J Solid State Electrochem (2009) 13:1091–1099

DOI 10.1007/s10008-009-0799-0

REVIEW

Metallurgical factors in stress corrosion cracking (SCC)

and hydrogen-induced cracking (HIC)
M. Elboujdaini & R. W. Revie

Received: 15 August 2008 / Revised: 23 January 2009 / Accepted: 27 January 2009 / Published online: 25 March 2009
# Her Majesty the Queen in Right of Canada, as represented by the Minister of Natural Resources 2009

Abstract Nonmetallic inclusions can affect resistance of Keywords Stress corrosion cracking (SCC) .
steels to both general and localized corrosion, including Hydrogen-induced cracking (HIC) . Nonmetallic inclusions .
pitting corrosion, stress corrosion cracking (SCC), and Metallurgical factors
hydrogen-induced cracking (HIC). Because stress corrosion
cracks frequently initiate at pits, and pits nucleate at
sulfides, the presence of sulfides is likely to affect the Introduction
SCC process. Nonmetallic inclusions increase susceptibility
of steel to HIC, which occurs by the formation of internal Cracks in linepipe steel
hydrogen blisters or blister-like cracks at internal delami-
nations or at nonmetallic inclusions in low strength There are many reasons for cracks to occur in a linepipe:
materials. HIC occurs when H atoms diffusing through a cracks can develop from: (a) material defects; (b) during the
linepipe steel become trapped and form H2 molecules at plate to pipe rolling fabrication; (c) from hydrogen in the
inhomogeneities in the steel. A planar, gas-filled defect is welds; and (4) in root beads or fill passes which are too thin
created, which grows parallel to the pipe surface as it or too weak. Defects in the linepipe can grow due to fatigue
continues to trap more diffusing H atoms. If the defect during the pipe operation. In-service crack growth mecha-
grows sufficiently large, it may develop into a blister. HIC nisms include, stress corrosion cracking (SCC) and
failure occurs if a mechanism exists for linkage of hydrogen-induced cracking (HIC).
defects or blisters with the internal and external surfaces. SCC is a form of environmentally assisted cracking
The H atom source is normally the cathodic reaction of an (EAC) that is of great significance to the oil and gas
acid corrosion mechanism occurring at the internal pipeline industry. When ground water penetrates under the
linepipe surface, i.e., the reduction of hydrogen ions, pipe coating, cracks may develop and grow through the
H + : Anodic reaction: Fe ! Fe2þ þ 2e
Cathodicreaction: external pipe wall. Over the last decades, thousands of
2Hþ þ 2e
! 2Hads colonies of such cracks have been found in pipelines.
These cracks frequently become dormant at depths of
about 1 mm. Occasionally, the cracks continue to
propagate, leading to pipe rupture [1].
HIC occurs in a steel if there is a susceptible micro-
Dedicated to the 85th birthday of John OM. Bockris. structure (metallurgical factor) and sufficient diffusing
M. Elboujdaini (*) : R. W. Revie hydrogen (H) atoms to initiate and propagate damage
CANMET Materials Technology (environmental exposure factor). These two factors are
Laboratory—Natural Resources Canada,
interrelated. All steels have a unique critical or threshold
568 Booth St.,
Ottawa, ON K1A OG1, Canada value of H atom concentration for initiation of hydrogen
e-mail: [email protected] damage. If the concentration of diffusing H atoms (COH
1092 J Solid State Electrochem (2009) 13:1091–1099

