Materials Science and Technology

ISSN: 0267-0836 (Print) 1743-2847 (Online) Journal homepage: http://www.tandfonline.com/loi/ymst20

Critical Assessment 17: Mechanisms of hydrogen

induced cracking in pipeline steels

K. O. Findley, M. K. O'Brien & H. Nako

To cite this article: K. O. Findley, M. K. O'Brien & H. Nako (2015) Critical Assessment 17:
Mechanisms of hydrogen induced cracking in pipeline steels, Materials Science and Technology,
31:14, 1673-1680, DOI: 10.1080/02670836.2015.1121017

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Published online: 16 Dec 2015.

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 CRITICAL ASSESSMENT
Critical A ssessment 17: Mechanisms of
hydrogen induced cracking in pipeline steels
K. O. Findley*1, M. K. O’Brien1 and H. Nako2
Hydrogen induced cracking (HIC) remains a prominent issue for oil and gas exploration in
challenging environments. This assessment discusses HIC in light of hydrogen transport through
pipeline steel microstructures and crack initiation and propagation processes. While there has
been significant research in hydrogen permeation through steel alloys, additional understanding
is necessary in microstructures specific to pipeline steels. Furthermore, a standard model for
crack initiation and propagation processes needs to be established; a fracture mechanics based
model, which has been used by some researchers, is presented in the present paper to predict
crack propagation. Advanced characterisation techniques can help elucidate mechanisms of
hydrogen induced crack growth. Ultimately, linking hydrogen transport and cracking processes
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during HIC will enable optimised alloy and microstructure design.

Keywords: Hydrogen induced cracking, Hydrogen trapping, Pipeline steels

Introduction deoxidation, casting and hot rolling practices, to achieve

As new oil and gas exploration takes place, pipeline
steels are being used in more challenging environments,
including sour service conditions. Sour service is defined
as oil and gas environments containing a partial pressure
of H2S w0.3 kPa.1 In these conditions, hydrogen
induced cracking (HIC) due to ingress of hydrogen into
steel from H2S gas is a significant concern. An electron
backscatter diffraction (EBSD) micrograph of HIC
induced by laboratory testing of an X52 alloy is shown
in Fig. 1.
The microstructure of alloys produced from flat rolled
steel products can consist of ferrite and pearlite, other
ferrite morphologies such as acicular and granular fer-
rite, and smaller volume fractions of microconstituents
such as microalloy precipitates and martensite/austenite
islands.2,3 Thermomechanical processing and micro-
alloying have been used to develop stronger and tougher
pipeline alloys through grain refinement, precipitation
and removal of large carbides from the microstructure.
Alternatively, seamless pipe, produced from bar steel,
can have ferrite–pearlite or martensitic microstructures.
Several of these microstructural features may influ-
ence vulnerability to HIC. There have been substantial
research and development efforts in the steel industry to
design HIC resistant steels, primarily through inclusion
control, reduction of hard, segregated bands in the
microstructure, and accelerated cooling. Modifications
have been made to alloying, sulphur levels,
1
G.S. Ansell Department of Metallurgical and Materials Engineering,
Colorado School of Mines, Golden, CO, USA
2
Materials Research Laboratory, Kobe Steel, Kobe, Japan
*Corresponding author, email Kfindley@mines.edu
better HIC resistance.4–6
While prominent reviews of hydrogen embrittlement
have been published in the past including those by
Oriani7 and Hirth,8 the purpose of this paper is to pro-
vide a critical overview of the mechanisms of HIC in
pipeline alloys, particularly in light of the desire to use
higher strength pipeline steel grades to enable larger
diameter and smaller thickness pipes, and identify issues
that have yet to be solved. While hydrogen embrittle-
ment susceptibility generally increases with strength, it is
also sensitive to microstructural features and inclusions
and thus does not always increase proportionally with
strength. Therefore, it is essential to understand HIC
resistance in thermomechanically processed microstruc-
tures in order to help guide future microstructural design
and alloy application for pipelines in sour service
environments.
Transport of hydrogen through steel
alloys in sour environments
HIC is affected by hydrogen trapping at both low and
high energy binding sites and transport of hydrogen to
existing flaws in the microstructure. The most common
test method for HIC susceptibility is the NACE TM-
0284 standard test9 where steel specimens are immersed
in either a sodium chloride–acetic acid solution or syn-
thetic sea water solution that is saturated with H2S gas
at ambient temperature and pressure. The specimens are
held in the solution for 96 h and then removed and
inspected for cracking. There is no externally applied
stress during testing. This method is an accelerated and
thus aggressive test, where alloys are qualified for service
if they do not exceed a threshold level of cracking.
Because of the safety challenges associated with using
H2S gas in laboratory environments, electrochemical

