Engineering Fracture Mechanics 199 (2018) 609–618

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Engineering Fracture Mechanics

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Hydrogen induced cracking of pipeline and pressure vessel steels: A

T
review
⁎
Goutam Ghosha, , Paul Rostronb, Rajnish Garga, Ashoutosh Pandaya
a
University of Petroleum and Energy Studies, Dehradun, India
b
The Petroleum Institute, Khalifa University, Abu Dhabi, United Arab Emirates

A R T IC LE I N F O ABS TRA CT

Keywords: Pipelines and pressure vessels made of carbon and low alloy steels have suffered from Hydrogen
Hydrogen Induced Cracking (HIC) Induced Cracking (HIC) in wet hydrogen sulfide environment in the oil & gas industry. Hydrogen
Inclusion which is produced at cathode due to corrosion reaction, diffuses into the steel and result in
Microstructure cracking in wet hydrogen sulfide environment. Hydrogen assisted cracking usually manifests in
Diffusion
carbon and low alloy steels with unique crack initiation and propagation characteristics. The
origin and morphology of cracks are dependent on various factors viz., mechanical properties &
composition of the material, manufacturing process including heat treatment, applicable stresses
etc. Hydrogen assisted cracking is commonly classified into three categories based on initiation,
morphology and stress requirement in cracking as, Hydrogen Induced Cracking (HIC), Sulfide
Stress Cracking (SSC) and Stress Oriented Hydrogen Induced Cracking (SOHIC).
The current paper discusses the metallurgical factors which play a major role in Hydrogen
Induced Cracking of flat rolled steels commonly used in manufacturing of pipelines and pressure
vessels in oil & gas industry as found in several studies.

1. Introduction

Pipelines, as well as, pressure vessels made of carbon or low alloy steels, suffer from cracking in sour environment by Hydrogen
Assisted Cracking (HAC) process. Cracks generally originate on metal surface or at defects inside the metal thickness. Hydrogen,
when diffused in metal and occupying interstitial locations, degrades mechanical properties of the metal, thereby rendering the
material susceptible to cracking at a stress lower than even yield stress which is applicable to all HAC processes [1,2].
The role of stress differs in different hydrogen assisted cracking mechanisms e.g., in SSC and SOHIC where additional stress is
considered as necessary to initiate the cracking, whereas, in case of HIC external load is not considered as a prerequisite, rather
internal stress is considered to be developed by hydrogen molecules accumulated in defect locations inside the metal thickness.
‘Hydrogen Induced Cracking’ or HIC has often been used in generic way to describe hydrogen assisted cracking processes in lit-
eratures [3].
Hydrogen diffusion and entrapment in microstructural defect sites are considered as responsible factors for internal HAC of steels.
Hydrogen induced cracking is generally considered as a complex problem involving hydrogen transport to susceptible sites, e.g.,
inclusions, interfaces, grain boundaries etc. The failure mechanism is considerably dependent on chemical composition, micro-
structure, density & type of hydrogen traps, strength level of steels and environmental conditions. Depending on processing including
heat treatment, steels develop microstructures with specific type of precipitates. HIC sensitivity depends on microstructure and

⁎
Corresponding author.
E-mail addresses: goutamkw@gmail.com (G. Ghosh), prostron@pi.ac.ae (P. Rostron), rgarg@ddn.upes.ac.in (R. Garg), apanday@ddn.upes.ac.in (A. Panday).

https://doi.org/10.1016/j.engfracmech.2018.06.018
Received 7 March 2018; Received in revised form 18 April 2018; Accepted 13 June 2018
Available online 15 June 2018
0013-7944/ © 2018 Published by Elsevier Ltd.
G. Ghosh et al. Engineering Fracture Mechanics 199 (2018) 609–618

resultant precipitates.

