Rev 3-4-09

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Hydrogen Lmbrittlement
Hydrogen embrittlement is generally associated with high-strength asteners made o carbon and alloy
steels. loweer, it is worth noting that een precipitate hardened stainless steels, titanium, and aluminum
alloys can be ulnerable. lydrogen embrittled asteners or parts under stress can ail suddenly without
any warning. 1here are many dierent theories on the exact cause. 1he ollowing is our comprehension
o the subject.
lydrogen is the most common element in the world and many acidic and oxidation reactions with steel
will liberate hydrogen in arious amounts depending on the speciic chemical reaction.
lydrogen embrittlement can occur
wheneer atomic or protonic
hydrogen is produced rom a reaction,
e.g. acid pickling can react iron and
hydrochloric acid to diuse hydrogen
in iron. During acid pickling
hydrogen can be diused into the
iron. Llectroplating is another process
to introduce hydrogen into a metal in
both the acid pickle and the plating
processes. Another example o
hydrogen production is rom high
pressure steam. 1he table on the right
shows the simpliied chemical
reactions o the processes mentioned
herein.

Internal hydrogen embrittlement is the more common orm o hydrogen embrittlement and can occur
any time atomic hydrogen is absorbed into the astener rom any chemical process beore exposure to an
externally applied stress.
lrequently, hydrogen is introduced to the astener during the electroplating process. In these cases, the
hydrogen is absorbed into the astener during the acid cleaning or descaling process and is then trapped
in the part by the plating. A subsequent baking process is typically employed to remoe or displace the
trapped hydrogen. Len proper baking is no guarantee o reedom rom hydrogen. \hen tension is
applied to the astener, the hydrogen tends to migrate to points o high stress concentration ,under the
head o the astener, irst engaged thread, etc.,. 1he pressure created by the hydrogen creates and,or
extends a preexisting crack which grows under subsequent stress cycles until the bolt breaks.
Metallic Reactivity in the Presence of Acids
lydrochloric Acid le,s, - lCl,aq, le,s, - l - 'Cl2,g, lel,s,
Llectroplating
M - l2O - e
-
M - l - Ol
-
Ml - Ol
-

M - l3O
-
M - l
-
- l2O Ml
-
- l2O
ligh-Pressure Steam 4le,s, - 6l2O,g, 2le2lO3 - 5l2,g,
Key:
Llement Symbol
Iron le
lydroden l
\ater l2O
lydrochloric Acid lCl
Generic Metal M
Generic Acid l3O
-

Llectron e
-

Note: the end product always has hydrogen embedded in a metal


Rev 3-4-09

Although the most
common hydrogen
embrittlement
ailures are directly
underneath the head
o the astener ,A,,
they can also occur
elsewhere gien
proper circumstances
,B,. Lab analysis is
always necessary to
determine the proper
cause o a ailure.

Unortunately this is only one o seeral models o hydrogen embrittlement. As mentioned preiously,
any chemical process that introduces hydrogen into the material can lead to embrittlement. Other sources
o hydrogen can include the melting o steel, processing parts, or een welding. Regardless o the means
o transmission, all internal hydrogen embrittlement is the result o hydrogen absorption by the base metal
prior to the application o stress.
Lnvironmental hydrogen embrittlement ,LlL, is another orm o hydrogen embrittlement. 1his is
generally caused by hydrogen introduced into the steel rom the enironment ater being placed in serice.
In this case, the hydrogen can come rom a number o external sources or as by-product o general
corrosion, or a by-product o a common reaction.
Stress corrosion ,a orm o enironmental hydrogen embrittlement, represents a particular condition
where cracks are induced and propagated under combined eects o stress and corrosion enironments.
It is the least understood corrosion related phenomenon, but by ar the most dangerous. Under the right
conditions, any metal is susceptible to this type o corrosie attack. 1he initial corrosion may occur at a
point o high stress causing the ormation o a microscopic crack, which can be either intergranular or
transgranular. Continued exposure to the corrosion enironment will propagate the crack, resulting in
serious and possibly catastrophic ailure.
Stress corrosion, along with other material ailure modes such as stress embrittlement, enironmental
hydrogen embrittlement, and hydrogen assisted stress corrosion dier rom internal hydrogen
embrittlement because they are all related to the serice enironment. 1hese ailures occur ater
installation due to hydrogen being introduced by a chemical reaction induced by the serice enironment.
Methods for Iighting Hydrogen Lmbrittlement
Below are a ew methods used to ight hydrogen embrittlement:
Hardness is a major contributor to hydrogen embrittlement. larder, stronger materials are more
susceptible to ailure than weaker, soter ones. In general, i the hardness o the astener is less than 35
A B


