American Welding Society – Welding Journal Page 1 of 5

Understanding Hydrogen Failures

The effects of hydrogen can be lessened or even eliminated through careful selection of base
metals, weld metals, and fabrication practices, as well as adherence to procedures

BY J. R. STILL

Fig. 1 —If hydrogen is introduced, the piping systems on this floating production storage and
offloading vessel can be susceptible to corrosion and corrosion-assisted cracking.

The ingress of hydrogen into metals can occur in several ways depending on material type,
the presence of hydrogen in the form of atomic hydrogen, and factors such as the solubility
of atomic hydrogen, the pressure of hydrogen, and stress (Refs. 1, 2).

Carbon and carbon-manganese steels and weld metals are susceptible to hydrogen ingress
from several sources. Two primary sources are the ingress of atomic hydrogen into the piping
material and weld metal resulting from the processing of reservoir fluids and the ingress of
hydrogen resulting from the presence of moisture during welding of process piping.

The first route involves separating reservoir fluids into oil, gas, and formation water. Figure 1
shows an offshore processing facility on a floating production storage and offloading (FPSO)
vessel. The FPSO facility consists of piping systems linked to equipment associated with the
separation process. Failures linked to the ingress of hydrogen in process piping systems are
associated with corrosion or corrosion-assisted cracking. One of the products of corrosion is
hydrogen.

The second route is associated with the introduction of hydrogen into the weld pool during
welding (Refs. 3, 4). In this instance the failure mechanism results from the breakdown of
moisture, where hydrogen is absorbed by the weld pool from the arc atmosphere. The failure
mechanism is then similar to that experienced in the processing of reservoir fluids.

Corrosion and Corrosion-Assisted Cracking

Depending on the reservoir composition, compounds such as carbon dioxide (CO2),
hydrogen sulfide (H2S), or a combination of both can be present in hydrocarbons. The terms
"sweet" and "sour" are used in the oil and gas industry to identify hydrocarbons that contain
CO2 and H2S, respectively. Carbon dioxide and hydrogen sulfide in the presence of water
when subjected to pressure and temperatures during separation are two main contributors to
corrosion of process facilities and piping systems. Following are examples of corrosion
failure types experienced during processing of hydrocarbons.

Weight Loss Corrosion

Fig. 2 —An example of weld metal failure due to weight loss

corrosion.

An example of weight loss corrosion (Refs. 5, 6) is illustrated in

Fig. 2. This form of failure is mainly attributed to carbon dioxide
and water forming carbonic acid. The presence of carbonic acid
(H2CO3) reduces the pH of the water, resulting in localized
corrosion such as pitting. A similar effect occurs with hydrogen
sulfide except that the reaction produces iron sulfide, which is
unprotected and easily removed. One of the products of this
reaction is atomic hydrogen. The reactions for H2CO3 and H2S
are outlined below:

H2CO3 Reaction:

Fe+H2CO3->FeCO3+H2

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H2S Reaction:

Fe+H2S+H2O->FeS+2H

Environmental Cracking

Fig. 3 —Environmental cracking in the weld HAZ.

The term "environmental cracking" (EC) is used to describe

sulfide stress cracking (SSC) and stress corrosion cracking
(SCC) (Ref. 7). An example of environmental cracking (Ref. 8)
in the heat-affected zone (HAZ) of a weld is illustrated in Fig. 3.
Materials and weld metals subjected to mechanical stresses such as thermal processing,
residual stresses, and manufacturing practices within a low pH production fluid that contains
hydrogen sulfide can experience cracking. Hydrogen sulfide dissociates into atomic
hydrogen and ferrous sulfide.

Atomic hydrogen penetrates the weld metal, pipe material, or HAZ lattice structure and,
when subjected to mechanical stress, local embrittlement occurs. Examples of environmental
cracking include the following:

Sulfide stress cracking (SSC), also referred to as sulfide stress corrosion cracking
(SSCC)

Stress corrosion cracking (SCC)

Hydrogen stress cracking (HSC), also known as hydrogen embrittlement (HE).