2. Role of microstructure on hydrogen induced cracking

Steels, used in manufacturing of pressure vessels and pipelines are produced by various manufacturing processes and heat
treatments. Unalloyed or low alloyed steels are produced by normalizing where strength level is usually moderate to low (up to grade
70). However, the contribution of strengthening mechanism comes from alloying elements i.e., mainly carbon, silicium, manganese,
and sometimes other elements e.g., Cu, Ni etc. By exploiting other strengthening mechanisms, as performed by applying
Thermomechanical Control Process (TMCP) or Quenching & Tempering (QT), requirement of alloy addition can be controlled to
achieve higher strength which minimizes susceptibility to HIC [4]. Normalized and QT steels are generally medium carbon steels
having ferrite-pearlite or tempered martensitic microstructure, whereas, TMCP steels are low carbon grades with microstructures
which depend on heat treatment in manufacturing process, often a combination of phases with various precipitates are observed in
microstructures. The microstructure, grain size, volume fraction of inclusions and precipitates, and dislocation density can vary
within a particular strength grade.
Studies found that microstructure plays important role in hydrogen assisted cracking of steels. Uniform microstructure with
minimum defects, improves HIC resistance. Susceptibility to HIC is particularly related to steel composition, deoxidation practice and
processing history, as these parameters affect nonmetallic inclusions (type, size, morphology) and the material’s ability to accom-
modate hydrogen. Large inclusions such as elongated Manganese Sulfides (MnS) and clusters or stringers of oxides increase the HIC
susceptibility in steel [5]. It is found that the hot rolling produces the most susceptible structure to HIC degradation as hot rolling
produces planer defects which are favorable locations for hydrogen entrapment and initiation of HIC. Steels containing S > 0.002
were found to be susceptible HIC as MnS forms planer defects in hot rolling which act as traps for hydrogen to initiate HIC. Nor-
malizing-quenching & tempering had shown to reduce susceptibility of steels to HIC, particularly in low sulfur steels. Banded Ferrite
Pearlite was identified as one of the most susceptible microstructures in several studies. HIC is found to initiate at interfaces of ferrite
and pearlite bands. Hydrogen degradation effect was found to be enhanced in banded ferrite-pearlite in fracture toughness study with
different microstructures [6–8]. Control of phosphorus and carbon content increases HIC resistance by lowering microsegregation
and thereby reducing banding in steels. However, researcher also observed that there was no significant effect of microstructural
banding on HIC for special clean steel (A516-60, S < 0.008%) [9]; although, it was not investigated in the study if diffusible
hydrogen trapped in banding in special clean steel was not enough to reach to a critical level to initiate HIC in absence of other type
of microstructural defects [10].
Thermo-mechanically controlled processed (TMCP) steels with low sulfur content and low carbon equivalent had shown sig-
nificant resistance to HIC cracking. The effect was considered as a result of reduction in ferrite/pearlite banding in steels. Carbide rich
bands were considered as secondary sites which also initiated HIC in low sulfur containing steels [6]. Generally, rolling schedule is
targeted in TMCP steels to produce microstructure of fine grain, mixture of massive pearlite and low carbon bainite without pearlite
or bainite bands, and reheating is usually selected to dissolve large carbonitrate inclusions to increase cracking resistance [11].
Refined and homogeneously quenched and tempered bainite/martensite microstructure was found to have better performance for
HIC than ferrite-pearlite microstructure in pipeline steel [12]. Researcher also believed that lower bainite could offer lower sus-
ceptibility to Hydrogen cracking than quenched and tempered martensite [13]. However, it was found that segregated zones with
bainitic and matersitic structures had a high tendency for crack initiation and HIC susceptibility [14]. Study found that high strength
granular bainite had lower intrinsic hydrogen embrittlement (HIC) resistance than tempered martensitic steel. It was postulated that
hydrogen in granular bainite might concentrate at microstructures composed of martensite islands and retained-austenite locations.
Researcher has observed that the retained austenite itself in M/A constituents did not trap hydrogen significantly, but the interfaces
between the retained austenite and martensitic layer might be the possible trapping sites. Interface area of cementites in bainitic
structure will be larger than that in pearlite and it could increase the reversible hydrogen trapping efficiency of bainitic structure
[15]. However, granular bainite steel showed higher extrinsic resistance than conventional tempered martensite steel because of
granular bainite steel reportedly trapping less hydrogen than tempered martensite steel [16].
The effect of hydrogen in microstructure appears to change in duel phase microstructures as apparent from several investigations.
Investigation by Xian-bo SHI et al., on effect of microstructure on HIC in experiment with X80 pipeline steel for three different duel
phases i.e., ferrite+bainite, ferrite+martensite/austenite-islands, and ferrite+martensite respectively, found that ferrite+bainite
and ferrite+martensite/austenite-islands(M/A) both had higher deformability and HIC resistance, whereas, harder microstructure of
ferrite+martensite (F+M) had the worst HIC resistance. The hard martensite phase existed in bands and believed to be responsible
for HIC susceptibility. It is concluded that duel phase containing a softer phase exhibit higher straining capacity and superior de-
formability [17].
Park et al., considered that generally lower bainite offered higher resistance than quenched and tempered martensite at com-
parable strength levels, but no study was made to compare acicular ferrite with bainite with respect to hydrogen diffusion [13]. Jing
Li et at, observed in experiment with X80 pipeline steel that granular bainite+acicular ferrite, as well as, quasi polygonal ferrite
microstructure presented excellent HIC resistance, whereas, lath bainite+granular bainite microstructure containing bainite lath and
martensite/austenite phases showed poor HIC resistance [18].
The mechanism of formation of duel phases was postulated by Mohtadi et al., that in the acicular ferrite+granular bainite
microstructure, acicular ferrite nucleates intragranularly in deformed austenite, and the formation requires sufficient deformation
ratio in the non-recrystallization zone. The formation of M/A constituents is influenced by acicular ferrite transformation and ability
of carbon atoms to diffuse. Residual austenite becomes more stable due to increasing impingement effect between ferrite laths

