Embrittlement of Steels

4/1/2007 by Fred Hochgraf

Practical advice on the embrittlement of steels and new steels that can
enhance the performance of critical mechanical parts.
This issue of Nuts and Bolts is a wakeup call for our clients that make parts
out of hardened steels. Through-out this issue I am referring to only
hardened steels. Don't read into this discussion anything about the
behavior of any ductile metals.
New steels are becoming available that can enhance the performance of
critical parts such as bearings, gear teeth, parts subjected to high and low
cycle fatigue, and large parts including turbines and paper mill rolls.
The changeover to the new steels has taken place in steam turbine
forgings. My crystal ball says that rolling contact bearings are the next
candidates and there are murmurings that some bearings are now being
produced from the new steels.
These new steels take advantage of finer grain sizes than ever achieved
before in mill quantities and/or lower impurity levels than we could have
ever imagined. It has been found that the impurity atoms tend to migrate
to the grain boundaries. The finer the grain size the greater the total grain
boundary surface and the more "dilute" are the impurity atoms. It is also
well established that the higher the strength and hardness, the greater the
detrimental effects of the impurity atoms.
Why is embrittlement important?
Perhaps most crucial are its effects on damage tolerance and working
stress through decreased impact strength, decreased low cycle fatigue
strength, and the rather different phenomena of high cycle fatigue fracture
initiation and fatigue fracture propagation. With the new steels we can
operate at significantly higher levels of service stress, stress intensity and
impact strength.
The performance level of any hardened steel is determined by the stress
levels at which cracking commences in the grain boundaries. The cracking
starts as either decohesion of the grain boundaries or cracking across or
around hard particles in the grain boundaries. More often than not the hard
particles are carbides.
How do we describe embrittlement?
One way is via the Izod and Charpy tests that measure the energy to break
a notched bar 1 cm square by 10 cm long at a strain rate in the ballpark of
1000 strain units per sec. Higher strain rates interest the military. Higher
strain rates also occur during impacts such as railroad wheels impacting
across a gap in the track at a switch or crossing. High strain rates include a
cam being slammed by a cam follower. Low strain rates include the tensile
tests, tests of stress rupture and hardness tests.
It is very important to note that the low strain rates of a hardness test will
not detect embrittlement.
What are Temper Embrittlement and Tempered
Martensite Embrittlement? They are the embrittlement that is seen after
tempering or slowly cooling hardened steels or using them too long within a
critical temperature range. The low temperature phenomenon is called
"tempered embrittlement" and it is irreversible except by reaustenitizing
and repeating the entire heat treating cycle. In a higher temperature band
it is called "tempered martensite embrittlement". Depending on the steel
chemistry there can by one embrittling band or two.
Examples
Consider the "tempered martensite embrittlement" of 4140, figure 2.
Because of this embrittlement 4140 cannot be tempered or used in the
range 180-500C (350-930F).
Now consider the same pair of curves for 4340, figures 3 and 4. As before,
"tempered martensite embrittlement" occurs in a low temperature range
while this time we add "temper embrittlement" in a high temperature
range. The high temperature "temper embrittlement" is reversible through
appropriate retempering that either redissolves the harmful grain boundary
precipitates or disperses the solute atoms that have migrated to the grain
boundaries. "Tempered martensite embrittlement" is not reversible.

(Figure 1. The hardness of 4140 steel following tempering. With the low strain rates of
a hardness test the curve drops smoothly with increasing tempering temperature.
Ref Metals Handbook, ASM, 9th ed, vol. 1, p469)
As shown in figures 1 and 3, hardness varies smoothly through the
tempering range however at the higher strain rates of the impact tests
there is the unacceptable embrittlement, figures 2 and 4. That's why we
have to stay away from tempering in those ranges, and that's why the
bands of hardness values and strengths we would expect following
tempering in those ranges are, practically speaking, unavailable to the
engineer.

(Figure 2. The notch toughness of 4140 steel following tempering. We see the dramatic
loss in toughness accompanying tempering in the range spanning 180- 500C.
Ref Metals Handbook, ASM, 9th ed, vol. 1, p469)
Or suppose your bearing or hardened part is subject to soak-back heating
to near 375C after normal shut down of a gas turbine or emergency
shutdown of high temperature processing equipment. Well, these hardened
steels can't be used. Too bad because the alternative steels tend to be
expensive.
The Trace Elements
The irreversible, low temperature embrittlement is attributable to fracture
in the prior austenite grain boundaries. These fractures initiate at grain
boundary carbide particles. With these particles present phosphorous,
manganese and silicon correlate with increased embrittlement.
Sulfur and phosphorous are the principal contributors to reversible temper
embrittlement. Neither can be adequately refined out of the steel so control
is through pure melting stock, often made via chemical processes rather
than traditional steel making. Sulfur levels of 0.002% are available.
Tin and antimony contribute to embrittlement. They operate through co-
segregation with nickel so that low nickel steels are sometimes preferred.
Besides being one of the least expensive contributors to hardenability,
manganese contributes to embrittlement. When the sulfur is extremely low
there is no longer a necessity for the manganese. However we must look to
other alloying elements to enhance hardenability.
Carbon that preferentially diffuses to grain boundaries makes important
contributions to grain boundary strength. We must be watchful lest
elements such as chromium precipitate carbides in the prior austenite grain
bound- aries, thereby reducing the amount of available carbon and thereby
denying us the beneficial effects of carbon on grain boundary strength.
Molybdenum and vanadium tend to be beneficial to grain boundary
strength, apparently by not localizing the carbon atoms the way that
chromium does. Additionally molybdenum is principally responsible for the
secondary hardening that we exploit in the tool steels and numerous other
high temperature applications for hardened steels.

