is also susceptible, though austempered steel (and cess, known as “baking”, is used to overcome the weak-
possibly other austempered metals) display increased re- nesses of methods such as electroplating which intro-
sistance to hydrogen embrittlement.[8] Steel with an ul- duce hydrogen to the metal, but is not always entirely
timate tensile strength of less than 1000 MPa (~145,000 effective.[17]
psi) or hardness of less than 30 HRC is not generally con- In the case of welding, often pre- and post-heating the
sidered susceptible to hydrogen embrittlement. In tensile metal is applied to allow the hydrogen to diffuse out be-
tests carried out on several structural metals under high- fore it can cause any damage. This is specifically done
pressure molecular hydrogen environment, it has been with high-strength steels and low alloy steels such as the
shown that austenitic stainless steels, aluminium (includ- chrome/molybdenum/vanadium alloys. Due to the time
ing alloys), copper (including alloys, e.g. beryllium cop- needed to re-combine hydrogen atoms into the hydrogen
per) are not susceptible to hydrogen embrittlement along molecules, hydrogen cracking due to welding can occur
with a few other metals.[9][10] As an example of severe over 24 hours after the welding operation is completed.

1
2 6 REFERENCES

2 Examples F1624-06 Standard Test Method for Measurement of Hy-

drogen Embrittlement Threshold in Steel by the Incre-
mental Step Loading Technique.[22][23] and ASTM STP
• In 2013, six months prior to opening, the East Span
962, “Hydrogen Embrittlement: Prevention and Con-
of the Oakland Bay Bridge failed during testing.
trol.”
Catastrophic failures occurred in shear bolts in the
span, after only two weeks of service, with the fail-
• NACE TM0284-2003 (NACE International) Resis-
ure attributed to embrittlement, possibly from the
[18] tance to Hydrogen-Induced Cracking
environment.
• ISO 11114-4:2005 (ISO)Test methods for selecting
metallic materials resistant to hydrogen embrittle-
ment.
3 Related phenomena
• Standard Test Method for Process Control Verifica-
If steel is exposed to hydrogen at high temperatures, tion to Prevent Hydrogen Embrittlement in Plated
hydrogen will diffuse into the alloy and combine with or Coated Fasteners[24]
carbon to form tiny pockets of methane at internal sur- • Standard Test Method for Mechanical Hydrogen
faces like grain boundaries and voids. This methane does Embrittlement Evaluation of Plating/Coating Pro-
not diffuse out of the metal, and collects in the voids cesses and Service Environments[25]
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 decar-
burization of the steel and loss of strength and ductility.
5 See also
Copper alloys which contain oxygen can be embrittled if • Hydrogen analyzer
exposed to hot hydrogen. The hydrogen diffuses through
the copper and reacts with inclusions of Cu2 O, forming • Hydrogen damage
H2 O (water), which then forms pressurized bubbles at the • Hydrogen piping
grain boundaries. This process can cause the grains to
literally be forced away from each other, and is known • Hydrogen safety
as steam embrittlement (because steam is produced, not • Low hydrogen annealing
because exposure to steam causes the problem).
• Nascent hydrogen
A large number of alloys of vanadium, nickel, and tita-
nium absorb significant amounts of hydrogen. This can • Oxygen-free copper
lead to large volume expansion and damage to the crys-
tal structure leading to the alloys becoming very brit-
tle. This is a particular issue when looking for non- 6 References
palladium based alloys for use in hydrogen separation
membranes.[19] [1] “Study reveals clues to cause of hydrogen embrittlement”
(Press release). McGill University. November 19, 2012.
Retrieved November 20, 2012.
4 Testing [2] Vergani, Laura; Colombo, Chiara; et al. (2014).
“Hydrogen effect on fatigue behavior of a quenched
and tempered steel”. Procedia Engineering. Else-
There are two ASTM standards for testing embrittlement
vier. 74 (XVII International Colloquium on Me-
due to hydrogen gas. The Standard Test Method for chanical Fatigue of Metals (ICMFM17)): 468–71.
Determination of the Susceptibility of Metallic Materi- doi:10.1016/j.proeng.2014.06.299. Retrieved 9 May
als to Hydrogen Gas Embrittlement (HGE) Test,[20] uses 2015.
a diaphragm loaded with a differential pressure. The
Standard Test Method for Determination of Susceptibil- [3] Djukic, M.B.; et al. (2014). “Hydrogen embrittlement
of low carbon structural steel”. Procedia Materials Sci-
ity of Metals to Embrittlement in Hydrogen Containing
ence. Elsevier. 3 (20th European Conference on Frac-
Environments at High Pressure, High Temperature, or
ture): 1167–1172. doi:10.1016/j.mspro.2014.06.190.
Both[21] uses a cylindrical tensile specimen tested into an Retrieved 9 May 2015.
enclosure pressurized with hydrogen or helium.
[4] Djukic, M.B.; et al. (2015). “Hydrogen damage of
Another ASTM standard exists for quantitatively testing steels: A case study and hydrogen embrittlement model”.
for the Hydrogen Embrittlement threshold stress for the Engineering Failure Analysis. Elsevier. 58 (Recent
onset of Hydrogen-Induced Cracking due to platings and case studies in Engineering Failure Analysis): 485–498.
coatings from Internal Hydrogen Embrittlement (IHE) doi:10.1016/j.engfailanal.2015.05.017. Retrieved 9 May
and Environmental Hydrogen Embrittlement (EHE) - 2015.
 3

