HydrogenĆInduced Cracking in Surface
Production Systems: Mechanism,
Inspection, Repair, and Prevention
J.D. Burk, Amoco Corp.ĆAmoco Research Center
Summary
Hydrogen-induced cracking (HIC) is a materials- and corrosion-re-
lated problem that occurs in surface production systems. Steels used
to construct sour-gas production facilities and flowlines may cor-
rode from wet hydrogen sulfide (H2S) gas in the production stream.
The corrosion process generates hydrogen that may damage the
steel, resulting in HIC and other forms of damage from hydrogen.
HIC control and prevention are an important consideration in oper-
ating surface-facility equipment in a safe and efficient manner. By
effectively controlling or preventing HIC damage in surface-facility
equipment, operating costs are reduced, potential costly downtime
from equipment failure is avoided, and a safe work environment is
more easily realized.
We developed an overall approach to understand and deal with
the HIC problem in sour-surface production facilities. The approach
dealt with understanding the mechanism in steel materials used in
surface-facility equipment; implementing state-of-the-art inspec-
tion techniques; fitness-for-service (FFS) evaluation to assess dam-
age effect on performance; repair procedures on existing equip-
ment; and finally, establishing steel performance and fabrication
requirements to eliminate or reduce HIC damage risk for newly fab-
ricated equipment.
This paper presents the results of laboratory examinations of over
40 steels covering both new and existing equipment, leading to the
approaches developed for controlling HIC in existing equipment
and for controlling or preventing HIC in new construction. We also
present the basis for the approaches developed to deal with HIC in
surface production facilities.
Introduction
Wet H2S- or cyanide- (CN-) cracking in surface production process
equipment, such as pressure vessels, is now a major concern in the
industry. Industry attention turned to this potential cracking prob-
lem in the mid-1980’s, following the catastrophic rupture of an
amine contactor at the Union Oil refinery in Lemont, IL.1
Two steps were taken to address this concern in production opera-
tions: 1) special requirements were placed on steel, vessel fabrica-
tion, and operation to avoid process equipment and vessel cracks af-
ter understanding the steel-cracking mechanism, and 2) a sour-gas
plant inspection/maintenance program was initiated2 in the operat-
ing plants with an FFS capability developed to assess cracking sig-
nificance on equipment service ability. This overall approach has an
industry-wide impetus.
To address materials performance in hydrogen-charging environ-
ments for new construction, we initiated an effort to study the per-
formance of pressure vessel steels in wet H2S/CN environments.
From these studies, recommendations about the benefit of spe-
cialized chemistry control, normalization after rolling, special met-
allurgical processing techniques, and other controllable variables
were determined. These recommendations were then incorporated
into a material-purchase specification.
Wet H2S/CN Cracking Mechanisms in Process Equipment. Wet
H2S- or CN- assisted hydrogen cracking (HC)—often known as
Copyright 1996 Society of Petroleum Engineers
Original SPE manuscript received for review June 1, 1993. Revised manuscript received July
13, 1995. Paper peer approved Aug. 15, 1995. Paper (SPE 25583) first presented at the 1993
SPE Middle East Oil Technical Conference & Exhibition held in Bahrain, April 3–6.
SPE Production & Facilities, February 1996
HIC to cover a multitude of related cracking mechanisms—occurs
in both refinery and production facilities. Upstream production faci-
lities are exposed to H2S, while downstream systems experience hy-
drogen charging into the steel from both H2S and CN. The hydro-
gen-driven cracking is observed in several modes. The modes or
mechanisms are sulfide-stress corrosion cracking (SSC), hydrogen
blistering, hydrogen-induced (stepwise) cracking (HIC), and stress-
oriented hydrogen-induced (stepwise) cracking (SOHIC).
Other forms of stress-corrosion cracking (SCC), by direct conse-
quence of the gas or by gas-treating agents, are also reported in re-
finery and production facilities that deal with wet acid gas. One SCC
type is related to amine cracking where the H2S- or CO2-rich gas-
process stream is sweetened by a lean amine such as monoethanol
(MEA) or diethanol amine (DEA). Cracking is observed in the H2S-
rich MEA or DEA stream. The second SCC type is carbonate/bicar-
bonate cracking. Both these cracking mechanisms are considered
similar, occurring in an alkaline environment and exhibiting inter-
granular branched crack growth in low-strength ferritic/pearlitic
steels.