Fig. 1 Small ‘SCC’ cracks that

are widespread in tape-coated
pipeline

a b

value) is measured at the charging surface, this threshold steel, residual stress in the steel as well as applied stress,
value is expressed as (COH)Th. water chemistry in the field, including CO2, oxygen, and
The effects of both metallurgical and environmental ionic concentrations in the groundwater near the pipe
factors on SCC and HIC are discussed in this paper. surface, may all have an effect on crack initiation and
propagation [2–6]. Stress corrosion cracking in pipelines
involves several steps: (a) the coating applied to the
Stress corrosion cracking phenomena pipeline during installation becomes degraded, an electro-
lyte comes into contact with the surface, and the environ-
SCC mechanism ment that causes SCC to develop; (b) the initiation and
growth of multiple cracks that form colonies; (c) these
SCC has been observed on the soil side of buried, natural gas cracks may continue to grow and coalesce; and (d) in the
pipelines since the early 1960s. Transgranular cracking occurs final step, a dominant crack reaches a critical size for rapid
in environments with pH about 6.5, and is referred to as near- growth to failure, producing either a leak or a rupture,
neutral pH stress corrosion cracking, as opposed to high-pH Fig. 1. The time to failure depends on a number of factors,
stress corrosion cracking, which is intergranular in nature. including the pipe material, stress history, environment, and
SCC results from multiple metallurgical, mechanical, crack distribution. Nevertheless, most colonies do not result
and environmental factors. Chemical composition of the in failure as the cracks become dormant.

Fig. 2 EDS spectra indicating

chemical composition of three
(a)
CaAlO3
different inclusions as associated
with the initiation of pits in X- d k
65 steel sample (before and after Al S Ca
test at σmax =90%YS, R=0.6 and
f=0.1 Hz in NS-4 solution satu-
rated with N2/5%CO2). Note the
rapid dissolution of CaS inclu-
sions and the formation of cor-
rosion pits around the inclusions (b)
[7]

Al S Ca
CaAlO3
CaS
20 µm

(c)
CaS
S
Al Ca
All dissolved

EDX Spectrum Before After

J Solid State Electrochem (2009) 13:1091–1099 1093

Fig. 3 a Development of pits from inclusions and b nucleation of cracks at pits in a sample of Steel X-65. The specimen was tested in NS4
solution saturated with CO2 at σmax =70% YS, R=0.6 and f=0.1 Hz. In c EDS spectrum reveals the elements: Na, Mg, Al, Si, P, S, Cl, K, and Ca

Nearly all studies of SCC have been carried out without on crack initiation, role of crack initiation sites, inclu-
distinguishing the characteristics of initiation from those of sions, factors governing crack growth, and the crack
propagation. Many of the studies on propagation have coalescence process in the context of low-pH SCC in
focused on growth of long cracks in pre-cracked specimens. linepipe steel.
Initiation of SCC is, however, studied using specimens that For the current research, the validation of the results
are not pre-cracked. The definition of an initiated crack is under accelerated test conditions is based on the assumption
not well defined, and there is no clear mechanistic that the micro-processes, microstructural features, and
interpretation of the events that lead to initiation. specific sites associated with initiation of cracks in
SCC has been observed to initiate from the base of laboratory tests are those associated with the initiation of
localized corrosion sites (i.e. pits, crevices) for a variety of SCC in operating pipelines.
metal–environment combinations [7–10]. There remains
debate on whether the stress intensification at the base of & The results of laboratory tests show that cracks initiate
the pit or the enhanced electrochemical conditions within at sites that are related to metallurgical factors, such as
the pit are the controlling factor in SCC [11–14]. Several nonmetallic inclusions (Fig. 2). Nonmetallic inclusions
investigators believe it is the localized environment that and other forms of surface discontinuity or surface
plays the biggest role in crack initiation and not necessarily defects exert a significant influence on pits and micro-
the stress concentration provided by the localized corrosion crack initiation. Nonmetallic inclusions can serve as
site [15, 16], whereas others believe that crack initiation in germs for the formation of pits and domains of intense
smooth samples requires the presence of a stress raiser [17]. etching of the surface of pipes.
The most common way to establish such a stress raiser is & The time-dependence of crack development includes
either through corrosion or mechanical damage. the following factors: (a) existence of an incubation
period, (b) changes in crack number density, crack size
Initiation of SCC with time, dormancy, and (c) the crack growth rate
(Fig. 3). Many cracks are found to become dormant,
There are generally three stages of the cracking process: and hence, are innocuous. Significantly, dormant cracks
(a) generation of an environment that causes cracks to are always found near the site of ruptures (Fig. 4), so it
initiate; (b) initiation of cracks; and (c) propagation of is felt that these cracks are sometimes precursors to
cracks until failure occurs. The present study is focused rupture [18]; and
Fig. 4 a Failure in hydrostatic
testing, SCC as root cause; b
magnetic particle inspection
(MPI) picture of SCC colony
found next to a pressure failure.
The outside pipe surface shows
additional, longitudinal cracks
adjacent to the fracture origin
1094 J Solid State Electrochem (2009) 13:1091–1099

