Hydrogen embrittlement

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Hydrogen embrittlement (HE) also known as hydrogen assisted

cracking or hydrogen-induced cracking, describes the embrittlement of a metal
by diffusible hydrogen. The essential facts about the nature of the hydrogen
embrittlement of steels have now been known for 140 years. [1][2][3] It
is diffusible atomic hydrogen that is harmful to the toughness of iron and steel. [4] It is
a low temperature effect: most metals are relatively immune to hydrogen
embrittlement above approximately 150°C.[5]
 In steels, diffusible hydrogen ions come from water that is typically introduced by a
wet electrochemical process such as electroplating. It must be distinguished from
the entirely different process high temperature hydrogen attack (HTHA) which is
where steels operating at high temperatures above 400°C are attacked by
hydrogen gas.[6]
For hydrogen embrittlement to occur, a combination of three conditions are
required:

1. the presence and diffusion of hydrogen atoms or ions

2. a susceptible material
3. stress
Diffusible hydrogen can be introduced during manufacture from operations such
as forming, coating, plating or cleaning. The most common causes of failure in
practice are poorly-controlled electroplating or bad welding practice with damp
welding rods. Both of these introduce hydrogen ions which dissolve in the metal.
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. Hydrogen atoms are very small and diffuse interstitially in
steels. Almost uniquely amongst solute atoms they are mobile at room temperature
and will diffuse away from the site of their introduction within minutes. [1]

Contents

 1History
 2Mechanisms
 3Material susceptibility
o 3.1Steels
o 3.2Copper
o 3.3Vanadium, nickel, and titanium
 4Fatigue
 5Sources of hydrogen
 6Prevention
 7Testing
 8Notable failures from hydrogen embrittlement
 9See also
 10References
 11External links

History[edit]
The hydrogen embrittlement phenomenon was first described by Johnson in 1875.
The following conclusions can justifiably be reached from this 1875 paper: [1]

1. it is hydrogen that embrittles steel, not acid;

 2. that the hydrogen is nascent or diffusible, not molecular;
3. it is diffusible hydrogen that embrittles, so the phenomenon is reversible;
4. the effusion of diffusible hydrogen from the steel leads to frothing (bubbles);
5. that stronger steel is more susceptible to embrittlement than softer versions.
It follows, therefore, that the harmful influence of diffusible hydrogen can be
mitigated by preventing its entry into steel or by rendering it immobile once it
penetrates the material.

Mechanisms[edit]
Hydrogen embrittlement is a complex process involving a number of distinct
contributing micro-mechanisms not all of which need to be present. The
mechanisms include the formation of brittle hydrides, the creation of voids that can
lead to high-pressure bubbles, enhanced decohesion at internal surfaces and
localised plasticity at crack tips that assist in the propagation of cracks. [7] There is a
great variety of mechanisms that have been proposed: [7] and investigated which
cause brittleness once diffusible hydrogen has been dissolved into the metal. [1] As
the hydrogen is diffusible and mobile, brittleness can only occur when (a) it is
captured in microscopic traps, and (b) these traps cause brittleness. [8] In recent
years, it has become widely accepted that HE is a complex, material and
environmental dependent process so that no mechanism applies exclusively. [9]

 Internal pressure: 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).[10]

 Hydrogen enhanced localised plasticity (HELP), 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. [9]
[3]

 Hydrogen decreased dislocation emission: molecular dynamics simulations

reveal a ductile-to-brittle transition caused by the suppression of dislocation
emission at the crack tip by dissolved hydrogen. This prevents the crack tip
rounding-off, so the sharp crack then leads to brittle-cleavage failure. [11]

 Hydrogen enhanced decohesion (HEDE), where the increased solubility of

hydrogen in a tensile strength field, for instance on the tip of a crack or in areas
with internal tensile strength or in the tension field of edge dislocations, reduces
the yield stress locally.[3]

 Metal hydride formation: The formation of brittle hydrides with the parent
material allows cracks to propagate in a brittle fashion. This is particularly a
 problem with Vanadium alloys[12] but most structural alloys do not easily form
hydrides.