These latter two mechanisms, amine- and alkaline-caused SCC,
are briefly summarized here because they are present in surface pro-
duction equipment exposed to H2S and CO2 acid gases. These
cracking mechanisms are typically reported in industry surveys.
Such mechanisms are found in recent cracking reports to the NACE
T8-16 committee on refinery equipment3 subjected to H2S/CN- and
H2S-production surface-equipment-inspection survey results re-
ferred to earlier2 in this paper.
HC Mechanisms. The wet H2S/CN HC mechanisms we observed
all require the presence of an aqueous phase, temperatures from am-
bient to 300°F, and the evolution of hydrogen by a corrosion reac-
tion at the environment/steel interface. The presence of hydrogen
ions does not strongly promote absorption into the steel at the inter-
face. The presence of the bisulfite (HS) or CN ions does strongly
promote hydrogen absorption into the steel, poisoning the recom-
bination of hydrogen into a gas in the corrosion reaction. Similar
types of HC damage are not associated with CO2 when the HS or CN
ions are not present. HS and CN ions promote the transport of hydro-
gen across the environment-metal interface and promote blistering,
HIC, and SOHIC.
The cracking mechanism for SSC requires extremely low con-
centrations of hydrogen in the metal (5 ppm). Low concentrations
of HS or CN can produce this level of hydrogen in the steel. There-
fore, SSC is usually controlled by material selection and hardness
control.4-6
The HC mechanisms active in production surface equipment,
based on metallurgical reviews of operating vessel wet flourescent/
magnetic particle testing (WFMT) indications, are primarily blister-
ing and HIC.2 Only limited instances of SOHIC and SSC have been
found.
Blistering. Hydrogen blistering occurs predominantly in low-
strength steels (yield strength less than 80 ksi) that are exposed to
hydrogen. Blistering occurs from molecular hydrogen that collects
at internal planar nonmetallic inclusions or laminations. Under the
internal hydrogen pressure the inclusion (lamination) disbonds
from the steel matrix and forms a blister. Blistering is observed in
pressure vessels, storage tanks, and piping. This form of hydrogen
damage is contrasted with high-temperature (greater than 600°F)
hydrogen damage in steels where hydrogen reacts with carbon
49
Fig. 1—HIC- and SOHIC-cracking morphologies in a steel-plate
cross section.
found in the pearlite colonies and forms methane that produces in-
tergranular fissuring, cracking, and severe loss of ductility.
Hydrogen blistering is not necessarily considered critical to the
pressure integrity of a vessel or pipe; often the blisters do not link
from one plane to another or break the surface. This influences ves-
sel FFS assessments and leads to extended service life. Typically,
blisters are observed on the internal surface of the vessel and may
be drilled to relieve pressure and reduce further deformation.
SSC. SSC has been extensively studied in carbon manganese,
low-alloy high-strength, and microalloyed steels (Ref. 6). SSC is a
specific form of hydrogen embrittlement that occurs in high-
strength steels and hard-weld heat-affected-zones (HAZ). Other re-
search characterizes cracking for steels as dependent on hardness,
temperature, H2S concentration, cold work, and alloy content. Al-
loys with higher alloying content, called corrosion resistant alloys
(CRA’s), can still be susceptible to SSC. SSC in CRA’s is influenced
by the same parameters. SSC is mostly observed in surface produc-
tion equipment at internal attachment clip welds where a hard HAZ
can be developed.
HIC. HIC is a hydrogen-damage mechanism that occurs in soft,
low-strength steels (yield strength less than 80 ksi). Cracking occurs
by the linking of small inclusions that have blistered. The linking
mechanism proceeds from one blistered inclusion to another in ani-
sotropic planes developed from the rolling process in plate manu-
facture. The linking is sometimes called stepwise cracking because
the cracking morphology appears as steps in a metallurgical section
(Fig. 1). Another common term that is applied is blister cracking.
HIC or blister cracking is differentiated from simple blistering by
the linking or cracking of the steel from one blister to another.