Complexities in SCC phenomena

1
1 SCC in steels for oil and gas pipelines is a very complex
and challenging phenomenon. The complexity of SCC is
reflected in the changes, with time, of the diverse
2 parameters influencing the cracking phenomena, whereas
the biggest challenge is in obtaining field-relevant repro-
2
ducible laboratory data. SCC encompasses major effects
from metallurgical, mechanical, and environmental param-
eters, all of which can be dominant under specific
conditions. Adding to the complexity are the loading
conditions in operating pipelines that define the mode of
failure as SCC or, considering dynamic loading, possibly as
corrosion fatigue (CF; Fig. 6).
3
3
Hydrogen-induced cracking
Fig. 5 Development of cracks showing the interaction and coales-
cence of cracks. (Observations were made on replicas) [7] HIC is one of several related mechanisms whereby
absorbed hydrogen atoms can compromise the integrity of
& The spatial distribution of cracks is also relevant. linepipe steels. The development of internal cracks in
Spacing affects crack interaction and coalescence and linepipe steels as a consequence of the trapping of absorbed
significantly influences the overall cracking behavior, hydrogen atoms (H atoms) as gas molecules (H2 molecules)
and hence, the lifetime of a pipeline. The linking or at inhomogeneities is termed HIC. The cracks most often
coalescence process for neighboring growing cracks (but not always) lie parallel to the rolling plane and to the
(Fig. 5) was proposed [19, 20] as a means to encourage surfaces of the steel component. Residual or applied tensile
growth, and was shown by measurements to be more stress is not needed for HIC development, Fig. 7. The HIC
likely associated with crack tip dormancy [21–23]. is typically associated with non-metallic inclusions such as
elongated manganese sulfides (MnS), Fig. 7b.
There are several implications of the above factors on the When hydrogen permeation causes the hydrogen con-
operation of a pipeline. The source of stresses that are centration to exceed a critical value, hydrogen induced
exerted on the pipe during its operation must be considered; cracking results, as shown in Fig. 8a. It is well-known that
e.g., the operating pressures in the pipeline and more the cracking in H2S environments is associated with the
importantly the pressure variation during operation. Other presence of non-metallic inclusions, especially MnS, and a
implications are concerned with the type of soil surrounding banded structure [24]. The interfaces between large MnS
the pipe and ground movements, including frost heave and inclusions and/or the banded structure and matrix usually
thaw settlement, which could apply external stresses to the act as sinks for hydrogen (Fig. 8b). Hydrogen tends to
pipe. The type of soil and how it could affect the acidity, or diffuse to these interfaces and reach the critical value. Since
pH, of the groundwater around the pipe is also important. the cracks initiate at the elongated MnS particles, the HIC
Metallurgical factors relate to nonmetallic inclusions in the susceptibility decreases with decreasing sulfur content.
steel from which the pipe is made and the steelmaking Rolling at lower temperature increases HIC susceptibility
practices used in its production. Other metallurgical factors by elongating the sulfide inclusions. The increased suscep-
relate to the mill welds used to make the linepipe and the tibility could be due to the interface reaction between steel
field welds that are used to join the pipes. and the wet H2S environment.