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induced by increasing nucleation sites for acicular ferrite. However, the impingement effect during bainite transformation produces a
higher amount of residual austenite which subsequently transforms to M/A constituents [10,19].
Huang et. al., observed in review (studies with X120 steel) that, investigation of the HIC process by different researchers was
focused on formation process of cracks, not on combined effect of different microstructures and presence of hydrogen, and the
cracking nature of HIC/SSC has not been clearly explained in literature [20].
Koh et al., in experiment observed that HIC did not occur in ferrite/acicular ferrite microstructure for a wide range of diffusible
hydrogen content and HIC susceptibility was found proportional in ferrite/bainite microstructure, implying that ferrite/bainite
microstructure was prone to HIC whereas, ferrite/acicular ferrite was the best microstructure for HIC resistance [21,22]. Researchers
found that acicular ferrite and ultra-fine ferrite had optimum HIC resistance and mechanical properties (SSCC resistance is better in
ultrafine ferrite than acicular ferrite) as observed by Park et al. [21] which was also supported by studies of several other researchers
[23,18]. It was postulated that acicular ferrite possessed high yield strength & toughness due to dispersed precipitation of carbo-
nitrides and was considered as the most preferable microstructure for HIC resistance. Acicular ferrite phase had randomly oriented
grain boundaries and high dislocation density, which improved hydrogen trapping efficiency than other microstructures. However,
Huang et al. observed in review that the role of acicular ferrite had not been properly explained in enhancement of Sulfide Stress
Cracking (SSC) resistance, which was likely to be closely related to hydrogen diffusion [13].
Costin et al., investigated acicular ferrite from weld of X70 pipeline material (E6010 weld) with micro-cantilever structure for
intrinsic HAC properties. Previous investigations reported that acicular ferrite seems to have most beneficial impact on strength,
toughness, as well as, HAC resistance including welds. The outcome demonstrated that threshold stress intensity factor (Kth) to
initiate crack propagation in acicular ferrite ranged between 1.56 MPa√m and 4.36 MPa√m. The range is significantly lower than Kth
reported for various ferrous alloys in standard macro tests. This indicates that subcritical hydrogen assisted cracks can grow at micro-
scale at stress intensity factors well below the stress intensity factor threshold measured with conventional tests at macro-scale. The
findings indicate that mechanisms and resistance to HAC at micro-scale could be significantly different than at macro-scale as not all
fracture toughening mechanisms may be activated at this scale level. The inherent difference was attributed to small grain size and
high density of high angle grain boundaries, which apparently increased the resistance to cleavage like fracture and simultaneously
acted as a hydrogen trap, thereby preventing the hydrogen to diffuse to more HAC susceptible regions. Plasticity induced closure of
cracks also might form part of the mechanism, needs further investigation [24].

3. Hydrogen trapping in steel

Hydrogen generated due to corrosion reaction in wet H2S environment is postulated to enter steel, the hydrogen atoms can be
present in diffusible (mobile) form at interstitial sites within the ferrite crystal structure or become trapped at defect sites. Diffusion of
hydrogen in steel is affected by microstructure i.e., phases present, grain boundaries, grain shapes, vacancies and dislocations,
interfaces with nonmetallic inclusions, precipitates and micro voids etc. These features can reduce mobility of hydrogen in steel by
acting as traps. Traps are classified into reversible and irreversible traps depending on the binding energy with the hydrogen.
Reversible traps, for example, grain boundaries, dislocations, and micro-voids are low energy traps, do not permanently trap hy-
drogen. Irreversible traps are high binding energy traps at ambient temperature, which include nonmetallic inclusion and pre-
cipitates/interfaces. Unsaturated traps reduce the permeability of hydrogen through steel.
Reversible trap sites modulate the flow of diffusible hydrogen and reduce the likelihood of critical concentration of hydrogen
accumulating at sites of stress concentration, which can be associated with strong traps. Reversible trapping is considered by many as
most important factor in HIC susceptibility. The most common reversible trap sites are dislocations. Dislocation density varies with
microstructures and plastic deformation, increase in dislocation densities is reported to result increase in reversible hydrogen traps
[18,25,26].
Thermo-mechanically processed micro-alloyed steels rely on precipitates for grain size control and strengthening. Coherency of
precipitates can be varied with heat treatment. It is also reported that elastic strain enhances hydrogen diffusion whereas, plastic
strain reduces hydrogen diffusion. It infers that increased dislocations in plastic-deformed or quenched & tempered steels traps more
reversibly diffusible hydrogen. It is observed that some researchers considered that binding energy > 60 kJ/mol, as irreversible traps.
Experimental studies found binding energies (kJ/mol) of different microstructural features are approximately as following (over-
lapping values of different studies covered in the range) [27]:

Dislocation: 10–60; Grain Boundary: 8.8–58.9; Crack: > 200; Interfaces (coherent) M2C: 11.4–11.6;
Precipitates TiC: 53–94.5; Al2O3, MnS (Incoherent): 70–90; NbC (semicoherent): 28–56, Fe3C: 8.4–15.7.