Ñ 2015 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 05 August 2015; accepted 06 August 2015
DOI 10.1080/02670836.2015.1121017 Materials Science and Technology 2015 VOL 31 NO 14 1673
 Findley et al. Mechanisms of hydrogen induced cracking in pipeline steels

1 EBSD inverse pole figure map of HIC in an X52 alloy induced by cathodic charging in sulphuric acid

charging has also been used to evaluate HIC.10–30 In any
method used to evaluate HIC, there must be correlation
between laboratory results and field performance.
Ideally, hydrogen entry and transport mechanisms in
laboratory experiments and in the field are similar.
Many have argued that different testing conditions
should be used to qualify alloys for less severe
environments since HIC susceptibility, and presumably
hydrogen entry into the steel is a function of the partial
pressure of H2S and pH of the environment.31–34
Overall, HIC resistance is a function of the amount of
hydrogen ingress into the alloy irrespective of the source of
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The traps can be classified into reversible traps that do
not permanently trap hydrogen and traps that irrever-
sibly trap hydrogen. Grain boundaries and dislocations
are examples of reversible trap sites, while inclusion
interfaces are examples of irreversible trap sites.
Traps are generally considered reversible or irreversible
based on their binding energies with hydrogen. It is
generally believed that traps with binding energies
w60 kJ mol21 are irreversible in nature, although this
definition is somewhat arbitrary and service timescales
are generally not considered in the assessment of rever-
sibility. Table 1 lists traps in steels and reported ranges

hydrogen. Within a sour service environment, the pro- for their binding energies, while Table 2 lists equations
duction of atomic hydrogen occurs through the anodic for the number of hydrogen ion traps per unit volume
dissolution of iron, which produces a free electron that for different types of trap sites. These tables list micro-
subsequently combines with a hydrogen ion during the structural features that are common in pipeline alloys,
cathodic reduction of hydrogen.35 This hydrogen atom is including some such as microalloy precipitates that are
thermodynamically unstable and thus seeks to recombine not commonly reported in literature.
with another hydrogen atom to form molecular hydrogen. Thermomechanically processed microalloyed steels
However, it is believed that the presence of H2S suppresses often rely on precipitates for grain size control and
this recombination reaction, facilitating hydrogen strengthening. Most studies of hydrogen trapping in
absorption into steel.36,37 Hydrogen ingress is often microalloy precipitates have been conducted with TiC
measured through permeability experiments using a precipitates.11,24,55,61,62 The coherency of these precipitates
Devanathan–Stachurski cell.38 Under the assumption that with the matrix can be varied through heat treatments, for
HIC occurs at a critical level of *hydrogen and this critical example, tempering conditions in quenched and tempered
level is proportional to a critical permeability, Hara et al.32 martensite. Coherent and semicoherent TiC precipitates
measured the permeability for various combinations of have lower binding energies and are reversible trap sites,
H2S partial pressure and solution pH and associated the while incoherent precipitates have extremely large binding
permeability with the extent of cracking. These types of energies (*95 kJ mol21).53,54 Wei and Tsuzaki11 suggested
permeability measurements have been performed fre- that the activation energy to move hydrogen into inco-
quently and are valuable to assess the influence of micro- herent TiC trap sites is too large for hydrogen ingress at
structure on hydrogen transport in a wide variety of alloys. room temperature. Therefore, the ability of incoherent TiC
Generally, a dilute solution such as 1N sodium hy- precipitates to serve as irreversible trap sites in pipeline
droxide is used to generate hydrogen ions, though Berko- steels operating in ambient conditions is questionable,
witz39 utilised H2S gas. Solutions such as 1N NaOH are which has possible implications in designing alloys for HIC
not completely representative of service environments resistance as described in the following section on mech-
because H2S interaction with the steel produces a corrosion anisms of HIC.
product (FeS) on the steel surface and H recombination is
Table 1 Binding energy ranges of various hydrogen trap
inhibited in the presence of H2S, although the recombina-
sites in steel alloys
tion inhibitor effect can be simulated by compounds such
as As2O3 in solutions. Since not all aspects of the corrosion Binding energy
process of steel in sour gas environments are captured by Trap type (kJ mol21) Reference(s)
typical Devanathan–Stachurski cell experiments, per-
meability results and measurements of cracking from Dislocation 18–59.9 7, 40, 44–50
Grain boundary 8.8–58.9 47, 51
electrochemical cells are most useful for qualitative rank- Void 29.1 45, 47
ings and mechanistic understanding of hydrogen inter- Crack > 200 52
action with steel. Interfaces
Many models have been developed to account for Coherent M2C 11.4–11.6 53
hydrogen trapping and diffusion of hydrogen through a precipitates
lattice with trap sites.7,8,40–43 Unsaturated hydrogen TiC
Incoherent 53–94.5 11, 54
traps reduce the permeability of hydrogen through steel. Coherency unknown 28 1 . 55
Semicoherent NbC 28–56 56
* The critical level of hydrogen generally decreases with increasing steel Fe3C 8.4–15.7 57–59
strength.
Ti substitutional atoms 26.1 54