Fig. 6 Surface morphology of

specimen (X-52), containing coalescence of cracks
cracks that developed during 1 2 4
pipeline operational service. The 3
cracks numbered linked during
testing in NS4 solution saturated
with 5%CO2/N2, leading
to failure
J Solid State Electrochem (2009) 13:1091–1099 1095

Fig. 7 Hydrogen induced cracking of carbon steel pipeline showing a HIC; b crack at MnS inclusion location and c near the pipe surface rough
convex bumps called “blisters”

Atomic hydrogen diffuses into the steel, forming blisters Role of inclusions in HIC
in the microscopic voids around nonmetallic inclusions.
The gas pressure in these blisters generates very high The EDX microanalysis revealed that the inclusions in
localized stress, which initiates cracking along lines of cracks are manganese sulfide. The present investigation
weakness in the steel. Blisters often occur when the shows that MnS inclusions are the dominant initiation sites
hydrogen-induced crack is unable to propagate further in for cracking. In fact, microvoids around MnS and other
the parallel-to-surface direction, and is unable to link up inclusions provided sites for hydrogen to accumulate,
with HIC on adjacent planes in the steel (Fig. 8b). This may leading to higher HIC susceptibility (Fig. 11).
be because the hydrogen atom-trapping inhomogeneity In order to quantify the relationship between HIC and
which caused the blister to form has a finite length; Fig. 8a non-metallic inclusions, specifically planar arrays of
A special form of HIC may occur when the local stress aligned inclusions, quantitative metallographic information
concentration is high in a sour service pipeline namely was developed for the inclusion population in a number of
“stress-oriented hydrogen induced cracking (SOHIC)”. linepipe steels that were assessed for HIC. Chemical
High stress fields can allow the hydrogen to accumulate compositions and yield strengths of these steels are listed
without the need for inclusions or other interfaces. For in Table 1. This was achieved by image analysis where two
example, some types of spiral-welded pipe exhibit highly types of inclusion geometry were identified and measured
stressed regions close to the seam weld, caused during the separately, namely, long strings of fragmented inclusions
edge-forming process, Fig. 9. The presence of tensile stress and other dispersed inclusions. The end map shown in
in the component may cause individual ligaments of HIC to Fig. 12 illustrates these two types. The map is basically a
form in a stacked, through-thickness array. This is a low magnification assembly of the metallographic informa-
necessary precursor to what is called SOHIC. This array tion observed at high magnification, indicating the overall
is oriented perpendicular to the principal applied stress. The image of the inclusion population through the wall
HIC may subsequently completely link up to cause thickness of the linepipe steel. The sample is covered by
through-wall cracking and loss of linepipe integrity, i.e., 12 microscopic fields through the wall thickness (6 mm)
SOHIC. Like SWC, SOHIC is probably a combination of and 46 fields in the longitudinal direction (each field is
HIC and either hydrogen embrittlement cracking (HEC) or 400×400μm). The end map shown in Fig. 12 identifies
sulfide stress cracking (SSC) as shown in Fig. 10. susceptible areas for hydrogen induced cracking on the
In the study reviewed in this paper, we examined the role sample as indicated by the thick solid lines (representing
of nonmetallic inclusions in the initiation and propagation long strings of fragmented inclusions) and the blister crack
of cracks in a series of linepipe steels. in Fig. 11.