[5] Djukic, Milos B.; et al. (2016). “Hydrogen Em- [19] Dolan, Michael D.; Kochanek, Mark A.; Munnings,
brittlement of Industrial Components: Prediction, Pre- Christopher N.; McLennan, Keith G.; Viano, David M.
vention, and Models”. Corrosion. NACE Interna- (February 2015). “Hydride phase equilibria in V–Ti–Ni
tional. 72(7) (Environment Assisted Cracking): 943– alloy membranes”. Journal of Alloys and Compounds.
961. doi:10.5006/1958. Retrieved 9 May 2015. 622: 276–281. doi:10.1016/j.jallcom.2014.10.081.

[6] Ambat, Rajan; Dwarakadasa (February 1996). “Effect of [20] “ASTM F1459 - 06(2012): Standard Test Method for De-
Hydrogen in aluminium and aluminium alloys: A review”. termination of the Susceptibility of Metallic Materials to
Bulletin of Materials Science. Springer India. 19 (1): 103– Hydrogen Gas Embrittlement (HGE)". Astm.org. Re-
114. trieved 2015-02-24.

[7] Eberhart, Mark (2003). Why Things Break. New York: [21] “ASTM G142 - 98(2011) Standard Test Method for De-
Harmony Books. p. 65. ISBN 1-4000-4760-9. termination of Susceptibility of Metals to Embrittlement
in Hydrogen Containing Environments at High Pressure,
[8] Tartaglia, John; Lazzari, Kristen; et al. (March High Temperature, or Both”. Astm.org. Retrieved 2015-
2008). “A Comparison of Mechanical Properties 02-24.
and Hydrogen Embrittlement Resistance of Austem-
pered vs Quenched and Tempered 4340 Steel”. Met- [22] ASTM STP 543, “Hydrogen Embrittlement Testing”
allurgical and Materials Transactions A. Springer US.
39 (3): 559–76. Bibcode:2008MMTA...39..559T. [23] Raymond L (1974). Hydrogen Embrittlement Testing.
doi:10.1007/s11661-007-9451-8. ISSN 1073-5623. ASTM International. ISBN 978-0-8031-0373-3.

[9] Jewett, R.P. (1973). Hydrogen Environment Embrittle- [24] “ASTM F1940 - 07a(2014) Standard Test Method for
ment of Metals. NASA CR-2163. Process Control Verification to Prevent Hydrogen Embrit-
tlement in Plated or Coated Fasteners”. Astm.org. Re-
[10] Gillette, J.L.; Kolpa, R.L. (November 2007). “Overview trieved 2015-02-24.
of interstate hydrogen pipeline systems” (PDF). Retrieved
2013-12-16. [25] http://www.astm.org/Standards/F519.htm

[11] Weman, Klas (2011). Welding Processes Handbook. El-

sevier. p. 115. ISBN 978-0-85709-518-3. 7 Further reading
[12] “Standard Test Method for Process Control Verification
to Prevent Hydrogen Embrittlement in Plated or Coated • ASM international, ASM Handbook #13: Corrosion,
Fasteners”. Astm.org. Retrieved 24 February 2015. ASM International, 1998
[13] Main contributor: Clive D. Pearce (2006). “Hydrogen
Embrittlement: An Overview from a Mechanical Fasten-
ings Aspect” (PDF). The Fastener Engineering and Re- 8 External links
search Association. Confederation of British Metalform-
ing. Retrieved 9 May 2015. • Resources on hydrogen embrittlement, Cambridge
[14] Bhardwaj, B.P. (2014). The Complete Book on Ferroal- University
loys. Khamla Nagar, New Delhi: Niir Project Consul-
• Zinc Plating and Hydrogen Embrittlement
tancy Services. p. 12. ISBN 978-93-81039-29-8. Re-
trieved 10 May 2015. • Hydrogen embrittlement
[15] US Patent 4335754, Alfred C. C. Tseung; Anthony I. • Corrosion-Doctors.org Hydrogen embrittlement
Onuchukwu & Ho C. Chan, “Prevention of hydrogen em-
brittlement of metals in corrosive environments”, pub- • Hydrogen purity plays a critical role
lished 1982-06-22, issued 1983-02-02, assigned to Alfred
C. C. Tseung and Anthony I. Onuchukwu • A Sandia National Lab technical reference manual.
[16] Chalaftris, George (December 2003). “Abstract”. • Hydrogen Embrittlement group
Evaluation of Aluminium–Based Coatings for Cadmium
Replacement (PhD thesis). Cranfield University School of • The Network of Excellence (NoE) in Hydrogen Em-
Industrial and Manufacturing Science. Retrieved 9 May brittlement
2015.

[17] Federal Engineering and Design Support.

“Embrittlement” (PDF). Fastenal. Fastenal Com-
pany Engineering Department. Retrieved 9 May
2015.

[18] Yun Chung (2 December 2014). “Validity of Caltrans’

Environmental Hydrogen Embrittlement Test on Grade
BD Anchor Rods in the SAS Span” (PDF).
4 9 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

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