(Figure 3. The hardness of 4340 varies smoothly with tempering temperature."
Ref Metals Handbook, ASM, 9th ed, vol. 1, p425)
Dissolved hydrogen in hardened steel migrates in response to stress, either
applied or residual. Hydrogen works together with the other embrittling
elements to cause grain boundary fracture. Low temperature sensitivity to
hydrogen is therefore reduced when the other elements are kept at low
levels.

(Figure 4. Toughness v Tempering Temperature for 4340 showing the pair of
embrittlement ranges as well as the dramatic improvement that comes with 50 ppm
phosphorous.
Ref. J. P. Materkowski and G. Krauss, Metallurgical Tr. v10A, 1979, p1643)
Looking Forward
Keep your eyes and ears open! Just as low phosphorous enhanced the 4340
in figure 4 expect that many more enhancements in the hardened steels
will be coming along.
Areas of embrittlement of hardened steels that I will save for another day's
discussion include quench embrittlement, liquid metal embrittlement, low
temperature embrittlement, weld cracking and more about hydrogen. Also
available if there is a ground swell of requests would be a Nuts and Bolts
discussing damage tolerance.
For an excellent overview see C. J. McMahon, Jr., Brittle Fracture of Grain
Boundaries, Interface Science 12, 141- 146, 2004.
For a review of the metallurgy of steels see G. Kraus, Steels, ASM
International, 2005


The Embrittlement Phenomena in Hardened &
Tempered Steel
By Daniel H. Herring
While the end-use application of a component dictates its heat treatment, as heat treaters we know that
we must achieve a delicate balance between the properties of strength and ductility. Nowhere is this fine
line more evident than in the tempering process where precise control of time and temperature are
critical to help produce a part with optimized microstructure and mechanical properties.
Essentially, tempering is the modification of this newly formed microstructure toward equilibrium. Almost
all steels that are subjected to any type of hardening process are tempered. A temper is a subcritical heat
treatment that alters the microstructure and properties. In general, tempering lowers strength and
hardness while improving ductility and toughness of the as-quenched martensite. However, this is not
always the case. Lets learn more.
What is Temper Embrittlement?
In general, embrittlement is a reduction in the normal toughness of steel due to a microstructural change
and chemical effects. Temper embrittlement is a phenomenon inherent in many steels, characterized by
reduced impact toughness. It occurs in certain quenched and tempered steels and even in ductile irons
with susceptible compositions. This form of embrittlement does not affect room-temperature tensile
properties but causes significant reductions in impact toughness and fatigue performance. Although
normally associated with tempered martensite, temper embrittlement can also occur if the matrix is
tempered to the fully ferritic condition.
Types of Temper Embrittlement
When tempering steel, several types of embrittlement must be avoided.
The first type, tempered martensite embrittlement (TME), is an
irreversible phenomenon that occurs in the range of approximately 250
400C (480F750F) and is often referred to as blue brittleness or
350C (500F) embrittlement. The second type, temper embrittlement
(TE), is a reversible phenomenon occurring when steels are heated in or
slow cooled through the temperature range of 375575C (705F
1070F).

Fig. 1. Effect of temperature
on impact toughness[5]
Recently it has been reported that a transition from ductile to intergranular fracture in steel having
greater than 0.5% C has been observed in martensitic steels tempered at low temperatures. Under tensile
or bending stress, these higher-carbon steels are highly susceptible to intergranular fracture in both the
as-quenched condition and after tempering at low temperatures generally considered to be safe from
these embrittlement phenomena. In view of the fact that tempering is not required to render the
microstructure susceptible to intergranular fracture, this type of embrittlement phenomenon is referred
to as quench embrittlement. [2]
Why does it happen?
Tempered martensite embrittlement and temper embrittlement are examples of intergranular
embrittlement. A common factor in such failures is the presence of elements that segregate to the grain
boundaries. The chemical reaction rate or kinetics of segregation are such that they exhibit C curve
behavior in the 350C 550C (660F 1020F) range. In other words, segregation does not occur
uniformly. Both types of embrittlement are in part related to grain-boundary segregation of impurity
elements (e.g. arsenic, antimony, phosphorus, and tin). Usually indicated by an upward shift in ductile-to-
brittle transition temperature, both types of embrittlement develop during thermal processing after
austenitizing and quenching to martensite.
Tempered martensite embrittlement is thought to result from the combined effects of cementite
precipitation on prior-austenite grain boundaries or interlath boundaries and the segregation of
impurities at prior-austenite grain boundaries.
Temper embrittlement that occurs in the range of 375575C (7051070F) is believed to be due to
segregation of impurity elements (P, Sn, As, Sb) to prior austenite grain boundaries. This causes
decohesion of the boundaries, resulting in the tendency for low-energy intergranular fracture under
certain loading conditions.