Fig. 8 a Hydrogen blister in

NPS 6 sour gas pipeline
(Canada 1997 Failure);
b Blistering and through-wall
crack in seamless linepipe
(arrow shows leak location at B list
Blist
sters
rs
blister; courtesy of M. Hay/Shell Leak Location at
Canada) a b
Blister
1096 J Solid State Electrochem (2009) 13:1091–1099

Fig. 9 SOHIC failure of NPS 16 spiral-welded linepipe (Canada 1979

failure; courtesy M. Hay/Shell Canada)
Fig. 11 Hydrogen-induced cracking. Blister crack

Data on length of inclusions were investigated by image

analysis (Fig. 12) and are reported in Table 2. The results products in the steel. The linking of nearby cracks takes
are correlated with threshold hydrogen concentration, place along bands of localized shear, which result from the
(COH)Th, and plotted in Figs. 13 and 14. Both volume internal hydrogen pressure acting on elongated blister cracks.
fraction and total length per unit area have a relationship Hydrogen, as an embrittling element in steels, is still a
with the threshold hydrogen concentration. It is clear from significant problem. The mechanism of hydrogen embrit-
these figures that the steel with minimum inclusions has the tlement in steels is not completely understood, especially
highest threshold hydrogen concentration. since no one theory in particular is able to describe all of
The size and shape of the inclusions were considered to the hydrogen–metal interaction phenomena observed. From
depend on the Ca/S ratio in steel. The Ca/S ratio [24, 25] in the various damage theories proposed, in the de-cohesion
Table 2 showed that increasing the ratio of Ca/S decreases theory both the adsorbed and absorbed hydrogen may be
the hydrogen damage susceptibility (i.e., steels CTR-2 and accepted. According to the reduced atomic cohesion/model
AM-2). According to the results, steel susceptibility to SSC for hydrogen embrittlement proposed by Oriani [26],
and HIC depends on the stress localization around large and hydrogen embrittlement might be interpreted as being due
hard inclusion particles. This localized stress could exceed to reduced atomic cohesion at the location of stress
the yield strength. concentration by the accumulation of hydrogen atoms.
The metallurgical aspects of HIC can be summarized as The higher the COH value, the greater the reduction in
follows: (a) the formation of internal blister cracks by the atomic cohesion at the stress concentration location.
accumulation of hydrogen at inclusion microvoids, (b) the
extension of these cracks parallel to the rolling plane by Avoidance of HIC in new linepipe
the internal hydrogen pressure, and (c) the linking of nearby
cracks along directions inclined to the rolling plane by Two measures can be taken to increase the HIC resistance
plastic deformation and fracture. The formation of blister of new linepipe: (1) lower COH, the surface concentration of
cracks seems to be directly related to the type and diffusing H atoms, and (2) raise (COH)Th, the threshold
distribution of nonmetallic inclusions in the steel. Extension surface concentration of diffusing H atoms to initiate HIC.
of blister cracks takes place along paths of low-fracture
resistance parallel to the rolling plane. The exact nature of Lowering the COH value
these fracture paths is not known, but it has been suggested
that the fracture paths are bands of certain transformation The COH value can be lowered by such measures as chemical
corrosion inhibition and encouraging the development of
passivating iron sulfide films. Generally, we should not rely
on coatings or corrosion inhibitors to protect steel (or other
materials) from environmental embrittlement mechanisms
such as HIC, SSC, and SOHIC. Materials should be selected
that are inherently resistant to all known cracking phenom-
ena. The COH value may be reduced in some sour environ-
ments by alloying the steel with certain elements; e.g., Cu.
Addition of Cu does not affect the (COH)Th value. It merely
Fig. 10 StepWise cracking in plate steel exposed to sour gas (Lab. prevents HIC in susceptible materials by keeping COH <
C-ring test) (COH)Th in sour environments with pH values in excess of
J Solid State Electrochem (2009) 13:1091–1099 1097

Table 1 Chemical analysis (wt.%)

Steel code C Mn P S Si Cu Ni Cr Yield strength, MPa (ksi)