1674 Materials Science and Technology 2015 VOL 31 NO 14


Table 2 Number density equations for various trap types
Trap Type Equation (traps cm23)
pffiffi
Dislocation cores N rt Krom ¼ abcc
2
rdis
N rt Song ¼ pb 2 rdis N l
Grain Boundaries N St ¼ 2bS v N l
Crack Face NC
t ¼8 V
N Fe
pd 2 kN v
Precipitates N TiðC;NÞ
t ¼  2
ðaÞ
rdis 5 dislocation density; a bcc 5 lattice constant of BCC iron; b 5 magnitude of Burgers vector; N l 5 3 Avogadro’s number
boundary surface area per unit volume; N Fe 5 Number of iron atoms on crack face; V 5 Unit volume of steel; k 5 number of
hydrogen atoms per unit cell; d 2 5 average precipitate diameter determined experimentally; N v 5 number of precipitates per unit
volume; ðaÞ2 5 average area of tetragonal unit cell
There have not been extensive studies of the binding
energies of hydrogen in microalloy precipitates con-
taining Nb, Mo and V, but some of the same principles
of trapping likely apply. Depending on the processing
path, microalloy carbonitride particles can form in
austenite, and thus are incoherent with the ferrite matrix
after austenite decomposition, or they can nucleate in
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ferrite, in which case they can have a semicoherent
interface with the ferrite at small particle sizes.63 In one
of the few studies of hydrogen interaction with these
microalloy precipitates, Wei et al.64 analysed exper-
imental compositions tailored to produce TiC, NbC or
VC precipitates and varied heat treatments to produce
populations of semicoherent and incoherent precipitates.
The binding energy of incoherent NbC and VC pre-
cipitates could not be measured, likely because of a
substantial activation energy to move hydrogen into the
traps (similar to incoherent TiC precipitates). The
binding energy of the semicoherent precipitates was
ranked as follows (Table 1): NbCwTiCw w VC. Atom
probe studies by Takahashi et al.65,66 provided some
experimental evidence for previous speculation 56,62 that
hydrogen is trapped at misfit dislocation cores in semi-
coherent precipitates. Ohnuma et al.67 provided further
experimental evidence of hydrogen trapping at semi-
coherent NbC precipitates through novel small angle
neutron scattering experiments.
As steel producers consider higher strength, HIC
resistant steel grades, further investigation is warranted
on the effect of coherency, composition and other par-
ticle characteristics on hydrogen trapping. For instance,
precipitates such as (Ti,Nb)(C,N) are more complex
than the simple binary carbides that have been men-
tioned thus far. Recent studies have also suggested that
Mo, another possible microalloying addition, affects
microalloy precipitate nucleation and growth processes,
which may have implications on ferrite–precipitate
interfacial energies68,69 and thus interaction of hydrogen
with the interface. In a recent study by Nagao et al.,70 it
was suggested that a dispersion of nanosized (Ti,Mo)C
precipitates reduced hydrogen embrittlement in medium
carbon tempered martensitic steels. Overall, a fine dis-
persion of irreversible traps could deplete the reversibly
trapped hydrogen that feeds HIC damage, though there
could be an insurmountable activation energy barrier in
these irreversible traps. In addition, Dadfarnia et al.71
recently showed through analytical models that the
amount of hydrogen trapped in a given type of trap site
at steady state is independent of the number density of
Findley et al. Mechanisms of hydrogen induced cracking in pipeline steels
Reference
Equation (1) Krom & Bakker42
40
Equation (2) Song et al.
40
Equation (3) Song et al.
Equation (4) Solano-Alvarez et al.52
Equation (5) Valentini et al.60
molar volume ; S v 5 Grain
other types of traps, which brings into question the
viability of utilising irreversible trap sites to reduce the
amount of reversibly trapped hydrogen. Further
experimentation and modelling are necessary to assess
the potential of engineering trap sites to mitigate HIC.
Similarly, cementite morphology and coherency with
ferrite affects hydrogen transport in steels.72,73
Bott et al.72 and Johnson et al.73 have independently
shown that hydrogen solubility is lower and diffusivity is
