Hydrogen embrittlement

From Wikipedia, the free encyclopedia

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.
[1]
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.
Contents
1 Process
1.1 Counteractions
1.2 Decision support tool
2 Related phenomena
3 Testing
4 See also
5 References
6 Further reading
7 External links
Process
The mechanism starts with lone hydrogen atoms diffusing through the metal. At high
temperatures, the elevated solubility of hydrogen allows hydrogen to diffuse into the metal
(or the hydrogen can diffuse in at a low temperature, assisted by a concentration gradient).
When these hydrogen atoms re-combine in minuscule voids of the metal matrix to form
hydrogen molecules, they create pressure from inside the cavity they are in. 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.
[2]
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.
[3]
For example of a severe embrittlement measured by Jewett, the elongation
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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 (for example in the coating of the 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).
[4]
Counteractions
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 3.3.3.1 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.
Decision support tool
To handle the frequency of occurrence of embrittlement in steel, decision support tools are
used
[5]
depending on the field of application.
[6]
Related phenomena
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 Cu
2
O, forming H
2
O
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(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).
Testing
There are two ASTM standards for testing embrittlement due to hydrogen gas. The
standard ASTM F1459-06 Standard Test Method for Determination of the Susceptibility of
Metallic Materials to Hydrogen Gas Embrittlement (HGE) Test (http://www.astm.org
/Standards/F1459.htm) uses a diaphragm loaded with a differential pressure. The test
ASTM G142-98(2004) Standard Test Method for Determination of Susceptibility of Metals to
Embrittlement in Hydrogen Containing Environments at High Pressure, High Temperature,
or Both (http://www.astm.org/Standards/G142.htm) 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.
[7][8]
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.
ASTM F1940-07a (http://www.astm.org/cgi-bin/SoftCart.exe/DATABASE.CART
/REDLINE_PAGES/F1940.htm?L+mystore+yvst4574+1196145312)- Standard Test
Method for Process Control Verification to Prevent Hydrogen Embrittlement in Plated
or Coated Fasteners
ASTM F519-06e2 (http://www.astm.org/cgi-bin/SoftCart.exe/STORE
/filtrexx40.cgi?U+mystore+yvst4574+-L+F519+/usr6/htdocs/astm.org
/DATABASE.CART/REDLINE_PAGES/F519.htm)-Standard Test Method for
Mechanical Hydrogen Embrittlement Evaluation of Plating/Coating Processes and
Service Environments
See also
Hydrogen analyzer
Hydrogen damage
Hydrogen piping
Hydrogen safety
Low hydrogen annealing
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Nascent hydrogen
Oxygen-free copper
References
^ "Study reveals clues to cause of hydrogen embrittlement" (http://www.mcgill.ca/newsroom
/channels/news/study-reveals-clues-cause-hydrogen-embrittlement-219051) (Press release).
McGill University. November 19, 2012. Retrieved November 20, 2012.
1.
^ Jewett, R.P. (1973). Hydrogen Environment Embrittlement of Metals. NASA CR-2163. 2.
^ "Overview of interstate hydrogen pipeline systems" (http://corridoreis.anl.gov/documents
/docs/technical/APT_61012_EVS_TM_08_2.pdf) (PDF). Retrieved 2013-12-16.
3.
^ ASTM F1940-07a Hydrogen Project (http://www.astm.org/cgi-bin/SoftCart.exe
/DATABASE.CART/REDLINE_PAGES/F1940.htm?L+mystore+yvst4574+1196145312)
4.
^ "Decision Support Tool" (http://www.naturalhy.net/docs/final_public_presentation
/09.%20WP6%20-%20Decision%20Support%20Tool.pdf) (PDF). Retrieved 2013-12-16.
5.
^ "Using the existing natural gas system for hydrogen" (http://www.naturalhy.net
/docs/Naturalhy_Brochure.pdf) (PDF). Retrieved 2013-12-16.
6.
^ ASTM STP 543,"Hydrogen Embrittlement Testing" 7.
^ Raymond L (1974). Hydrogen Embrittlement Testing. ASTM International.
ISBN 978-0-8031-0373-3.
8.
Further reading
ASM international, ASM Handbook #13: Corrosion, ASM International, 1998
External links
Zinc Plating and Hydrogen Embrittlement (http://www.beyondrigging.com/2014/02
/hydrogen-embrittlement/)
Hydrogen embrittlement (http://www.uni-saarland.de/fak8/wwm/research
/phd_barnoush/hydrogen.pdf)
Corrosion-Doctors.org Hydrogen embrittlement (http://www.corrosion-doctors.org
/Forms-HIC/embrittlement.htm)
Hydrogen purity plays a critical role (http://www.hydrogen.energy.gov
/pdfs/progress05/v_a_4_adams.pdf)
A Sandia National Lab technical reference manual. (http://www.sandia.gov
/matlsTechRef/)
Hydrogen Embrittlement group (http://www.linkedin.com/groups/Hydrogen-
Embrittlement-4991909?trk=myg_ugrp_ovr)
The Network of Excellence (NoE) in Hydrogen Embrittlement
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(http://milosdjukichydrogen.wordpress.com/2014/05/14/the-network-of-excellence-
noe-in-hydrogen-embrittlement/)
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Categories: Corrosion Hydrogen
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