SOHIC. SOHIC is a hydrogen-damage mechanism like HIC. The
damage mechanism, however, is driven not only by the high pres-
sures that are generated by the hydrogen at the inclusion to steel in-
terface, but also by the external applied stress.4 These stresses cause
the crack path between inclusions to move more directly through the
plate. The cracking morphology is more reminiscent of a ladder than
a stair step; the inclusions link not as stair steps, but more in a verti-
cal direction like the rungs on a ladder (Fig. 1). Another common
term that is used to describe this phenomenon is ladder cracking.
Corrosion Process: Hydrogen Generation and Transport. To
produce HC-blistering, SSC, HIC, or SOHIC, hydrogen must be
present at the steel surface and then be adsorbed into the metal. The
corrosion process generates hydrogen and involves the production
of iron at the anode that goes into aqueous solution as
Fe³Fe+2)2e–, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (1)
and at the cathode hydrogen is produced and either enters the steel
or forms hydrogen gas and bubbles off. When H2S is present,
2H+)2e– ³H°)H°. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2)
When H2S is not present,
H°)H° ³H2 (gas). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (3)
Hydrogen enters the steel first by adsorption onto the steel at the
water to steel interface and then by being absorbed into the steel as
hydrogen. The amount of hydrogen absorption depends on the cor-
50
Fig. 2—Steel corrosion and hydrogen entry in an H2S environ-
ment.
rosion rate of the steel surface and the concentration of anions, such
as CN or HS, that reduce the tendency to produce hydrogen gas,
shown in Eq. 2. CN and HS also promote hydrogen, H°, entry into
the steel. Fig. 2 shows that in a strictly acid environment without
H2S present, HIC, SOHIC, and SSC would not occur.
Produced wet sweet-acid gas (CO2) environments are an example
of the criticality of HS in the HC mechanisms. General weight loss
corrosion occurs, but HIC, SOHIC, SSC, and blistering in steels
does not occur when HS and CN are not present. Introduction of a
sour environment allows this to occur and these damage mecha-
nisms become active given a susceptible steel microstructure.
Acid-concentration, typically related to pH, has an influence on
damage. An example is acidizing to clean Fe2S-scaled carbon-steel
vessels or piping. Acidizing with a Fe2S scale present produces an
acidic environment with HS present. At pHu4,
Fe2S)acid³Fe+2)H+)HS–. . . . . . . . . . . . . . . . . . . . . . . (4)
At pHt4,
Fe2S)acid³Fe+2)H+)H2S, . . . . . . . . . . . . . . . . . . . . . . (5)
which then leads to either hydrogen charging of the steel with hydro-
gen or hydrogen gas evolution.
2H+)2e–³H°)H° , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (6)
and H°)H°³H2 (gas). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (7)
The presence of the HS promotes the transfer of hydrogen into the
steel (Eq. 6). Normally, acidizing is accomplished with acids with
a pH of 4 to 6, producing high fluxes of hydrogen and the risk of blis-
tering, HIC, or SOHIC from the acidizing alone.
Conditions for Blistering, HIC, and SOHIC. Blistering, HIC,
and SOHIC are interrelated and depend heavily on hydrogen entry
into the steel microstructure. Blistering occurs when the hydrogen
concentration, CH , at a discontinuity exceeds the critical threshold
hydrogen concentration, Cth . The internal discontinuity is usually
an inclusion, but can be produced by SSC of a hardened area where
high Mn segregation has occurred. The condition is expressed as
CH uCth , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (8)
and Cth is related to the material resistance to the hydrogen gas that
has recombined to produce a pressure on the inclusion nucleated
void. The pressure available for causing the inclusion to disbond
from the metal matrix is related to CH at the point where the inclu-
sion is located. Fig. 3 shows a typical profile of CH through thick-
ness in a pressure vessel steel wall, illustrating the conditions for
blistering, HIC, or SOHIC.