higher in microstructures containing ferrite and spher-
oidised cementite compared to microstructures with fine
dispersions of coherent Fe3C precipitates due to the
extent of hydrogen trapping by the carbides with
different morphologies and binding energies. However,
the two studies have contradictory hypotheses on the
role of pearlite in ferrite–pearlite microstructures. Bott
et al.72 postulated that the semicontinuous interface of
pearlite colonies at the pro-eutectoid ferrite grain
boundaries serves as a preferential hydrogen diffusion
path based on their observations of relatively high dif-
fusivity of hydrogen in these microstructures. In con-
trast, Johnson et al.73 suggested that cementite lamellae
in pearlite are reversible traps for hydrogen and thus
slow diffusivity compared to ferrite spheroidised
cementite microstructures.
Reversible trapping is considered by many to be the most
important factor in HIC susceptibility.10,20,23,53,74–76 The
most common reversible trap sites are dislocations. Dis-
location density varies with microstructure and also
increases during plastic deformation, for example, during
cold pipe forming processes. Johnson et al.73 measured
high concentrations of hydrogen in as quenched martensite
compared to quenched and tempered martensite micro-
structures, which they attributed to high dislocation den-
sity differences. Angus77 measured diffusible hydrogen in
four grades of cathodically charged plate steels with either
ferrite–pearlite or acicular ferrite/quasi-polygonal ferrite
microstructures with tensile strengths ranging from 480 to
804 MPa. The acicular ferrite microstructures had higher
diffusible hydrogen concentrations than a grade with a
ferrite pearlite microstructure; this result may be attributed
to differences in dislocation density or low and high angle
boundary surface area. Many researchers have found that
increasing amounts of cold work, and subsequent
increases in dislocation density, increase reversible hydro-
gen trapping.10,45,77,78
The hydrogen trapping density of dislocations has been
calculated using various models and the one-dimensional
line defect geometry of dislocations. For example,
Materials Science and Technology 2015 VOL 31 NO 14 1675
 Findley et al. Mechanisms of hydrogen induced cracking in pipeline steels
Song et al.40 assumed hydrogen atmospheres around the
dislocation core and calculated dislocation trap density as
equation (2) in Table 2. Krom and Bakker42 estimated trap
density in a one-dimensional model for edge dislocations
with , 111 . slip directions on {110} planes assuming one
trap per atom along the line length of the dislocation. The
resulting number of traps per unit volume is given in
equation (1) in Table 2. The two equations can be com-
pared
pffiffiffi if b is assumed to be approximately equal to
3abcc =2, the lattice parameter of BCC iron
abcc ¼ 2.87|1028 cm, the molar volume of iron Vm
¼ 7.09 cm3 mol21, and dislocation density equal to 1026
cm22 in a soft annealed state and 1012 cm22 in a cold
worked state.42 For the annealed condition,
Nrt Krom ¼ 4.93|1013 and Nrt Song ¼ 4.95|1016 traps
cm23. For the cold rolled condition, Nrt Krom ¼ 4.93|1019
and Nrt Song ¼ 4.95|1022 traps cm23. Since the two
models assume different dispersions of hydrogen around
dislocations, they predict trap densities that are three
orders of magnitude different, implying that prediction of
potential hydrogen trap sites at dislocations still needs
development.
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Mechanisms of HIC
HIC is a unique embrittlement phenomenon as it does
not require an externally applied stress or residual stress,
though these stresses can contribute to stress oriented
HIC.79,80 Instead, the internal hydrogen pressure theory
is typically used to explain HIC81,82 with contributions
from hydrogen enhanced localised plasticity and/or
hydrogen enhanced decohesion. It is postulated that
hydrogen atoms diffuse through the lattice and recom-
bine as H2 gas in areas of high hydrogen concentration.
When the gas pressure becomes sufficiently high, voids
and cracks develop and propagate.
Since many have suggested that HIC is dependent on
reversibly trapped hydrogen, it is not entirely intuitive