SEM photo of intergranular
temper
embrittlement (Courtesy of
Which steels are affected?
All steels are susceptible, so the real question becomes how susceptible and what factors affect that
susceptibility. For example, while plain-carbon steels may contain some of the impurity elements that will
cause the embrittlement phenomenon to occur, the segregation of these elements is often enhanced by
or caused by the presence of other alloying elements in substantial quantities. As a result, alloy steels
generally have more susceptibility than carbon steels.
It is important to understand that the degree of embrittlement is affected by the prior austenite grain size
and hardness. So, if we are dealing with a fine-grained plain-carbon steel of low hardness, it may not
experience embrittlement symptoms despite its phosphorous content whereas a more highly alloyed Cr-
Ni steel used at higher hardness is more susceptible to impurity content.
Widely used alloying elements such as chromium, nickel and manganese tend to promote temper
embrittlement with the highest embrittlement effect observed in Cr-Ni and Cr-Mo steels. Small additions
of molybdenum in Cr-Ni steels (0.2-0.3% in solution) can diminish temper embrittlement being caused by
phosphorus. Temper embrittlement can be diminished by keeping silicon and phosphorus levels as low
as possible, adding up to 0.15% molybdenum and avoiding the embrittlement heat-treating conditions.
Susceptibility also depends on impurity control, and here is where the steelmaking process is critical. For
example, in plain carbon and Cr-Mo steels (those with no Ni) where phosphorous is the most important
embrittlement element, the percentage can be controlled by the steelmaking process. In steels that
contain significant amounts of nickel, antimony and tin are more potent embrittlement elements.
Phosphorous has an effect, but not as large as it has in plain carbon and Cr-Mo steels. It should be noted,
however, that antimony and tin in plain-carbon steels could cause other hot-working issues.
How can we correct it?
Tempered martensite embrittlement (TME) is irreversible and its effects are permanent. By contrast, the
effects of temper embrittlement (TE) can be reversed. This is done by re-tempering above the critical
temperature of 575C (1070F), then cooling rapidly, or by re-austenitizing and cooling rapidly. Impact
toughness can be restored. If necessary, this process can be repeated.
A Simple Example
Alloy steel, which is susceptible to temper embrittlement, will exhibit a relationship such as shown below
(Fig. 1). The lower-temperature energy trough, 250400C (480F750F), is indicative of tempered
Matco Associates Inc.)
martensite embrittlement while the trough at the higher temperature, 450-650C (8401200F),
represents temper embrittlement.
Summing Up
The susceptibility of a given steel to temper embrittlement depends on a number of factors including
grain size, hardness, steel grade and the impurity control in the steelmaking process itself. Not all steels
and not all steelmaking processes are equal.
Finally, as heat treaters we must avoid the temptation to temper to a given hardness value without
understanding the consequences of our actions. Since we do not have a simple embrittlement test that
can be used on the shop floor, we must understand the phenomenon and question specifications that
put us into temper-embrittlement ranges.

HYDROGEN EMBRITTLEMENT High Strength
Steels Achilles Heel Part 1
Published on June 14, 2013 by Rob in News


Scanning electron microscopy of the fracture is an essential element of the failure analysis of this
Grade 8 High Strength fastener.
THE PHENOMENON
Sudden brittle fractures in high strength steels resulting from hydrogen embrittlement represent a
dangerous threat to industry. Not only are there the usual issues of cost such as warranty claims,
but in cases of personal injury or property damage, liability points clearly and directly at the
manufacturer. This is because hydrogen embrittlement is usually the result of deficient procedures
in the manufacturing process.
Well get into the why and how of hydrogen embrittlement in the next posting in two weeks. For now
though, lets just discuss some of the characteristics of this type of failure. Perhaps youll recognize
some of these from fractures youve encountered, but didnt realize at the time that hydrogen was
the cause.
Hydrogen embrittlement reduces ductility, often to the point where metals behave like ceramics.
Consequently, their resistance to fatigue fracture, their fatigue strength, is significantly reduced as
well. Fracture toughness, the ability of a metal to resist fracture growth when a small crack is
present, is also dramatically reduced. Brittle fracture due to hydrogen embrittlement occurs without
any visible distortion or other warning signs and can happen within hours of manufacture or after
years in service. Hydrogen embrittlement failures have even been observed in unassembled parts
in inventory, a phenomenon known as shelf popping.
Generally, the higher the strength of the steel, the more at risk it is to hydrogen embrittlement and
the more vulnerable it is to lower levels of hydrogen. Embrittlement at levels of 10 parts per million
and less are not uncommon. Some research suggests this relationship is exponential. In other
words, doubling the strength of the steel, quadruples its susceptibility to hydrogen embrittlement.
Although hydrogen embrittlement occurs in many different metal alloys, high strength steel appears
to be the most sensitive, is the most widely used, and accounts for the largest number of hydrogen
embrittlement failures. A professionally conducted failure analysis can definitely recognize hydrogen
embrittlement when present, what caused it, and how to prevent it.
In our next post we will discuss the phenomenon of hydrogen embrittlement from a metallurgical
perspective what actually occurs, on a microscopic scale that causes hydrogen embrittlement?
HYDROGEN EMBRITTLEMENT High Strength
Steels Achilles Heel Part 2
Published on June 20, 2013 by Rob in News