 Phase transformations: these occur for some materials when hydrogen is

present and the new phase may be less ductile.

Material susceptibility[edit]
Hydrogen embrittles a variety of metals including steel, [13][14] aluminium (at high
temperatures only[15]), and titanium.[16] Austempered iron is also susceptible, though
austempered steel (and possibly other austempered metals) display increased
resistance to hydrogen embrittlement. [17] NASA reviewed which metals are
susceptible to embrittlement and which only prone to hot hydrogen
attack: nickel alloys, austenitic stainless steels, aluminium and
alloys, copper (including alloys, e.g. beryllium copper).[18] Sandia has also produced
a comprehensive guide.[19]
Steels[edit]

Steels were embrittled with hydrogen through cathodic charging. Heat treatment (baking) was used to
reduce hydrogen content. Lower bake times resulted in quicker fracture times due to higher hydrogen
content.[20]

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 fracture toughness decreases, so the
likelihood that hydrogen embrittlement will lead to fracture 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[edit]
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 2O,
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[edit]
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.[12]

Fatigue[edit]
While most failures in practice have been through fast failure, there is experimental
evidence that hydrogen also affects the fatigue properties of steels. This is entirely
expected given the nature of the embrittlement mechanisms proposed for fast
fracture.[8][10] In general hydrogen embrittlement has a strong effect on high-stress,
low-cycle fatigue and very little effect on high-cycle fatigue. [18][19]

Sources of hydrogen[edit]
During manufacture, hydrogen can be dissolved into the component by processes
such as phosphating, pickling, electroplating, casting, carbonizing, surface
cleaning, electrochemical machining, welding, hot roll forming, and heat
treatments.
During service use, hydrogen can be dissolved into the metal from wet corrosion or
through misapplication of protection measures such as cathodic protection.[18] In
one case of failure during construction of the San Francisco–Oakland Bay Bridge
galvanized (i.e. zinc-plated) rods were left wet for 5 years before being tensioned.
The reaction of the zinc with water introduced hydrogen into the steel. [21][22][23]
A common case of embrittlement during manufacture is poor arc welding practice,
in which the hydrogen is released from moisture, such as in the coating of welding
electrodes or from damp welding rods.[16][24] To minimize this, special low-hydrogen
electrodes are used for welding high-strength steels.
Apart from arc welding, the most common problems are from the chemical or
electrochemical processes which generate hydrogen ions at the surface which
rapidly dissolve in the metal. One of these chemical reactions involves hydrogen
sulfide in sulfide stress cracking (SSC), a significant problem for the oil and gas
industries.[25]
After a manufacturing process or treatment which may cause hydrogen ingress,
the component should be baked to remove or immobilise the hydrogen. [22]

Prevention[edit]
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 Low
hydrogen annealing or "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.
[4]
 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. [19] 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.

Testing[edit]
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.
[26]
 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.[27] 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).[28][29] 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.[30] 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 [31]

Notable failures from hydrogen embrittlement[edit]

 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 (see details above).[23][21]
 In the City of London, 122 Leadenhall Street, generally known as 'the
Cheesegrater', suffered from hydrogen embrittlement in steel bolts, with three
bolts failing in 2014 and 2015. Most of the 3,000 bolts were replaced at a cost
of £6m.[32][33]

See also[edit]
 Hydrogen analyzer
 Hydrogen damage
 Hydrogen piping
 Hydrogen safety
 Low hydrogen annealing
 Nascent hydrogen
 Oxygen-free copper

References[edit]
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External links[edit]
 Resources on hydrogen embrittlement, Cambridge University
 Hydrogen embrittlement
 Hydrogen purity plays a critical role
 A Sandia National Lab technical reference manual.
 Hydrogen Embrittlement, NASA

https://en.wikipedia.org/wiki/Hydrogen_embrittlement