It is observed that most studies of hydrogen trapping in micro-alloyed precipitates have been carried out with TiC. Coherent and
semi-coherent TiC precipitates had lower binding energies and were reversible trap sites, while incoherent precipitates had extremely
large binding energy (∼95 kJ/mol). The author observed that enough studies were not carried out for microalloy precipitates with
Nb, Mo and V, but generally researchers considered that similar principle of trapping were likely to be applicable and binding
energies of semi-coherent precipitates of Nb, Ti and V were ranked in the order of NbC > TiC > VC. However, some researchers
also considered TiC, NbC, VC and complex Ti,Nb(C,N), Ti4C2S2 etc. as irreversible trap sites only [27,18,28].
It is observed that MnS has been considered to result in moderate to strong trapping of hydrogen. Several researchers had
contradictory considerations for MnS, i.e., strong irreversible, as well as, reversible trapping sites for hydrogen. It was reported that
trapping efficiency increased with sulfur content [18].

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It was postulated that grain boundaries can have opposite effects i.e., either increase the diffusion of hydrogen by providing faster
paths or reduce mobility by acting as reversible hydrogen trapping sites at nodes and junction points. To explain the contradictory
effects, Ichimura et al. suggested that hydrogen diffusion coefficient will be maximum at an optimum grain size which was confirmed
by modelling and experiments by others. Increase in yield strength & hardness with decreasing grain size led to increased HIC
susceptibility according to Hallmark-Patch effect was also postulated [18,28,29].
Hydrogen trapping was studied by several researchers for combination of phases, Park et al. supported that trapping efficiency for
X65 steel varied in the order as acicular ferrite > bainite > degenerated pearlite. Although bainite has lower trapping efficiency
than acicular ferrite, but bainite is more HIC sensitive than acicular ferrite. The author also observed that ferrite grains smaller than
45 µ can reduce mobility of hydrogen at nodes and triple junctions [18,27,28].
Similarly, Dunne et al., found in experiment that H trapping (X70 steels) varied in the order as, Banded Ferrite-
Pearlite > Equiaxed Ferrite-Pearlite > Ferrite-Granular Bainite > Bainitic Ferrite, which commonly indicates degree of cracking
tendency of different microstructures [28].
However, HIC behavior of API X70 pipeline steel was studied by Mohtadi-Bonab et al., concluded that higher amount of per-
meated hydrogen inside steel is not a reliable measure for HIC evaluation which was also observed by Escober et al., and concluded
that there was no direct relationship between diffusible hydrogen content and primary microstructure, even internal inclusions do not
affect the diffusible hydrogen content when compared with different heats of steels which was also concurred by Koh et al., in
experiment. It was observed that HIC did not occur in ferrite/acicular ferrite microstructure for a wide range of diffusible hydrogen
content and HIC susceptibility was found proportional in ferrite/bainite microstructure, implying that ferrite/bainite microstructure
was prone to HIC [21,22].