Expanded grain boundaries produced during a hydrogen embrittlement failure are clearly visible in
this image taken using a scanning electron microscope.
THE METALLURGICAL PHENOMENON
In our last post on Hydrogen Embrittlement and its effects on high strength steel we discussed the
characteristics of hydrogen embrittlement failures and some of the types of material that are
affected. In this post, we will describe how hydrogen embrittlement occurs, from a microscopic and
metallurgical perspective.
Hydrogen atoms are the smallest of any element. So small, that they easily travel between iron
atoms in steel and other ferrous alloys. Structurally, metals are composed of multi-atom crystals, or
grains, that are analogous to the cells that make up biological organisms. Typically, the grains in
metals are microscopic and the space between the grains, called the grain boundaries, is virtually
immeasurable. But in comparison to the size of a hydrogen atom, the grain boundaries are gapping
canyons.
Under unfavorable conditions individual hydrogen atoms can enter these grain boundaries and
move, or diffuse, into a metal component. Once absorbed in this manner, hydrogen atoms are
attracted to microscopic crystal defects, or misalignments, where there is slightly more space
between grains. They are also attracted to areas under tensile stresses that result in a very slight
increase in the space between grains from the opposing pull of the stress. A typical example of
this condition is a bolt that has been tightened.
As more hydrogen atoms accumulate at these areas, they combine to form hydrogen molecules.
Although composed of two hydrogen atoms, a hydrogen molecule (H
2
) is significantly larger than
two individual hydrogen atoms. This produces pressure between grains, expanding the size of the
defect or grain boundary interface, attracting more hydrogen atoms and accelerating the process.
This cycle produces a raising tensile stress inside the component which eventually results in a
micro-crack. These micro-cracks grow rapidly and simultaneously at numerous locations within the
part, reducing the actual intact load bearing cross section by as much as 10-20%.
In order for hydrogen embrittlement to occur, three conditions must coincide:
1. The part must have a tensile strength in excess off approximately 130,000 psi. This
generally corresponds to a hardness of Rockwell C 35.
2. The part must be in contact with a source of hydrogen. This may occur during manufacture,
in service, or both.
3. The part must be subjected to a tensile stress.
This last condition can be deceptive because parts do not need to be assembled or in service to be
under tensile stress. Residual internal stresses from casting, forging, welding and other
manufacturing processes are significant and, in fact, are probably the root cause of most hydrogen
embrittlement failures. Heat treating to raise strength levels above 130,000 psi induces substantial
levels of residual stress. The disturbing phenomenon of shelf popping, unassembled parts
cracking in storage or inventory with an audible pop, results from hydrogen embrittlement resulting
from residual stress.
Since the hydrogen is absorbed through the grain boundaries, hydrogen embrittlement cracking is
primarily intergranular (fracture at the grain boundary) rather than transgranular (fracture through
the grains) as in some other forms of brittle cracking.
In our next post, we will discuss potential sources of atomic hydrogen and conditions that make
components susceptible to hydrogen embrittlement.

HYDROGEN EMBRITTLEMENT High Strength
Steels Achilles Heel Part 3
Published on July 2, 2013 by Rob in News


Acid cleaning of this transmission input shaft during manufacture resulted in failure by hydrogen
embrittlement.
In our last post we discussed the metallurgical aspects of hydrogen embrittlement what actually
occurs that results in hydrogen absorption in metals and how it affects their material properties. In
this post we will look at the potential sources of hydrogen, what materials are susceptible to
hydrogen embrittlement, and why.
HYDROGEN SOURCES
One of the challenges in predicting and preventing hydrogen embrittlement is the wide range of
available sources of hydrogen, in both the manufacturing and the service environments.
Thermal dissociation of hydrogen from water is a prime source of hydrogen in manufacturing
processes. This can occur in the initial steel making process, as well as subsequent casting or
forging operations. Hydrogen can also be absorbed during grinding, abrasive blasting or tumbling,
soldering, brazing and welding. At these stages, hydrogen can be dissociated directly from high
dew point atmosphere, or from water absorbed in process related media, such as welding electrode
flux coatings, abrasive grinding wheels and fine absorbent dust in blasting and tumbling media.
Acid cleaning or pickling, and electro-plating, however, are the most common source of hydrogen in
manufacturing. Hydrogen containing acids used in these operations invariably infuse susceptible
parts with atomic hydrogen.
Service related sources of hydrogen include incidental contact with hydrogen containing acids or
cleaning solutions, or absorption from hydrogen containing product that is being processed, such as
chemicals, food, or even waste water.
The most common source of hydrogen in service by far, however, is corrosion. Corrosion can also
act as a source of hydrogen in the manufacturing process as well. Rusted ingots and scrap used in
casting melts, welding on parts that have corroded, and heat treating corroded parts, are potential
sources of absorbed hydrogen, particularly when exposed to elevated temperatures which increase
the mobility of hydrogen atoms.
SUSCEPTIBLE MATERIALS
High strength steels with tensile strengths above 130,000 psi and a hardness of Rockwell C35 or
greater are the most prone to hydrogen embrittlement. Steels below these tensile and hardness
levels are generally immune to hydrogen embrittlement. Why?
Increased hardness, most commonly by heat treating, is accompanied by a corresponding
decrease in ductility. In simple terms, ductility is the ability of a material to deform under stress
rather than crack or fracture. When hydrogen atoms combine into molecules in a steel that exceeds
the tensile strength and hardness thresholds, the steel cracks under the stress increase. But if the
tensile and hardness levels are below the critical threshold, the higher degree of ductility allows the
steel to deform, absorbing and redistributing the stress increase, rather than cracking.
Susceptibility to hydrogen embrittlement increases in alloy steels with heat treatment to higher
strength. The strength/susceptibility relationship, in fact, approaches exponential levels. In other
words, doubling the strength through heat treating, quadruples the steels susceptibility to hydrogen
embrittlement.
Identifying and sorting embrittled parts from good components before they fail is virtually
impossible. The detection limit of hydrogen by chemical analysis is generally well above the 5 to 10
ppm level at which embrittlement has been shown to occur. Even if such detection capability was
available, hydrogen tends to concentrate at specific locations within the part. This leaves the
majority of the part with low or undetectable hydrogen levels. Chemical analysis of parts after
failure, to determine if hydrogen embrittlement was the cause, is also not viable since the hydrogen
diffuses from the part after fracture.
Since most hydrogen embrittlement results from hydrogen absorbed during the manufacturing
process, parts which are batch processed are usually either all embrittled or all good. The failure
of one part from a batch, therefore, is usually a good indication that others from the same batch
will fail.