that HIC often occurs around inclusions, which serve as
irreversible trap sites with high binding energies.4,19 It is
possible that HIC is a two-stage process. In the first
stage, a high concentration of hydrogen gathers at in-
clusions since they serve as irreversible trap sites, and
subsequently, the hydrogen recombines to form hydro-
gen gas. When the hydrogen gas pressure is sufficiently
high, voids or cracks develop around the inclusions. In
the second stage, crack propagation is driven by the
internal hydrogen pressure within the crack as well as
hydrogen being fed by reversible trap sites to the crack
tip, lowering the toughness of the surrounding material.
Crack propagation can be enhanced by cracks linking up
with other nearby cracks initiated at inclusions. How-
ever, inclusions may also be implicated in HIC because
they are present in segregated zones and hard bands in
the microstructure, which are also susceptible to
hydrogen embrittlement.83 Inclusions, by themselves,
may not be deleterious for HIC resistance. For example,
Chou and Szklarska-Smialowska84 and Kobayashi and
Szklarska-Smialowska21 cathodically charged 0.25 wt-%
carbon steels with two different levels of sulphur, pro-
ducing two different populations of MnS inclusions. The
recovery of tensile ductility after aging of the low sul-
phur steel was less than the high sulphur steel. The
authors attributed this difference in tensile ductility to a
larger density of irreversible trap sites in the high
1676 Materials Science and Technology 2015 VOL 31 NO
sulphur steel that decreases the amount of reversibly
trapped hydrogen available to facilitate embrittlement.
Similarly, Domizzi et al.83 performed HIC experiments
on eight grades of pipeline steel with various inclusion
contents and degrees of microstructural banding
through thickness and concluded that inclusion control
is less important than the presence of hard bands.
HIC initiation is most often observed around
manganese sulphide inclusions. MnS inclusions are
likely more deleterious than other types of inclusions
because they are usually present in much larger volume
fractions and are significantly more deformable than
other inclusion types, so they elongate to larger sizes in
the rolling direction. If a crack nucleates around these
elongated inclusions, the resulting stress concentration is
more severe than for smaller, globular inclusions. This
behaviour is corroborated by Brown and Jones4 who
showed that elongated MnS inclusions were more sus-
ceptible to HIC than spherical inclusions. Residual
stresses around inclusions due to differences in thermal
expansion with the steel matrix may also be important
but have not been explored in depth. The coefficient of
thermal expansion for MnS inclusions, spinel inclusions
and steel is 18.1|1026uC21, 8.4|1026uC21 and
11.9|1026uC21 respectively.85 Owing to the significant
variation in residual stresses between the inclusions and
steel, it can be expected that microresidual stresses
would be generated around the inclusion–matrix inter-
face during thermomechanical processing, which may
affect interactions with hydrogen and crack initiation
processes.
Once HIC initiates, hydrogen gas pressure drives
crack propagation and can be assisted by other hydro-
gen embrittlement mechanisms including hydrogen
enhanced localised plasticity and hydrogen enhanced
decohesion.44,86,87 Furthermore, the hydrogen concen-
tration at the crack tip is likely increased due to the
hydrostatic stresses at the crack tip and increased dis-
location density in the plastic zone of the crack.88–92 This
theory has recently been corroborated by three-dimen-
sional neutron tomography that showed hydrogen
accumulation within hydrogen induced cracks and
around crack surfaces.16 The researchers attributed
high hydrogen concentrations in the areas adjacent to
HIC to the high dislocation density associated with the
plastic zone.
A simple two-dimensional model for crack propa-
gation may be derived from a fracture mechanics sol-
ution93 for a crack extending from a circular cavity,
modelling a void around an inclusion in this case, and
subjected to internal pressure as shown in Fig. 2. The
stress intensity factor, KI, is defined as follows:
 