Blistering, HIC, or SOHIC damage conditions are determined by
the following critical variables: (1) pressure, pc , (2) steel matrix to
inclusion resistance or fracture-toughness, KIC , and (3) the length
SPE Production & Facilities, February 1996

Fig. 3—Condition for HIC in a steel plate based on CH and Cth re-
quired for HIC or blister formation.
of the inclusion, a. These variables are related by the condition for
inclusion disbonding and crack growth as7
pc tKIC/2(p/a)–½, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (9)
where pc +F(a,CH ), . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (10)
where a is the fraction of hydrogen absorbed into the steel lattice,
pc is the pressure at the inclusion location, and CH is the concentra-
tion of hydrogen at the inclusion location. The CH decreases from
a maximum at the absorption interface where the concentration of
hydrogen (C°H) is maximum to zero at the external surface. This is
expressed in Eq. 11 as (Ref. 8)
CH +C°H (1*x/h), . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (11)
where h is the steel-vessel wall thickness and x is the distance in
from the surface exposed to the environment.
This basic condition for blistering, HIC, or SOHIC given in Eqs.
8 and 9 shows that the inclusion size, the amount of hydrogen enter-
ing the steel to produce the internal pressure, the location of the in-
clusion, and the steel matrix to inclusion interface toughness is criti-
cal in determining whether HIC damage occurs. Treating practices
that reduce the hydrogen entry or reduce the size of inclusions
would reduce or preclude damage to the steel-pressure vessel wall.
Techniques to Control or Prevent Damage. Techniques to control
or reduce the hydrogen entry are (1) water washing to reduce con-
centrations of HS, (2) treating with inhibitors to reduce corrosion
and available hydrogen, and (3) lining the steel areas that are subject
to corrosion with corrosion-resistant claddings like austenitic stain-
less steels.
Steel Resistance. Steel resistance to damage is improved by steel
production techniques that reduce the inclusion or internal disconti-
nuity size. Techniques used to control inclusion size are (1) reducing
sulfur content to low (t0.012) or ultra-low (0.002) levels, (2) re-
ducing phosphorus and other elements like Mn, Cr, Ni, Mo, and Cu,
(3) using specialized continuous casting, slabbing, hot-topping, in-
got-casting, bottom-pouring, deoxidization, and calcium-treating
processes during steel making, (4) specialized cross-rolling practic-
es for thinner plate thicknesses in the ½- to 1½-in. range, and (5) in-
spection techniques to examine plate steel internally for cleanliness
before finishing rolling or after finishing rolling and shipping accep-
tance.
Steel to inclusion toughness or resistance to void extension (KIC)
is indirectly controlled by the toughness of the steel matrix and the
interaction of the inclusion with the steel grain size for ductile-tear-
ing fracture instabilities. Stronger steel will require more pressure
SPE Production & Facilities, February 1996
for an internal void or blister based on Eq. 9 to be formed. Steel grain
refinement should improve the material resistance. Techniques to
refine the grain size during steel production are (1) heat treating by
normalizing, (2) using an accelerated thermomechanical treatment,
and (3) using aluminum or silicon to semikill or fully kill the steels.
These approaches are effective in increasing the blistering, HIC, or
SOHIC resistance of a material.9,10
H2 S Stress-Cracking Control. HS– and CN–caused stress crack-
ing in carbon and low-alloy steels is controlled by limiting the mate-
rial strength. Prevention of hydrogen entry into the steel is not con-
sidered practical because bulk steel content of as little as 5 ppm of
hydrogen can result in cracking in a hard susceptible microstructure.
Water washing or inhibition would not be considered viable meth-
ods of controlling SSC.
Limiting strength is accomplished by placing hardness limits on
the carbon and low-alloy steels. The hardness is proportional to the
material strength. Hardness limits are used for weld metal. A 200
Brinell hardness (BHN) limit is typically used for refinery applica-
tions.4 This limit is based on NACE RP 0472-87. Hardness limits
placed on carbon steels, welds, and HAZ’s, as defined by NACE
MR-0175-92, were set at 22 Rockwell C-Scale (RC), which is
equivalent to 248 Vicker’s and 237 BHN. These limits are recom-
mended, but not required. When low-alloy steels, such as AISI 4130
or 4140, are properly heat treated to produce uniform microstruc-
tures virtually free of retained austenite and upper bainites, hardness
limits are extended to RC 26.
Some approaches to controlling strength or maximum hardness
in fabricated steel vessels and equipment are (1) using lower-
strength steels without a tendency to develop high hardnesses; (2)
controlling cooling rates below a critical rate during welding by
using higher heat inputs and/or preheat; (3) controlling material car-
bon equivalent or being aware of the carbon equivalent when weld-
ing; (4) controlling residual elements, such as Ni, Cu, Cr, Mo, and
V, to a maximum; (5) controlling cooling rates during mill produc-
tion; (6) using normalized carbon-manganese steels; and (7) using
a postweld heat treatment to act as a tempering heat treatment that
reduces hardness.