Hydrogen
Embrittlement
Part 1
Posted on 29. Nov, 2010 by Rob in Failure Analysis
Hydrogen Embrittlement Part 1
High Strength Steels Achilles Heel
The Phenomenon
Sudden brittle fracture in high strength steels resulting from hydrogen embrittlement
represents an extremely dangerous phenomenon to industry, particularly since it is usually
the result of factors that occur during the manufacturing process.
Hydrogen embrittlement reduces ductility, often to the point where metals behave like
ceramics. Consequently, fatigue strength and fracture toughness are also dramatically
reduced. Brittle fracture occurs without warning and can be immediate, within hours of
manufacture, or after years in service. Hydrogen embrittlement failures have even been
observed in unassembled parts in inventory, a phenomenon known as shelf popping.
Generally, the higher the strength of the steel, the more at risk it is to hydrogen
embrittlement and the more vulnerable it is to lower levels of hydrogen. Embrittlement at
levels of 10 parts per million and less are not uncommon. Some research suggests this
relationship is exponential. In other words, doubling the strength, quadruples the
susceptibility to hydrogen embrittlement.
Although hydrogen embrittlement occurs in many different metal alloys, high strength steel
appears to be the most sensitive, is the most widely used and accounts for the largest
number of hydrogen embrittlement failures. This article offers an overview on hydrogen
embrittlement as it relates to high strength steels only, though details of the phenomenon
generally apply to other susceptible metals.
First Appearance
In the late 1940s a revolution was underway in aviation. Jet propulsion was rapidly
replacing the old piston engine driven propeller technology and aircraft performance began
to exceed levels that had been considered physically impossible just ten years earlier.
Weight reduction and more power propelling airframes that could withstand higher loading
were critical to these improvements. This resulted in demands for higher strength alloys
from which smaller, lighter and stronger components could be made.
Low alloy steels such as 4130 had been used in aviation in the past. However, these
materials were typically used in the normalized heat treated condition, at tensile strengths in
the 90,000 to 120,000 psi range well below levels susceptible to hydrogen embrittlement.
In response to demands for more strength, radical heat treatments to tensile strengths
approaching 200,000 psi were applied to 4130 and other anemic low alloy steels. Some
of the first hydrogen embrittlement failures appeared, though they werent initially
recognized as such.
Enhanced low alloy steels, such as 4140 and 4340 were used in response to these failures,
and the cycle was repeated, with the demand for more performance from smaller
components resulting in processing to ever higher strength levels.
One of the unfortunate consequences of increasing the strength of low alloy steels is a
corresponding reduction in corrosion resistance. To combat increased corrosion in service,
a variety of electroplated coatings, such as chromium, nickel and cadmium, were applied.
With a new potent source of hydrogen now available from the plating baths used in these
processes, a dramatic increase in hydrogen embrittlement failures occurred in both the
aerospace industry and in other industries to which the new materials technology had
filtered down.