4. Role of inclusions on hydrogen induced cracking

Diffusion of hydrogen through metal body and trapping at defect sites are considered as basic mechanisms for hydrogen assisted
cracking in metals. Inclusions and precipitates play important role in such cracking. Hydrogen diffusion in steel is dependent on the
size, number and binding energy of trapping sites with hydrogen. Micro-alloying elements e.g., Cu, Ni, Mo and Ti are often added to
low alloy steels to achieve required mechanical and corrosion properties [30]. Studies found that depending on the processing path,
micro-alloyed carbonitride particles could form in austenite which would be incoherent with ferrite matrix after austenite decom-
position, or they could nucleate in ferrite in which case they would have a semi-coherent interface with ferrite at small particle sizes.
The coherency of these precipitates can be varied through heat treatments. Coherent and semi-coherent precipitates have lower
binding energies and are reversible trap sites, while incoherent precipitates have large bonding energies [27]. Guenter Herbsleb et al.,
observed that cracks (HIC) within a narrow zone (1 mm) from the surface was not necessarily associate with any nonmetallic in-
clusions as origin. It was observed that such cracks were not truly parallel to the surface, and lengths were limited by the angle with
the surface. It was concluded that lower pressure would suffice generating cracks near a surface than inside a material and this could
even occur in pure metals, but HIC in thickness greater than 1 mm from the surface would necessarily be associated with nonmetallic
inclusions [31].
Most of the researchers considered that non-coherent inclusions with metal matrix as one of the dominant factors for HIC in-
itiation. Several types of inclusions were characterized in pipeline and pressure vessel steels e.g., elongated MnS, spherical Al, Si, and
Ca-Al-O-S enriched inclusions [32,33].
Studies have found different inclusions to be responsible for crack initiation in presence of hydrogen in steels [19,32,34,35,8].
Several studies found that MnS promoted hydrogen assisted cracking in various steels and researchers generally considered that MnS
inclusions were commonly associated with HIC initiation in steels [8,36], it was also concluded that oxide inclusions did not pose any
threat to HIC in pipeline steels (TMCP), rather cracks started from complex carbo-nitride particles which were known to be hard,
brittle and incoherent with metal matrix in low sulfur steels [14,8]. However, studies found that along with MnS, spherical Al-oxide
inclusions initiated HIC in ASTM A537 normalized or QT pressure vessel steels [32]. Mohtadi-Bonab et al., in experiment with
pipeline steel (X60, 0.0027%S) did not identify MnS inclusions in steel, and HIC was found initiated from inclusions of mixed oxides.
It was generally considered that MnS, as well as, carbonitride inclusions were harmful for HIC on the basis of stress concentration
factor and shape of inclusions to promote HIC in steels. Carbonitride precipitates are known to be hard, brittle and incoherent with
the metal matrix. e.g., (Ti, Nb, V)(C,N) [19,8]. Xue et al., found in study with X80 steel (0.01%S, 4% MnS) that HIC crack did not
initiate at MnS inclusions, rather it initiated from inclusions reach in Si and Al oxides. The author concluded that amount of MnS was
low and inclusions rich in Al and Si oxides were hard and incoherent with the matrix, contained microvoids with the matrix interface.
Similar observations were recorded by other researchers also [25,37].
Contrary to conclusions that oxide inclusions are no threat for pipeline steels (TMCP), several studies have reported HIC initiation
at oxide inclusions, e.g., Kim et al., observed in review that HIC primarily nucleated at inclusions enriched with Ca and Al oxides. Xue
et al. and Jin et al. showed that HIC primarily nucleated at inclusions enriched in Si and Al oxides [32]. Ding et al., in experiment
with X100 pipeline steel found that cracks initiated primarily at inclusions such as, aluminum-oxides, titanium-oxides, and ferric
carbides at interfaces of microstructure with banded martensite-ferrite microstructure [31]. Xue et al., found cracks originated from
inclusions primarily associated with Si and Al enriched oxides in X80 steel having polygonal ferrite and bainitic microstructure with
martensite/austenite constituents distributed along grain boundaries. Inclusions found enriched with Si, Al-oxide, Ferric carbide, and
Al-Mg-Ca-O mixture, majority of inclusions are found Si enriched [25]. The role of SiO2 has also been reported to minimize oc-
currences of HIC, it is found in studies that cracks did not initiate around SiO2 inclusions in HIC tests for steels, it is postulated that
SiO2 could be easily deformed relieving effectively residual stress, moreover SiO2 inclusions are sphere shaped, causing relatively less

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lattice deflection which reduce severity for HIC [32,20].

Guenter Herbsleb et al., observed that cracks (HIC) in pipeline steels originated from MnS, as well as, oxide inclusions, and
concluded that, apparently composition of inclusions is not the decisive factor for originating HIC, rather, the shape and size of
inclusions which are responsible for initiation of cracks [31]. Studies found that Size of precipitates also affect HIC in steels. Pipeline
steels (TMCP) are found to contain plenty of tiny spherical Nbx(C,N)y particles in grains and sub-grains and finely dispersed car-
bonitrides in grains. The composite carbonitride precipitations of Ti and Nb are cubic particles found about 50–100 nm in size. Fine M
(C,N) (M:Nb or Ti) carbides (< 100 nm) are postulated to arrest dislocations and decrease their mobility, also fine precipitates can
behave as non-saturated hydrogen traps which can partake the hydrogen pressure, thereby improving HIC resistance of steels which
was supported by HIC tests on pipeline steels (X80) [19]. Zhao et al. also indicated that in microalloyed steels, nano-sized carbo-
notrides behave as innocuous hydrogen traps which help in hydrogen redistribution in numerous sites.
In modern low sulfur steels, microalloying elements (Nb, Ti) are highly susceptible to segregation, as well as, precipitation of large
particles carbonitrides in the slab centerline zone. It gives rise to shrinkage cavities and formation of hard micro-constituents which
are attractive sinks for atomic hydrogen. Mohtadi-Bonab et al., found that density of irreversible traps are high at centerline. It was
found that during hot rolling, accumulated hydrogen hinders annihilation of the cavities, instead creates pressure and forms hairline
cracks. It is reported that chemically enriched centerline was the likely location to contain hard transformation products such as
martensite during cooling after hot rolling and microcracks might occur at martensite-inclusion (TiN, TiNbCN, MnS etc.) interfaces
[11,8,22]. Of course, researchers concluded that sizes of inclusions were more imperative than location, study found that there was
no difference in dislocation structure in crack sensitive & insensitive regions (welded samples) but crack sensitive region consistently
contained relatively high concentration of 100–200°A diameter Nb rich precipitates. High concentration of < 50°A, or few > 500°A
precipitate did not apparently affect cracking sensitivity [13].
It has been concluded that presence of inclusions is one of the dominant factors for HIC initiation, and sizes impact the initiation
of HIC in steels. Domizzi et al., observed in experiment with pressure vessel and pipeline steels that no clear correlation could be
found between sulfur content or average length of inclusions and HIC resistance of steels [5].