Production-Facility Service Environments. HC occurs in specific
production gas plant and refinery locations. While the focus of this
paper is on production equipment, locations in refineries are being
mentioned to provide a complementary view of downstream prob-
lem similarity.11
The conditions for blistering, SSC, HIC, and SOHIC have been
discussed. These conditions typically occur in the following refin-
ery units: fluid catalytic-cracking units (FCCU), hydrotreating/hy-
drocracking units, amine absorbers, sour-water strippers, and liq-
uid-propane-gas (LPG) storage vessels. These units, however, will
not be discussed in detail here. In production gas plants, the condi-
tions are also present in amine absorbers and sour-gas/water strip-
pers.
Amine Absorbers and Strippers. Amine absorbers, common to
both refineries and production-acid-gas CO2 and H2S sweetening
plants, are prone to HC when HS or CN are present. Wet sour-gas
feed is sweetened by intermixing with H2S/CO2 and lean amine
through a series of bubble trays. The process occurs between tem-
peratures of approximately 100° to 250°F. These temperatures are
associated with the lower portion of the absorber column. HIC dam-
age occurs primarily near wet sour-gas-inlet areas in absorbers as
the gas feed contacts the steel. SOHIC damage occurs near internal-
attachment welds associated with the bubble-cap trays. Strippers
force the highly condensed H2S and CO2 out of the rich amine.
Strippers could potentially experience SSC, HIC, or SOHIC further
downstream in the outlet area for the H2S where aqueous condensa-
tion has occurred. These stripper overheads are treated to avoid cor-
rosion, discussed previously.
Sour-Water Strippers. Sour-water stripping of single or multi-
phase sour-gas and oil feeds leads to acidic aqueous environments
in the bottom of sour-gas/water strippers or at outlets in multiphase
separators. These areas are prone to blistering, HIC, and SSC. Tem-
peratures associated with separators may vary greatly and depend
51
ÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁ
ÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁ
ÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁ
TABLE 1—WFMT INDICATIONS
ÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁ
Number of Total Vessels
Cracking-Cause Vessel Inspected
ÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁ
Mechanism/Source Instances (%)
ÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁ
Weld Fabrication 185 17
ÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁÁ
Blistering or HIC 64 10
Sulfide Stress 29 5 cracks and other types of discontinuities present allow for repair or
ÁÁÁÁÁÁÁÁ
ÁÁÁÁÁÁÁÁÁÁÁÁÁ
ÁÁÁÁÁÁÁÁÁÁÁ
Alkaline Stress Cracking 15 3 replacement strategies based on sound performance criteria. Three
ÁÁÁÁÁÁ
Total 293
on feed-stream input temperature and extreme climactic conditions.
Water strippers or knock-out drums typically operate at tempera-
tures from ambient to 200°F. This temperature range is within the
range of susceptibility for HC mechanisms to operate.
Surface Production Equipment and Vessel Inspection
After the Lemont failure1 that drew a significant amount of industry
attention to wet H2S/CN cracking in pressure vessels, refinery oper-
ations formed a task force in early 1988 to address specific questions
about HC in sour-service vessels. The refinery-task-force activities
led to recommended guidelines for constructing, operating, inspect-
ing, and repairing vessels in sour-service process streams. Produc-
tion operators initiated inspection and repair programs to identify
and use wet H2S/CN cracking in pressure vessels and update vessel-
materials specifications.
The inspection programs are showing that many WFMT indica-
tions are caused by fabrication and suggest that a lesser percentage
of actual indications are a direct result of HC mechanisms in pres-
sure/vessel steels subjected to wet H2S/CN environments.
Inspection Techniques. Vessel inspection for HIC, SOHIC, blister-
ing, and SSC is preferably done with a WFMT technique. This tech-
nique requires the opening up of equipment and sand blasting or
flapper-wheel cleaning of the internal surface to detect HIC, SOH-
IC, or SSC.