Hydrogen
Embrittlement
Part 2
Posted on 06. Dec, 2010 by Rob in Failure Analysis
Hydrogen Embrittlement Part 2
High Strength Steels Achilles Heel
The Metallurgical Phenomenon
Hydrogen atoms are the smallest of any element. So small, that they easily travel between
iron atoms. The boundaries between crystals, or grains, which are the structure of metals,
are gapping canyons in relative size to hydrogen atoms. Once absorbed, hydrogen atoms
are attracted to microscopic crystal defects, or misalignments, where there is slightly more
space between grains. They are also attracted to areas under tensile stress that cause a very
slight increase in the space between grains from the opposing pull of the stress.
As more hydrogen atoms accumulate at these areas, they combine to form relatively very
large hydrogen molecules (H
2
) which raises internal pressure, expands the size of the defect
or grain boundary interface and attracts still more hydrogen atoms, accelerating the process.
This cycle produces a raising tensile stress inside the component which eventually results in
a micro-crack. These micro-cracks grow rapidly and simultaneously at numerous locations
within the part, reducing the actual intact load bearing cross section by as much as 10-20%.
In order for hydrogen embrittlement to occur, three conditions must coincide:
1. The part must have a tensile strength in excess off approximately 130,000 psi. This
generally corresponds to a hardness of Rockwell C 35.
2. The part must be in contact with a source of hydrogen. This may occur during
manufacture, in service, or both.
3. The part must be subjected to a tensile stress.
This last condition can be deceptive because parts do not need to be assembled or in service
to be under tensile stress. Residual internal stresses from casting, forging, welding and
other manufacturing processes are significant and, in fact, are probably the root cause of
most hydrogen embrittlement failures. Heat treating to raise strength levels above 130,000
psi induces substantial levels of residual stress. The disturbing phenomenon of shelf
popping, unassembled parts cracking in storage or inventory with an audible pop, results
from hydrogen embrittlement associated with residual stress.
Since the majority of the hydrogen is absorbed through and accumulates at the grain
boundaries, hydrogen embrittlement cracking is primarily intergrannular (fracture at the
grain boundary) rather than transgrannular (fracture through the grains) as in some other
forms of brittle cracking.
Hydrogen Sources
One of the challenges in predicting and preventing hydrogen embrittlement is the wide
range of available sources of hydrogen, both in the manufacturing and service environment.
Sources from manufacturing include the original steel making process, subsequent casting
or forging, grinding operations, soldering and brazing fluxes, blasting and tumbling media,
welding electrodes, acid cleaning or pickling and electro-plating, etc.
Service related sources of hydrogen may include incidental contact with acids or hydrogen
containing cleaning solutions, or absorption from hydrogen containing product by
equipment used in its processing. The most common source in service by far, however, is
corrosion. Corrosion can also act as a source of hydrogen in the manufacturing process.
Rusted ingots and scrap used in casting melts, welding on parts that have corroded, and
heat treating corroded parts, are potential sources of absorbed hydrogen, particularly when
exposed to elevated temperatures which increase the mobility of hydrogen atoms.
Hydrogen
Embrittlement
Part 3
Posted on 13. Dec, 2010 by Rob in Failure Analysis
Hydrogen Embrittlement Part 3
High Strength Steels Achilles Heel
Susceptible Materials
While some stainless steel grades are susceptible, high strength steels with tensile strengths
and hardness above 130,000 psi and Rockwell C35, respectively, are the most prone to
hydrogen embrittlement. Steels below these tensile and hardness levels are generally
immune. Why?
Increasing hardness, most commonly by heat treating, is accompanied by a corresponding
decrease in ductility. In simple terms, ductility is the ability to deform under stress rather
than crack or fracture. When hydrogen atoms combine into molecules in a steel that
exceeds the tensile strength and hardness threshold, the steel cracks under the pressure
increase. But if the tensile and hardness levels are below the critical threshold, the higher
degree of ductility allows the steel to deform, absorbing and redistributing the pressure
increase, rather than cracking.
Susceptibility to hydrogen embrittlement increases in alloy steels with heat treatment to
higher strength. The strength/susceptibility relationship, in fact, approaches exponential
levels. In other words, doubling the heat treated strength, quadruples the steels
susceptibility to hydrogen embrittlement.
Identifying and sorting embrittled parts from good components before they fail is virtually
impossible. The detection limit of chemical analysis for hydrogen is generally well above
the 5 to 10 ppm level at which embrittlement has been shown to occur. Even if such
detection capability was available, hydrogen tends to concentrate at isolated locations
within the part. This leaves the majority of the part at low or undetectable hydrogen
levels. Chemical analysis of parts after failure, to determine if hydrogen embrittlement is
the cause, is also not viable since hydrogen diffuses from the part after fracture.
Since most hydrogen embrittlement results from hydrogen absorbed during the
manufacturing process, parts which are batch processed are usually either all embrittled
or all good. The failure of one part from a batch, therefore, is usually a good indication
that others from the same batch will fail over a similar time period.
Prevention
The two keys to avoiding hydrogen embrittlement are at the design stage and during the
manufacturing process. Designers with little metallurgical training may not realize the
implications of the materials and manufacturing processes they call for in the drawing
specifications. As with other failure modalities, hydrogen absorption can inadvertently be
designed into a part.
On the manufacturing side, avoiding reducing acids where possible removes an abundant
source of hydrogen from potential exposure to the part. Where electro- plating is required,
minimizing plating time and maximizing current density reduce the volume of absorbed
hydrogen. Consideration of electroless plating or vapor deposition as alternatives eliminates
the possibility for hydrogen absorption from the coating process altogether.
Protecting furnace charges or components that will be welded from corrosion, or cleaning
them prior to use will avoid hydrogen introduction by these routes. This applies equally to
parts that will be heat treated. Any processing that will elevate the temperature of the part,
and most do, will also raise hydrogen to a higher level of mobility, increasing the potential
for absorption.
Hydrogen Management
Despite the most stringent precautions, processing requirements will sometimes introduce
hydrogen to parts that exceed the hydrogen embrittlement tensile and hardness threshold.
Fortunately, there is a procedure that will effectively remove absorbed hydrogen. This oven
heating process, referred to as baking, is performed as follows:
1. Parts must be baked within 4 hours of hydrogen exposure. Less is better.
2. Parts must be baked at 400 F.
3. Parts must be held at 400 F for a minimum of 4 hours. Longer may be required
depending on part size, processing, etc.
To be effective, the time and temperature parameters must be strictly followed. Short-cuts
or delays on any step will dramatically reduce the effectiveness of the entire process. For
example, twice as much hydrogen will be baked out at 400 F versus 350F, and doubling
the bake time doubles the amount of hydrogen that is baked out.
The sooner baking begins after exposure to hydrogen, the better. The 4 hour window is a
maximum. Note that baking must be performed after each hydrogen exposure if 4 hours
will elapse between multiple exposures. No amount of baking will salvage embrittled parts
if these time and temperature parameters have not been met.
A final word of caution. A 30 year analysis of hydrogen embrittlement failures in the
aircraft industry found that over 70% resulted from improper baking procedures.
Closing
There are competing theories on the mechanism by which hydrogen embrittlement occurs.
That presented here appears to be the most widely accepted by the scientific community.
The subject of this article has been limited to hydrogen embrittlement in low alloy steels.
Other alloys are subject to hydrogen embrittlement, thought the mechanisms discussed are
the same. However, other hydrogen driven failure mechanisms have been observed, though
they appear to be less common. These include hydrogen induced blistering, internal
hydrogen precipitation and hydride formation in nonferrous metals.