pffiffiffiffiffiffi a
K I ¼ p paF ð6Þ
Rþa
 thecrack length, R is
where p is the applied pressure, a is
the radius of the inclusion and F Rþa a
is ageometrical
correction factor that decreases as Rþa a
increases.
Crack growth occurs when KI exceeds Kth, the stress
intensity above which crack growth occurs in the
presence of hydrogen91 or when KI exceeds KIC if the
deformation rates are too high for time dependent
hydrogen embrittlement mechanisms. Kth is much
smaller than KIC, and crack growth below the fracture
toughness in the presence of hydrogen is called
14

2 Two-dimensional model of a circular cavity and crack subjected to internal pressure. A plastic zone is shown at the right
side of the schematic with hydrogen atoms diffusing preferentially to that region.
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subcritical crack growth. This type of approach has been
used to predict conditions for crack growth during
HIC.41,94 Other toughness parameters that allow a small
amount of plasticity, such as the J integral, may also be
appropriate. Clearly, Fig. 2 is a simple model that may
need modification such as changes to inclusion mor-
phology. Further shown in Fig. 2 is hydrogen diffusing
to the plastic zone and region of hydrostatic stress
adjacent to the crack tip, presumably lowering the local
toughness. In one of the early studies of HIC, Tetelman
and Robertson81 observed that crack growth occurs
discontinuously during HIC in an iron–3 wt-% silicon
alloy. This behaviour is attributed to pressure build-up
within the cracked region until the fracture toughness is
exceeded. As the crack propagates, the pressure inside
the crack decreases as the volume increases, thus low-
ering the stress intensity. When the stress intensity drops
below the fracture toughness or Kth, the crack ests. It is
only in these periods of crack arrest that hydrogen can
accumulate within the crack volume to increase pressure
and at the crack tip to lower fracture resistance.
Overall, these models and observations indicate that
alloy subcritical crack growth resistance and fracture
toughness, especially when modified by hydrogen, are
important parameters to consider for HIC resistance.
Chatzidouros et al.95 measured the fracture toughness of
a controlled rolled X70 alloy and an X52 alloy with a
ferrite–pearlite microstructure both in air and during
cathodic charging. The X70 alloy had a superior fracture
toughness in both environments. Some studies3,77,96
have found that despite having a higher hardness and
more reversible hydrogen trap sites, controlled rolled
acicular ferrite microstructures have only slightly higher
or comparable HIC susceptibility to lower strength
steels with ferrite–pearlite microstructures. In contrast, if
the inclusion population and carbon additions are suf-
ficiently high, controlled rolling at lower working tem-
peratures may elongate inclusions and produce harder
centreline segregated zones, resulting in increased HIC
susceptibility.4,97 In cases of lower alloy content and
controlled inclusion populations and sizes, HIC resist-
ance is also likely affected by alloy toughness.
Findley et al. Mechanisms of hydrogen induced cracking in pipeline steels
Furthermore, the alloy toughness can vary through the
cross-section, especially in segregated and banded
regions. Thus, it may be more important to consider
local fracture behaviour. For example, Krom et al.41 and
Traidia et al.94 have fit a local fracture toughness value
that is one-half to one-third of the macroscopic
measured fracture toughness to model the rate of crack
growth during HIC.
Researchers have also been examining the effects of
texture on HIC resistance13,20,98–103 since crystal-
lographic texture may be altered through thermomech-
anical process variations and influence alloy toughness.
EBSD imaging is a valuable tool in assessing the inter-
action of local microstructure orientation and cracking.
Assuming that HIC occurs transgranularly parallel to
the rolling plane, it has been postulated that reducing the
number of {001} planes parallel to the rolling plane
results in enhanced HIC resistance. These studies show
potential validity to this hypothesis, though further
characterisation of HIC with respect to both cleavage
and intergranular cracking should be performed. The
influence of high and low angle boundary characteristics
on intergranular HIC has also been performed using
transmission electron microscopy and EBSD.20,22,102
Given the unique texture and boundary types that can
be produced in controlled rolled acicular ferrite and