Ultrasonic P-scanning techniques are also used when vessels are
not opened. This technique is capable of generating large quantities
of detailed information, but does not clearly identify whether or not
indications are caused by HIC or SOHIC damage, or by inclusions
(discontinuities) normally associated with steels from which the
equipment is fabricated.
Ultrasonic shearwave techniques, such as crack tip diffraction
techniques, are most helpful in determining the extent of crack
depth and morphology—a determination critical in FFS assess-
ments to be discussed later in this paper.
Industry Inspection Programs. NACE committee T8-16 has
conducted a survey of the refinery-industry process vessels that are
subject to wet H2S/CN cracking and found that 1,285, or 26%, of the
4,987 inspected vessels contained cracks.3
Internal Inspection Programs. Inspecting thousands of internal
refinery and production vessels, which costs tens of millions of dol-
lars, is nearing completion, and monitoring continues as required.
The refinery results were provided to the NACE T8-16 Committee
as part of an inspection survey. The industry survey suggests that
many of the cracks detected and originally thought to be related to
HIC, SOHIC, or SSC are related to fabrication discontinuities.
Of all the production equipment and vessels inspected, 618 (57%)
of over 1,084 showed WFMT indications. The indications are
grouped according to the mechanisms or causes described in Table
1.
These results show that production equipment contains a relative-
ly high percentage of as-fabricated discontinuities that have existed
in the equipment for an extended time period. The percentage of
HIC-related cracking is under 10%.
FFSĊVessels and Repair
Production surface equipment with discontinuities or cracks are
quite common, according to the inspection survey data. These ves-
sels have operated for a number of years with original fabrication
52
discontinuities. The question is how to determine whether the
equipment or vessel is fit for service and can continue to be operated
safely and profitably. To address this question, a FFS is being ap-
plied to process vessels.12 The FFS technology is not new, and has
had success in application in the aerospace, nuclear, and offshore-
structures industries, among others.
Application to process vessels after inspection has shown that
levels of analysis are available, each one being more involved than
the one before. Through this analysis, acceptance criteria are set that
allow safe and productive operation of a process vessel with cracks
or discontinuities.
Blistering. Blisters in the center of the plate are treated simply and
directly by FFS technology. Blisters that remain in the plane of the
plate parallel to the stressed direction are benign and simply ig-
nored. Blisters with ends that extend towards the surface of the plate
require a more detailed analysis.
Internal Surface Cracks and Weld Repair. Surface cracks found
by WFMT inspection are typically ground or excavated by arc
gouging. Typically, when the grinding or excavation depth exceeds
the corrosion allowance, weld repair is required. By using FFS tech-
nology, many of these ground areas do not require weld repair.
HIC and SOHIC Materials Performance
Field and Supplier Steels. Steel pressure/vessel materials ASTM
A285C, A515, A516 Grades 60 and 70, A537 Class II and A841
were obtained from both field-process service locations and from
international and domestic steel suppliers where steels are produced
with various processes, representing current steel-production tech-
nology.
Steels From Operating Vessels. Field sample sources were devel-
oped as available with the support of the operating locations to in-
clude pressure/vessel steel grades such as ASTM A285 Class C,
A212, A515, and A516 Grade 60 or 70 in the as-welded or postweld
heat treatment (PWHT) condition.
Steel-Producer Sources. Materials were obtained from vessels
that had been in wet H2S/CN service with evidence of HC found by
WFMT inspections. Supplier steel pressure/vessel samples were
obtained from both domestic and international sources to provide
materials fabricated with different state-of-the-art steel-making
technologies. These steels included ASTM A516 and A841 with
supplemental requirements in both the as-rolled, normalized, ther-
momechanically processed (TMCP), and quenched and tempered
finished conditions.
Steel Chemistries and Mechanical Properties. Steel chemistry
and mechanical properties were measured for both the field and the
steel-supplier samples evaluated. Heat analysis results were not
used in an effort to characterize the actual plates tested and did not
consider variations in properties within a heat. Weldability parame-
ters were also calculated from the individual chemistries according
to the following formulas from the IIW.
HIC-Testing. Steel pressure/vessel materials ASTM A285C,
A515, A516 Grades 60 and 70, A537 Class II and A841 were tested
in both pH 3.5 and 4.5 solutions. Tests were run in both the more
aggressive pH 3.5 solution (TM 01 77) and the pH 4.5 solution (TM
02 84) to see the relative differences in the corrosion and hydrogen-
charging effects of the two solutions.