Microstructure Effects on Hydrogen
Embrittlement in Austenitic Steels: A
Multidisciplinary Investigation
S. Evers,
1
T. Hickel,
2
M. Koyama,
3
R. Nazarov,
2
M. Rohwerder,
1
J. Neugebauer,
2
D.
Raabe,
3
M. Stratmann
1

1 Department of Interface Chemistry and Surface Science
2 Department of Computational Materials Design
3 Department of Microstructure Physics and Alloy Design
Hydrogen atoms, which can be absorbed into steel during production and service, often
have a detrimental embrittling effect on the mechanical properties of iron and steels. It is
meanwhile known that hydrogen embrittlement (HE) is also affected by the microstructure
of the material. Consequently, previous indications that hydrogen atoms are trapped by
vacancies, dislocations, and grain boundaries led at MPIE to investigations of
superabundant vacancy formation, hydrogen-enhanced local plasticity (HELP), and
hydrogen-enhanced decohesion (HEDE). Despite these efforts, any proof of a HE
mechanism to be active in a given steel sample has so far been a formidable task, which
cannot be achieved by a single method. A direct experimental observation of hydrogen
impurities is difficult due to the low solubility and high mobility of hydrogen in steels,
whereas pure theoretical investigations are challenged by the complexity and diversity of
microstructural features present in steels.
We therefore follow a multidisciplinary strategy to derive a deeper understanding of HE in
steels.
This strategy combines novel potentiometric methods based on the Kelvin probe technique
to detect the local hydrogen content in materials (GO department), ab initio determination
of the same quantities including the local behaviour at grain boundaries (CM department),
and characterization of hydrogen induced materials failure (MA department) using
orientation-optimized electron channelling contrast imaging (ECCI). Selected findings of
these investigations and their relevance for austenitic steels are summarized in the
following:
The crucial idea for the new hydrogen detection method is the observation that hydrogen
dissolved in a palladium matrix leads to the formation of a hydrogen electrode on the
palladium surface, even in dry atmospheres. The origin is the presence of a nanoscopic
water layer adsorbed on the surface, enabling the formation of a corresponding
electrochemical double layer [1, 2]. As the electrode potential for the hydrogen electrode
depends logarithmically on the activity of H in Pd, this potentiometric method is extremely
sensitive especially at low activities.
The idea can be employed for the investigation of steels (and various other materials) by
evaporating a thin film of Pd on their surface. Since the chemical potential of H in iron-
based materials is much higher than in Pd, H diffuses into the Pd film. Time dependent
measurements of this accumulation can be used to perform extremely sensitive and laterally
resolved measurements of H permeation through and its presence in materials. In the latter
case an effective activity of H is measured, providing information about depth and
density of traps sites. Main challenges of this method are the need for an exact calibration
of the potential-concentration correlation for H in the evaporated Pd films, the precise
calibration of the Kelvin probe tip in the dry nitrogen measurement atmosphere, as well as
its long term stability.
As an example the measurement of H in a H-charged austenitic steel sample, comprised of
mainly austenitic and ferritic grains, is shown in Fig. 1. It can be seen that the austenite
contains much more H, as the potential decreases much faster over the austenite grains.
Especially active sites are located at boundaries between ferrite and austenite.