Other forms of SCC, such as chloride stress corrosion cracking (CSCC), are treated
similarly to other forms of environmental cracking.

Cracking in an H2S Environment

Fig. 4 —Hydrogen-induced cracking in A333 Grade 6 pipe

material used in an H2S environment.

Cracking associated with a sour environment is classified as

hydrogen-induced cracking (HIC) (Ref. 9).

Failure in this instance is similar to environmental cracking (Ref. 10), where hydrogen
sulfide dissociation into atomic hydrogen penetrates the weld metal, pipe material, or HAZ
lattice structure. In this instance, the hydrogen atoms encounter nonmetallic inclusions and
then the hydrogen recombines to form molecular hydrogen. This process results in the
buildup of molecular hydrogen, with an increase in pressure within the nonmetallic inclusion.
This continues until the pressure buildup is sufficient to initiate fracture. A number of factors
such as pH, volume of hydrogen diffused, volume-fraction, and the shape of inclusions
present, and the surrounding microstructure influence the process. Stress in this instance is
not as critical compared with SCC and SSC (Ref. 7). Failure types include the following:

Hydrogen-induced cracking (HIC)

Stepwise cracking (SWC)

Stress-oriented hydrogen-induced cracking (SOHIC)

Hydrogen blistering
Figure 4 provides an example of hydrogen-induced cracking in which the material
contained a high-volume-fraction of inclusions. It is recommended (Ref. 11) that sulfur
levels of materials for wet H2S service be controlled at 0.002% maximum to avoid
HIC. Additions of inclusion shape control elements, such as calcium or rare earth
elements (Ref. 12), are used to prevent HIC.

Preferential Weld Corrosion

Fig. 5 —Schematic of the cathodic

reactions that can occur in
seawater injection systems, which
result in preferential weld

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corrosion.

While not directly associated with separating hydrocarbons, seawater injection systems are
used for injecting seawater into the reservoir to maintain pressure. They are susceptible to
preferential weld corrosion (Ref. 13). This form of corrosion is the result of galvanic
coupling, whereby the weld metal acts as an anode and the pipe material as a cathode (Ref.
14). The anodic and cathodic reactions involved are outlined in Fig. 5.

The corrosion reaction involved produces hydrogen, which reduces the pH of the seawater
resulting in an increase in the acidity.

Fig. 6 —Preferential weld corrosion in A106 Grade B pipe.

Oxygen content of the seawater also has to be present to

promote formation of ferrous oxide, which is readily removed
when the velocity of the seawater is in the region of 2.5 m/s.
The process continues until the outer surface of the weld is
penetrated. An example of this form of corrosion is illustrated in
Fig. 6. To avoid preferential weld corrosion, the oxygen content of the seawater has to be low
and the weld deposit and HAZ must behave cathodically with respect to the pipe. This is
achieved by selecting an electrode of suitable composition that behaves in a cathodic manner.

Hydrogen Cracking Associated with Welding Process Piping

Cracking associated with corrosion-assisted cracking such as HIC and SWC is similar to
other forms of hydrogen cracking. This involves weld metal and HAZ cracking encountered
during welding if procedures are not adhered to (Ref. 15). Types of weld metal and HAZ
cracking attributed to hydrogen include the following.

Heat-Affected Zone Cracking

Fig. 7 —An example of hydrogen-induced cracking in a weld heat-affected zone.

An example of HAZ cracking of a pipe HAZ is illustrated in Fig. 7. The HAZ cracking
mechanism (Ref. 16) is similar to environmental cracking. Factors influencing HAZ cracking
in carbon and carbon-manganese steels include the following:

Hydrogen.The source of hydrogen is the moisture retained within the electrode coating.
Baking of electrodes to ensure the moisture is removed prior to welding is essential. Other
potential sources of hydrogen involve paint and grease and failure to remove moisture from
the weld area prior to welding. Material hydrogen levels can also contribute to HAZ
cracking.

