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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.
H2CO3 Reaction:
Fe+H2CO3->FeCO3+H2
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H2S Reaction:
Fe+H2S+H2O->FeS+2H
Environmental Cracking
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.
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:
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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.
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.
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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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.
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.
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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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