5. Effect of alloying elements and composition on hydrogen cracking

Addition of alloying elements are carried out to enhance mechanical properties of steels, however, alloying of elements beyond
certain limits, singly or in combination with other elements, may produce adverse effects on hydrogen cracking susceptibility of steels
by modifying microstructure and inclusion characteristics which finally affect hydrogen diffusion in steel [38]. Therefore, it is
important to have a judicious selection & proportion of alloying elements to meet both, high strength, as well as, HIC resistance.
Alloying elements commonly used for pipeline steels are Mn, Mo, Cr, Ni, Nb, V, Ti, Cu etc. [20].
Koh et al., observed that hydrogen assisted cracking initiated at inclusions and propagated in quasi cleavage manner regardless of
composition of steel. The study also observed that the number of Inclusions which acted as crack initiation sites, was not influenced
by addition of alloying elements to the steel. However, it was recognized that alloy addition increasing hardness of steel, increased
susceptibility to HIC [30].
Experiment by Dayal et al., with different compositions and strength levels of steels showed that degree of hydrogen cracking
susceptibility depended on strength, grain boundary segregation, and hydrogen activity in the environment. Cracking path shifts from
transgranular to intergranular in high strength steels [39].

5.1. Carbon (C), Manganese (Mn) & Phosphorus (P)

Carbon and Manganese have high tendency to segregate in solidifying steels, forming hard bainitic or martensitic microstructure.
Segregation ratio of manganese is found to depend on carbon content. Role of Mn segregation is found to promote HIC by way of
Hydrogen-Enhanced-Decohesion-Effect (HEDE), as well as, Hydrogen-Enhanced-Localized-Plasticity (HELP) [6].
Phosphorus also has shown strong segregation tendency during solidification which is influenced by carbon and manganese
content in steel. This is considered due to decrease of carbon activity in presence of Mn which allows higher P migration to grain
boundaries. In normalized steel, P content in grain boundary is expected to be lower by 5–7 atomic%. Low strength carbon steels can
sustain higher P segregation than high strength low allow steels [39]. Phosphorus below 0.008 wt% is found to maintain effective
resistance of steels against HIC in steel. Relative effect of P on HIC susceptibility is shown in Fig. 1 [40].

5.2. Sulfur (S) content

Effect of sulfur on number, size and aspect ratio of MnS inclusions is recognized which in turn affects HIC susceptibility of C-Mn
steels [38,41]. Elongated MnS inclusions, are highly susceptible to HIC [33]. During continuous casting, Mn has a strong tendency to
segregate to centerline region and combine with sulfur at last stage of solidification to produce MnS in hot rolled steels [18]. Globular
sulfide inclusions, due to shape isotropy, are resistant to deformation, results reduction in HIC occurrences. Calcium treatment has
been carried out in steel manufacturing to induce shape control of sulfide inclusions. The benefit of calcium treatment and correlation
between sulfur content and HIC behavior of steel, as found in study, is shown in Fig. 2. Maintaining Ca/S ratio above 1.5 is re-
commended for steel with sulfur content > 0.001%.
Fig. 3 shows significance of Ca/S ratio on HIC for API 5L and ASTM A 516 grades of steels with S% less than 0.001% [4]. Below
0.001%S, calcium treatment is not effective as sulfide inclusions are considerably less, instead, calcium treatment for very low sulfur

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Fig. 1. The figure shows effect of phosphorus content on HIC cracking susceptibility (results based on > 100 low sulfur normalized steel plates)
[40]

Fig. 2. Above schematic diagram (a) shows change of shape parameter of inclusions with calcium treatment, and (b) difference in HIC susceptibility
between calcium treated & untreated steels [38].

Fig. 3. Influence of calcium to sulfur ratio on CLR for plates with sulfur contents ≤0.001% (HIC test: NACE TM 0284-96 solution A) [4].

steels may cause harm by producing calcium oxide inclusions which may induce cracking in steels [6,9,38].
However, it is also found in studies (with X65 steels) that controlling the sulfur content is not enough to control HIC susceptibility,
CLR (crack length ratio in HIC test) was found independent of sulfur content. Indeed, level of sulfur has an influence on sensitivity for
HIC, but even for very low sulfur content, very high CLR is found which means that high sensitivity to HIC is possible even with low
sulfur content. Therefore, low sulfur content appears to be a necessary condition but not a complete remedy for HIC.

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Fig. 4. Cu containing (0.28%) and similar composition copper free API 5L X65 grade of steels were tested at 5.3 pH in H2S containing environment
(0.1 MPa PH2S) showed different hydrogen diffusion and corrosion rates [43].