Rev 3-4-09
lRC, there will probably be little diiculty with hydrogen embrittlement. loweer, i the astener has
hardness aboe 40 lRC, problems are more likely to occur.
lydrogen concentration is another actor that contributes to hydrogen embrittlement. Coating processes
such electroplating can introduce hydrogen during the acid cleaning stage. During this stage, the material
to be plated is immersed in an acidic solution. ligher acid concentrations and long exposure times will
increase the hydrogen concentration in the astener material, thus increasing the likelihood o hydrogen
embrittlement.
Using a coating process that does not introduce hydrogen into the material ,particularly those that do not
utilize acids or cleaning, will help aoid this problem. A number o dip-spin coatings are considered
hydrogen embrittlement ree` because they use mechanical processes ,abrasie blasting, or descaling.
Additionally, some o these coatings oer higher corrosion resistance and thereore less ulnerability to
LlL.
Coating porosity also has an impact on hydrogen concentration. Llectroplated coatings are dense enough
to trap` or seal hydrogen in the base material. Once the hydrogen is sealed in the astener, it is more
likely to produce an embrittlement ailure. Mechanical coatings are more porous ,less dense,. 1hereore,
any hydrogen in the base material o a mechanically coated astener will hae a better opportunity to
escape without causing an embrittlement ailure.
I electroplating is still desired, ensure that the plater uses the proper procedures and bakes the asteners
correctly based on the hardness o the astener.
AS1M l1941 has a hydrogen embrittlement relie requirement or coated asteners made rom steel heat
treated to a hardness o lRC 40 or aboe, case hardened asteners, and asteners with captie washers
,SLM screws, made rom hardened steel. 1he exact time and temperature o the bake is not speciied,
but times between 2 and 24 hours at temperatures between 350 and 450l are listed as suitable depending
on type, size o astener, geometry and other ariables.
Lnironment ought to be one o the major concerns o bolted joint design. Proper selection o the
astener material or the serice enironment can reduce the risk o embrittlement. 1he potential or
hydrogen embrittlement cracking ,een or asteners below lRC 35, is accelerated i the astener is acting
as the cathode in a galanic couple. Caustic or sour enironments may require much lower hardness
leels to lower the susceptibility to hydrogen embrittlement.
1emper Lmbrittlement
1emper Lmbrittlement (1L) occurs in some alloys that contain certain tramp elements i.e. antimony,
arsenic, phosphorus, and tin. I these alloys are held between a critical temperature range or a period o
time, tramp elements can segregate to grain boundaries. 1here is a time actor to 1L, as more impurities
build up on the grain boundaries the alloy becomes more brittle in nature. 1he susceptible temperature
range and hold times will ary between alloys, but in general the embrittlement temperatures can range
rom 660 l to 1060 l. Again, please note, each metal will hae its own range o temperatures to aoid.


Rev 3-4-09
1emper embrittlement can occur at any time the alloy passes through the embrittlement temperature
range or an extended period o time, e.g. during tempering and,or during slow cooling. Large pieces o
alloy are more susceptible to 1L due to the interior not being able to cool as quickly. See +HDW7UHDWPHQW
or more explanation on the topic o uniorm cooling.
1o reduce temper embrittlement, make sure to temper outside the critical temperature range. Also,
make sure to ast cool the alloy through its embrittlement temperature. 1his will assure the tramp
elements do not hae time or energy to segregate to grain boundaries.
1emper embrittlement is reversible! I parts are suspected o being tempered or slow cooled between
the embrittlement temperature range the parts can be re-tempered ,at a temperature outside the range,. By
re-tempering, 1L can be drastically ,i not completely, reduced.