WC-1 0.105 1.03 0.010 0.0270 0.075 0.20 0.08 0.05 518 (75)
G-2 0.130 1.09 0.012 0.0084 0.165 0.22 0.07 0.06 646 (93)
AM-1 0.120 0.69 0.006 0.0031 0.008 0.33 0.095 0.17 597 (86)
PC-1 0.090 0.73 0.013 0.0036 0.200 0.23 0.08 0.06 538 (78)
CTR-2 0.100 0.84 0.018 0.0013 0.175 0.005 0.25 0.03 526 (76)
AM-2 0.120 0.80 0.003 0.0016 0.410 0.011 0.015 0.027 572 (85)

about 4.5. The presence of Cu is believed to stabilize the iron 3. The correlation between pits and non-metallic inclu-
sulfide scale formed on the steel. sions indicates that pitting results from effects associ-
ated with inclusion composition.
Raising the (COH)Th value 4. Some steels show a greater susceptibility than others.
On occasion, this difference in material susceptibility
The (COH)Th value will be increased by: (a) eliminating has been the main factor in determining whether near-
type II MnS inclusions, Al2O3 particles, the anomalous neutral-pH SCC is an operational problem.
micro-structure, and other nonmetallic inclusions, e.g., 5. The harmful influence of hydrogen on steel depends on
silicates, slag, iron oxides, massive niobium carbonitride the character of hydrogen interaction not only with the
particles, etc; (b) reducing the segregation of trace/impurity crystal lattice of iron, but also with structural compo-
elements in the steel; and (c) increasing the homogeneity of nents and nonmetallic inclusions, in particular, manga-
the microstructure. The addition of calcium to form nese sulfides (MnS).
spherical, non-deformable calcium sulfide (CaS) inclusions
is now the favored method of shape-controlling steels for HIC
HIC-resistant plate and linepipe. The Ca/S ratio must be
6. There is a good correlation between inclusion measure-
controlled within a narrower range if the S content is higher
ments and HIC.
than 0.003%. For a 0.004% S content steel, the maximum
7. HIC depends on both material composition and
Ca/S ratio should be 2.5, whereas it should be 2.0 for a steel
hydrogen concentration COH. The HIC susceptibility
with 0.005% S. Shape control is not recommended if the
would increase due to increased COH as the conse-
sulfur content exceeds 0.005%.
quence of decreased diffusion coefficient, D.
8. The elongated MnS and planar arrays of other
inclusions are primarily responsible for HIC.
Conclusions
9. Lower volume fractions of inclusions correspond to
higher resistance to HIC.
SCC
10. The microstructure may also play a role in HIC, in
1. Multiple types of crack initiation sites exist for stress particular, heavily banded microstructures could
corrosion cracking of pipeline steel in low-pH solutions. enhance HIC by providing low fracture resistance
2. Stress corrosion crack initiation is a competitive paths for cracks to propagate more easily. The
process; cracks initiate at the most favorable sites first, balance of C and Mn has an overriding effect on
then at other sites. resistance to HIC.

Fig. 12 The image analysis

methodology where maps are
constructed and used to measure
long microscopic features that
run through more than one mi-
croscopic field. Measurements
of non-metallic inclusions in
line pipe steels
1098 J Solid State Electrochem (2009) 13:1091–1099

Table 2 Linepipe steels data on inclusions

Sample Vol.% Av. size (μm) #/mm2 Length/mm2 Ca/S ratio Threshold hydrogen concentration,
(COH)Th, mL (STP)/100g

WC-1 0.387 1.73 16963 29.3 0.15 0.3±0.1

G-2 0.338 2.45 5729 14.1 0.50 0.6±0.15
AM-1 0.209 3.71 1774 6.5 0.96 0.4±0.15
PC-1 0.205 4.96 1382 6.9 1.31 1.2±0.3
CTR-2 0.042 3.25 278 0.9 2.62 >1.5±0.2
AM-2 0.034 1.41 1614 2.2 2.50 >2.0±0.2

Fig. 13 Effect of the volume

fraction of inclusions (%) on
threshold hydrogen concentra-
tion for cracking (Cth)

Fig. 14 Effect of the total

length inclusions on threshold
hydrogen concentration for
cracking (Cth)
J Solid State Electrochem (2009) 13:1091–1099 1099

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