Fig.1: Detecting hydrogen on a 5050 m surface area of a H charged austenitic
steel after evaporation of a 100 nm Pd film. a) A topographic image obtained by
AFM indicates austenitic (due to surface preparation topographically higher) and
ferritic (lower, i.e., darker) regions. b) and c) Potential maps of this area obtained
after 28 h and 44 h in the Kelvin probe mode. Above the austenites the potential
decreases faster than above the ferrites due to the larger amount of stored hydrogen.
The dark spots in b)-c) indicate sites with especially high hydrogen concentrations
(traps).
An additional insight into the relevance of the different phases and their boundaries has
been obtained by ab initio calculations based on density functional theory (DFT). They
clearly confirm the increased solubility of H in austenite grains as compared to the ferrite
grains. Mn yields further increase of the austenite solubility by straining the lattice (volume
effect). One of the new insights obtained by the calculations is that small amounts of further
alloying elements (like Ca, Nb, Si, Ti, and in particular Mo) considerably enhance the
preference of H for austenite [3].

Fig. 2: Potential energy surface for a single H interstitial next to a 11[1-10](113)
grain boundary in fcc iron. The minimum energy path for a diffusion in a (1-10) /
(113) plane perpendicular / parallel to the boundary is indicated by white dots. In
the upper part the corresponding energies along the same path are plotted.
In order to understand the experimental results on microstructures, we have additionally
used DFT to study the solubility and diffusion of hydrogen in austenite twin and grain
boundaries [4]. We generally find that the solution energy of H strongly depends on the
local coordination and that it is in this case only moderately correlated with the actual
volume of the interstitial site. Within open structures, such as the
11
[1-10](113) fcc grain
boundary, various different interstitial sites are favorable for the incorporation of H atoms,
providing effective trapping centres (Fig. 2). Only if these traps are filled by other H atoms,
efficient diffusion channels along (113) planes might become active. We further find that
the critical strain required to fracture the material is reduced by the presence of hydrogen in
this grain boundary. For twin boundaries, the DFT calculations show that interstitial H
atoms are actually slightly repelled. As origin for this unusual and unexpected behaviour
the structural similarity between the octahedral interstial configurations in the twins and in
austenitic bulk has been identified.
These theoretical insights are highly relevant for experiments, which investigate the
fracture mode in austenitic steels. For this purpose the recently developed orientation-
optimized ECCI method has proven to be particularly useful to reveal deformation twins
and complex dislocation substructures in TWIP steel. The actual measurements have been
performed for a H charged Fe18Mn1.2C austenitic steel [5], for which the tensile
ductility was drastically reduced by H charging during tensile testing. The central region of
these samples, which have not been reached by hydrogen, showed a ductile fracture
surface. In contrast, a brittle fracture surface was observed from the surface down to about
150 m. The facet size of the brittle fracture areas is about 50 m, which corresponds to the
grain size, indicating that intergranular fracture was caused by H charging.

Fig. 3: ECCI micrograph for the crack propagation in Fe18Mn1.2C austenitic
steel. The cracks initiate at a grain boundary, where deformation twins are
intercepting. The crack propagation afterwards continues along the deformation
twins.
An advantage of the employed ECCI method is that in addition to the cracks primary and
secondary deformation twins on (11-1) and on (1-11) planes become visible with bright
contrast (Fig. 3). The measurements therefore revealed that cracks typically occur at grain
boundaries with intercepting primary deformation twins. The stress concentration at these
points and the reduction of the cohesive energy by hydrogen loading apparently yields
crack initiation. While the primary fracture mode is intergranular, one additionally observes
crack propagation following primary and secondary deformation twin boundaries (Fig. 3).
Since the ab initio calculations predict that perfect twin boundaries are not sensitive to H,
the stresses due to the interception of twins with grain boundaries or of primary with
secondary twins need to be responsible for such a transgranular fracture along twin
boundaries. Being crucially important, because deformation twinning is essentially
required to achieve the superior mechanical properties of TWIP steels, further
investigations of this effect are currently performed.
[1] Senz, C.; Evers, S.; Stratmann, M.; Rohwerder, M., Scanning Kelvin Probe as a
Highly Sensitive Tool for Detecting Hydrogen Permeation with high local Resolution,
Electrochemistry Communications 13 (2011), 1542-1545, DOI:
10.1016/j.elecom.2011.10.014
http://edoc.mpg.de/577499
[2] Evers, S.; Rohwerder, M., The hydrogen electrode in the dry: A Kelvin probe
approach to measuring hydrogen in metals, Electrochemistry Communications 24 (2012),
85-88, DOI:10.1016/j.elecom.2012.08.019
http://edoc.mpg.de/624681
[3] Nazarov, R.; Hickel, T.; Neugebauer, J.: in preparation
[4] Du, Y. J. A.; Ismer, L.; Rogal, J.; Hickel, T.; Neugebauer, J.; Drautz, R., First-
principles study on the interaction of H interstitials with grain boundaries in alpha- and
gamma-Fe, Phys. Rev. B 84 (2011), 144121, DOI: 10.1103/PhysRevB.84.144121
http://edoc.mpg.de/581728
[5] Koyama, M.; Akiyama, E.; Sawaguchi, T.; Raabe, D.; Tsuzaki, K.: Hydrogen-induced
cracking at grain and twin boundaries in an FeMnC austenitic steel, Scripta Materialia
66 (2012), 459-462, DOI: 10.1016/j.scriptamat.2011.12.015