Chemistry.The chemical composition provides a guide, through the carbon equivalent, to

the level of preheat required to ensure that the HAZ microstructure hardness levels are within
the NACE MR0175 requirements.

Preheat temperature. The preheat temperature applied must be capable of ensuring that
the time to cool between øt 800 to 500°C produces acceptable microstructure and hardness
levels.

Heat input. Heat input is determined by the welding parameters. Low heat inputs in the
absence of preheat will produce high HAZ hardness levels. It is essential that the interpass
temperature is not allowed to reach temperatures that affect the øt 800 to 500°C cooling rate
and thus the properties of the material.

To avoid hydrogen cracking in welds and HAZs, the controls listed above must be strictly
adhered to.

Fisheyes

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Fig. 8 —An example of a fisheye.

Fisheyes (Ref. 16) are a form of hydrogen embrittlement that is confined to as-welded
structures. Hydrogen can be retained within a weld defect such as a pore. When a weld joint
tensile test is subjected to a slow strain rate, necking of the tensile specimen starts. The
hydrogen retained within the pore and surrounding area is subjected to a further increase in
the applied strain, resulting in local embrittlement. When the tensile specimen fractures, the
pore appears as a brittle area with a ductile structure, as illustrated in Fig. 8. This form of
hydrogen failure is found mainly in tensile specimens from procedure pipe welds that have not
been subject to the controls listed above.

Other Forms of Hydrogen Cracking

Fig. 9 —An example of chevron cracking.

The following is a brief description of types of hydrogen cracking

associated with fabrication of process piping, pressure-retaining
facilities, and structural fabrications:

Chevron cracking. This type of cracking (Ref. 17) has never been known to occur in
process piping and is mainly confined to thick-wall multipass welds deposited in carbon and
carbon-manganese steels. The cracking mechanism is attributed to poor housekeeping of the
submerged arc flux, which has been allowed to absorb moisture. During welding, the
moisture dissociates into hydrogen and oxygen. The oxygen may form oxides within the
weld, or recombine and evaporate. Hydrogen becomes trapped as the weld metal cools and, if
sufficient hydrogen is present, cracking can occur. The cracks take the shape of a chevron,
hence the name chevron cracking as illustrated in Fig. 9.

Fig.
10
—
An
example
of
lamellar
tearing. The type of failure
associated with hydrogen
has been nearly eliminated
since the introduction of
"clean" steels with low-
sulfur contents.

Lamellar tearing. The

existence of lamellar
tearing is widely accepted
as being the result of weld
shrinkage stress acting
through the thickness
direction of steels with
high inclusion contents
(Ref. 16). However, prior
to the introduction of clean
steels in the 1970s, the
diffusion of hydrogen
from deposited weld
metals was recognized as
one of the factors
influencing lamellar
tearing (Ref. 17). Research
carried out in 1972 (Ref.

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18) reported that lamellar

tearing was influenced by
a combination of
contracting stress,
presence of nonmetallic
inclusion, and hydrogen
diffused from the weld
metal. Hydrogen in this
instance acts in a similar
way to that reported for
cracking associated with
an H2S environment. It
was concluded that
inclusion content was the
main factor and must be
limited if lamellar tearing
was to be controlled.
Figure 10 shows an
example of lamellar
tearing.

Lamellar tearing has

virtually been eliminated
due to the production of
clean steels with sulfur
levels below 0.005%.

Summary
The selection of suitable
materials and weld metal
on new and mature
installations is now
common practice,
provided the fluid or gas
composition, in
conjunction with operating
conditions, warrants their
selection. Provided the
material and weld metal
selection is correct, the
effect of corrosion can be
stemmed and in some
instances eliminated.

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