5.3. Copper (Cu) addition

Among the alloying elements, Cu has a special effect because Cu produces fine Cu rich precipitates by itself which are desirable in
improving both strength, as well as, resistance to HIC in steels. Nano-scale Cu-rich precipitates are believed to play important role in
enhancing HIC resistance by providing hydrogen traps and achieving high strength in steels [42]. Also, Cu is found to form protective
layer, and thereby reduce diffusivity of hydrogen in steel. Diffusible hydrogen content and corrosion rate decrease with addition of
copper as shown in Fig. 4. Experiments indicated that Cu tends to locally enrich inner layer of corrosion product within 100 nm from
the steel surface [43]. Various types of protective surface film including mackinawite (FeS1−x) are identified with Cu > 0.2% in
steel. Above 0.29%Cu, HIC resistance is found to increase, however, Ni (0.3%) is found to interrupt such advantage. Random en-
richment of film is also found with Cu, and dominance of CuS could not be detected in several locations. Therefore, protection
mechanism by Cu still remains a matter of further study [6,22].
It is postulated that Cu provided protection by two possible mechanisms as (1) it formed complex sulfide scale such as (Fe, Cu)S
which worked as a barrier against hydrogen entry as it had very fine crystal structure and dense morphology. (2) It triggered
precipitation of other sulfides such as FeS, which was well recognized as an effect of co-precipitation (CPT). More FeS precipitates
near the steel surface as a result of CPT, the inner layer of corrosion product became dense and could play an important role as barrier
against corrosion and hydrogen entry. The results differed from observations by other researcher (Inagaki et al. and Smith et al.) who
reported Cu enriched the FeS film, identified by EPMA (Electron Probe Micro Analyzer) line scanning.

5.4. Chromium (Cr) and Molybdenum (Mo) addition

Interaction between Cr and Mo is complex. Cr and Mo addition have considerable effect on microstructure. These elements (like
Al, Si, V, W) can increase A3 and decrease Bs and Ms temperatures, delay the transformation of ferrite and pearlite. Thus increases
hardenability and promote low temperature transformation products (martensite/austenite constituent M/A-C) in the steel.
Increasing Cr, changed microstructure from ferrite-pearlite-small bainite to predominantly ferrite and bainite structure.
Cr addition suppresses HIC. Mo addition as reported, impairs hydrogen absorption resistance. Researchers found that 0.3% Cr was
most beneficial to HIC resistance in BP solution, while addition of 0.6% Cr had effect of lowering hydrogen absorption on steel surface
in HIC testing, but addition of 0.4% Mo was found to have contrary effect. As a combination, Cr and Mo values have synergistic effect
on the properties of the material, however Mo has more pronounced effect on generating M/A-C in steel. Researchers have also
analyzed relative effect of Cr and Mo with the help of International Institute of Welding (IIW) carbon equivalent formula (CEQ) and
Ito-Bessyo formula (Pcm) in combination of several other elements but no conclusion could be drawn [22].
Hydrogen permeation and HIC full scale tests of line pipes were conducted by HIC subcommittee from High Strength Line pipe
Research Committee of the Iron and Steel Institute of Japan. The above subcommittee conducted full scale tests of several line pipes
(X42–X65) of various compositions in various sour conditions. It was found that alloy additions reduced peak value and increased
decay rate of hydrogen diffusion. The Ni addition caused particularly rapid decay rate [44].
Researchers also found that effect of Cr and Mo on HIC resistance of steels had not been consistent [22].

5.5. Niobium (Nb) addition

Nb has the precipitation hardening and grain refinement, as well as, strengthening effect. Nb(CN) precipitates in ferrite phase
which elevates tensile strength of the steel. Addition of Nb has been found to decrease HIC resistance in steels in experiment. The
mechanism has been explained as addition of Nb could retard the recrystallization of austenite and increased the nucleation sites, as
well as, nucleation rates during ferrite transformation. This resulted in decrease of ferrite grain size, but it increased the deformation

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Fig. 5. HIC initiated mainly from tips of elongated MnS inclusions, Nb increased the aspect ratio of the inclusions [22].

resistance of gamma phase at high temperature. Deformation of inclusions (MnS) during rolling was controlled by the relative
strength between gamma phase and inclusions. The higher the deformation resistance of gamma phase, the more the inclusions were
elongated. The Fig. 5, shows increase in aspect ratio of inclusions with increase of Nb. Massive Nb carbonitride precipitates can act as
initiation sites, but combined action of Nb and Boron is found to increase HIC resistance [22].