bainite microstructures in higher strength pipeline
steels,104 it continues to be important to determine the
role of these microstructural features on HIC resistance.
Advanced characterisation and
modelling of HIC
While conventional hydrogen charging experiments,
including the NACE TM-0284 method and cathodic
charging of hydrogen, as well as subsequent character-
isation of cracking through light optical microscopy,
electron microscopy and acoustic microscopy will con-
tinue to be important to evaluate HIC resistance,
advanced characterisation methods will enable further
understanding of the mechanisms of HIC. There is
Materials Science and Technology 2015 VOL 31 NO 14 1677
 Findley et al. Mechanisms of hydrogen induced cracking in pipeline steels
certainly more information that can be extracted with
EBSD characterisation of microstructure around cracks
including cleavage planes, crack interaction with low
and high angle boundaries, and strain developed in the
microstructure around the crack path. Novel charac-
terisation methods are being developed for spatial
detection and local transport of hydrogen in multiphase
microstructures through scanning kelvin probe105–107
and scanning electrochemical microscopy.108 These
techniques utilise localised measurements of potential or
current between a probe and steel or coated steel sub-
strate to detect hydrogen within the limits of spatial
resolution of the probe utilised. On a larger scale, three-
dimensional tomography of HIC damage may help
elucidate hydrogen–microstructure interactions and
HIC mechanisms within the limits of resolution of cur-
rent capabilities, *25 mm in neutron tomography in
iron for example.16
Owing to the difficulty in experimentally observing
hydrogen in steels, computational and analytical models
are critical in developing understanding of hydrogen
trapping, transport and embrittlement mechan-
isms.90,109–111 These models can also help guide exper-
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imental studies and interpretation of measurements such
as thermal desorption spectroscopy studies. Recently,
models have provided insight on the potential
importance of hydrogen vacancy interactions,109,110
solute, precipitate and grain boundary interaction with
hydrogen,109 and crack initiation and growth.44,90
Summary
Concepts relevant to the transport behaviour of hydro-
gen and mechanisms of crack growth during HIC in
pipeline steels have been reviewed. There are several
critical open issues than remain to be resolved including
the following.
(i) Hydrogen trapping and diffusion is governed by
the presence of reversible and irreversible traps,
and further investigation, particularly for the
influence of alloying and microalloy precipitates
on hydrogen transport, is necessary.
(ii) Thermomechanically processed or controlled
rolled alloy microstructures such as acicular fer-
rite contain a higher dislocation density and
grain boundary area than lower strength micro-
structures such as ferrite–pearlite. Further in-
vestigation is required on the role of these
microstructural features on HIC resistance in
pipeline steels since they likely contribute to both
the reversible and irreversible trap populations.
(iii) In general, HIC resistance is governed by rever-
sibly trapped hydrogen, specifically in the vicinity
of a growing crack, though crack initiation often
occurs in regions where hydrogen is thought to
be irreversibly trapped around inclusions. How-
ever, the importance of inclusions independent of
hard bands and segregated regions of the
microstructure is not completely understood.
(iv) Based on the internal hydrogen pressure theory,
a fracture mechanics approach should be used to
predict HIC propagation. This approach requires
further experimental data on the fracture
toughness and subcritical crack growth beha-
viour of modern pipeline microstructures in the
1678 Materials Science and Technology 2015 VOL 31 NO
presence of hydrogen. Fracture mechanics
models in conjunction with an understanding of
hydrogen influenced local toughness should
continue to be developed to predict HIC
propagation.
(v) Advanced characterisation tools and modelling
should continue to be employed to elucidate
understanding of HIC and guide future exper-
iments and microstructural design.
Acknowledgements
The authors gratefully acknowledge the support of the
sponsors of the Advanced Steel Processing and Products
Research Center at the Colorado School of Mines.
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