Test results generally showed that the lower sulfur steels have a
tendency to produce lower values of crack/sensitivity ratio (CSR),
crack/length ratio (CLR), and crack/thickness ratio (CTR). Test re-
sults showed that materials can achieve a CLR below 30 when the
sulfur is less than 0.006 wt%, the material is normalized, and some
inclusion shape control practice is used. Finally, steels that are as-
rolled with higher sulfur content show a greater tendency to have
higher values of CLR and lower values of CTR relative to the
normalized steels with lower sulfur contents. Steels that are specifi-
cally produced for HIC resistance by the manufacturer for new
construction have a goal performance-acceptance criterion that
ranges from 10 to 15 CLR in the industry.
SPE Production & Facilities, February 1996
 SOHIC-Testing. The NACE TM 01 77 test method was selected
to simulate HIC cracking under stress, a reported prime influence on
property degradation and material performance in wet H2S/CN en-
vironments. The acidic-pH 3.5 aqueous NACE test solution with
H2S, 5% NaCl, and 0.5 wt% acetic acid was selected as the most se-
vere and therefore most conservative measure of a steel’s resistance
to HIC or SOHIC.
The threshold stress, expressed as a percentage of the actual yield
strength, typically ranges from 40% to 100%. We should note that
the results show that steels with relatively high HIC resistance do
not necessarily have high thresholds. Steels used for wet sour-gas
production as oil-country tubular goods (OCTG) must pass an 80%
criterion set by API Specification 5CT. Amoco requires a 90% ac-
ceptance criterion for tests run to this method. However, the crack-
ing mechanism for the OCTG is not SOHIC, but SSC, suggesting
that this acceptance criterion may or may not be applicable to SOH-
IC failure mechanisms that are different in pressure vessels.
Material-Performance Specifications. As a result of laboratory
testing and field-sample evaluation, specifications were established
for new construction and fabrication. These requirements are estab-
lished to reduce risk of blistering, HIC, SOHIC, and SSC in new
construction. Key points to steel resistance are control of sulfur, car-
bon equivalent, and HIC/SOHIC resistance through acceptance
testing. Fabrication factors in controlling SSC are welding proce-
dure, heat input, and PWHT.
Steel Requirements. Steels are required to be made to fine grain
practice (ASTM grain size 5 or smaller), normalized, and have a
maximum sulfur content of 0.012 wt%. The steel is also required to
pass a performance HIC test per NACE TM02 84 requirements,
using the more aggressive NACE TM 01 77 test solution. Accep-
tance criteria are set at a CLR of 15 % and CTR of 5%. CLR and CTR
to some degree measure material resistance to HIC and SOHIC.
Fabrication Requirements. PWHT is required after welding, with
WFMT inspection following. In selected situations, weld procedure
qualification is also required. As part of the procedure qualification
record (PQR), welds are hardness tested in the HAZ and must have
a hardness that is less than 248 BHN. Testing is done with a Vicker’s
hardness indentor with a 10-kg load. Carbon equivalent is con-
trolled to reduce the risk of hardness exceeding 248 BHN. Steels
with plate thicknesses of 1.5 in. or less must have a carbon equiva-
lent (CE) of less than 0.42, while steel with plate thicknesses that ex-
ceed 1.5 in. must have a CE of no more than 0.45. CE is computed
per the IIW formula.
CE+C)Mn/6)(Cr)Mo)V)/5)(Ni)Cu)/15. . . . . . (12)
These requirements add to the cost of a surface-process vessel.
Estimates of added cost range from 10% to 30% increase in steel
cost and 8% to 50% increase in as-fabricated cost of a process ves-
sel. However, these costs are easily offset by the cost of periodic in-
spection and dismantling of a vessel and making repairs, or, in ex-
treme cases, replacing the equipment.
Conclusion
HIC in surface production equipment is an important consideration
in operating equipment in a safe and efficient manner. Understand-
ing of the mechanism causing HIC, SOHIC, blistering, and SSC,
and the applications of FFS technology have shown ways of dealing
with the phenomenon in a cost-effective manner. Through inspec-
tion and repair strategies, process equipment in wet H2S service can
be maintained. Through specifications relating to material perform-
ance and fabrication control, new equipment can be placed in ser-
vice with more resistance to HIC, SOHIC, blistering, and SSC in wet
H2S service.