5.6. Titanium (Ti) addition

Ti has primarily the grain refinement effect. The effect of Ti addition on HIC varies with the size of TiN and Ti(C,N) particles.
Large cubic TiN particles are found to promote HIC [11,22].
HIC cracks are found to initiate at interface between rhombic TiN inclusion and the matrix. Some researchers have reported that
Ti has a faint tendency to cohere with MnS. Study found that TiN and MnS existed together and the combined inclusions cooperated
to result in HIC as shown in Fig. 6. It was also found that fine and dispersed Ti(C,N) < 0.1 micrometer diameter, decreased hydrogen
diffusion constant and increased HIC resistance by forming Ti(C,N) precipitates. Ti addition also increases strength of steel by forming
precipitates [1,30].
Shimizu et al., found that fine and dispersed Ti(C,N) suppressed hydrogen segregation at the inclusion-matrix interfaces, whereas,
coarse Ti(C,N) and TiN precipitates were reported to be HIC initiation sites [22].

6. Summary

Studies have found that diffusion of hydrogen to reversible and irreverasible trap sites has been the important factor which is
dependent on microstructure to promote HIC in materials. Furthermore, diffusible hydrogen content trapped reversibly in micro-
structure has been considered as more important than hydrogen flux permeating through the steel. Hydrogen diffusion is dependent
on the size, number and binding energy of trapping sites.

Fig. 6. The above figure (a) shows that HIC cracks are found to initiate at interface between rhombic TiN inclusion and the matrix. The TEM
micrograph (b) showing the morphology and orientation relationship of a compound TiN and MnS [22].

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Presence of nonmetallic inclusions was considered as one of the dominant factors controlling initiation of HIC in steels. Area and
volume fraction, including type of inclusions contributed to HIC cracking. Steels having similar inclusion levels might differ in HIC
sensitivity based on difference in diffusible hydrogen content. There appears to be no threshold level of inclusions to initiate HIC for
any specific microstructure, rather, it was identified that a critical level of hydrogen entrapment was required to initiate HIC which
was dependent on microstructure of the steel.
Several types of inclusions were characterized e.g., MnS, Al, Si, Ca-Al-O-S enriched inclusions, and complex carbonitride particles
(Ti, Nb, V)(C,N). Traps were considered irreversible if binding energies were high (generally above 60 KJ/mol). Commonly, MnS was
considered as the prime inclusion for initiating HIC and found to be considered as reversible, as well as, irreversible trap sites by
different researchers. TiC was found to be considered as coherent, semicoherent or incoherent traps depending on the binding
energies of the precipitates. However, some researchers considered TiC, NbC, VC and complex Ti,Nb(C,N), Ti4C2S2 etc. as irreversible
trap sites only. Researcher also observed that cracks (HIC) in pipeline steels originated from MnS, as well as, oxide inclusions, and
concluded that apparently composition of inclusions was not the decisive factor, rather, the shape and size of inclusions were
responsible factors for initiating cracks. It was also reported that trapping efficiency of hydrogen increased with increase in sulfur
content in steel. Presence of fine carbide precipitates (< 100 nm) was considered to decrease mobility of dislocations and improve
HIC resistance. It was postulated that nano-sized carbonotrides behave as innocuous hydrogen traps which helped in hydrogen
redistribution in numerous sites which improved HIC resistance in microalloyed steels. Researchers considered that microalloyed
precipitates were more complex than binary carbides and required further investigation on hydrogen trapping.
Manufacturing process and heat treatment result in different microstructures in steels. Homogeneous microstructures with uni-
formly distributed inclusions were found to improve HIC resistance. Correlation between hardness in microstructures and HIC
susceptibility was also recognized. Study found that hydrogen trapping efficiency for pipeline steel generally varied in the order as
Acicular Ferrite > Bainite Ferrite > Degenerated Pearlite, which was often considered as an indicator of degree of resistance to
cracking tendency of different microstructures in hydrogenated conditions. However, researcher also found that higher amount of
permeated hydrogen in steel was not a reliable measure for evaluation of HIC which possibly requires further investigation. It was
also demonstrated that mechanisms and resistance to Hydrogen Assisted Cracking at micro-scale could be significantly different than
that of macro-scale.
It is felt that effect of hydrogen on combination of different microstructures on the cracking nature of HIC was not clearly
explained in literature, requires more investigation and understanding.

7. Conclusion

Various modifications in steel making processes have been made to create non-detrimental trap sites e.g., control of sulfur-carbon-
nitrogen content, modify morphology of inclusions by calcium treatment, addition of micro-alloying elements, as well as, preventing
large conglomerates of carbonitride inclusions but elimination of HIC still remains a challenge to the steel manufacturing industry.
‘Control of nonmetallic inclusions’ and ‘homogeneity of microstructure’ were considered as most important factors to reduce
irreversible hydrogen traps and improve HIC resistance of steel. However, the measure of diffusible hydrogen, remained an unreliable
indicator for evaluation of HIC resistance of steel. Contrary to the prevailing understanding, several studies have reported that HIC
did occur beyond perceived limits of variables keeping a focus on level of inclusions, as well as, hydrogen in steels. Therefore, further
researches are warranted to reveal the complex relationship and synergy of variables to minimize or eliminate HIC occurrences in
steels.

Appendix A. Supplementary material

Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.engfracmech.
2018.06.018.

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