Nomenclature
a+ characteristic inclusion or crack length
a+ fraction of hydrogen absorbed into steel at interface
of steel and corrosive environment
CH + hydrogen concentration
SPE Production & Facilities, February 1996
CHo + hydrogen concentration at the absorbation interface
Ec + carbon equivalent (IIW formula)
KIC + material fracture toughness at tip of inclusion or
crack
pC + critical pressure
h+ wall thickness of pressurized equipment
x+ position from surface through wall of vessel
References
1. McHenery, H.I. et al.: “Examination of a Pressure Vessel that Ruptured
at the Chicago Refinery of Union Oil Company on July 23, 1984,” Re-
port No. NBSIR 86-3049, National Bureau of Standards, Boulder, CO
(March 1986).
2. Miller, C. and Sperling, E.: “Crack Inspection of Sour Service and
Amine Service Vessels in Hydrocarbon Production Operations,” paper
No. 44, CORROSION 92, Nashville (April 1992).
3. National Association of Corrosion Equipment (NACE) Committee
T8-16, Minutes, Fall Committee Week, Calgary 1992.
4. Merrick, R.D.: “Refinery Experiences with Cracking in Wet H2S Envi-
ronments,” Materials Performance (Jan. 1988).
5. Hudgins, C.M. et al.: Corrosion (1966) 22, No. 8, 238.
6. Tuttle, R.N. and Kane, R.D.: “H2S Corrosion in Oil and Gas Produc-
tion-A Compilation of Classic Papers,” Publication No. 51113, NACE,
Houston (1981).
7. Iino, M.: “The Extension of Hydrogen Blister-Crack Array in Line pipe
Steels,” Metallurgical Transactions (Nov. 1978) A, 1581-1590.
8. Hirth, J.P.: “Effects of Hydrogen on the Properties of Iron and Steel,”
Metallurgical Transactions (June 1980) A, 861-890.
9. Ikeda, A. et al.: “Development of Hydrogen-Induced Cracking Resis-
tant Steels and HIC Test Methods for Hydrogen Sulfide Service,” Paper
No. 6, Session 11, 1983 Annual Conference of Metallurgists-Canadian
Institute of Mining and Metallurgy, Edmonton, Alta, March.
10. NACE T8-16, State-of-the-Art “Report-Materials and Fabrication Prac-
tices for New Carbon Steel Pressure Vessels to be use in Wet H2S Refin-
ery Service,” Draft Report to T8-16 Members, NACE Fall Committee
Week 1992.
11. Kane, R. D., Whilhelm, S.M., and Oldfield, J.W.: “Review of Hydrogen-
Induced Cracking of Steels in Wet H2S Refinery Service,” paper pres-
ented at the 1989 International Conference on Interaction of Steels with
Hydrogen in Petroleum Industry Pressure Vessel Service, Paris, March.
12. Warke, W.M.: “Fitness-for-Service Approach for Pressurized Equip-
ment With Discontinuities,” 1992 ASME Pressure Vessel and Piping
Conference-Workshop on Fitness-for-Service in the Petroleum Indus-
try, New Orleans, June 24–26.
SI Metric Conversion Factors
°F (°F*32)/1.8 +°C
in. 2.54* E)00 +cm
lbm 4.535 924 E*01 +kg
psi 6.894 757 E)00 +kPa
*Conversion factor is exact. SPEPF
James D. Burk, an associate research engineer at Amoco Corp.
in Naperville, IL, received his BS, MS, and PhD degrees from the
U. of Illinois at UrbanaĆChampaign in materials science and enĆ
gineering. Before joining Amoco, he held either technical or suĆ
pervisory positions at McDonnell Douglas Astronautics, Shell DeĆ
velopment Co., and Brown & Root Intl., and studied or directed
work in materials environmental degradation, fatigue, and
fracture. James currently focuses his interests on materials and
corrosion behavior in petroleum production, refining, transĆ
portation, and marketing operations. He has published or preĆ
pared over 30 papers related to environmental degradation of
materials, corrosion, welding, fatigue, and fracture over the
course of his 25 year career.
53