Operator’s views of current status and

future research - H2S Cracking

John Martin
BP Exploration
Sour Service (H2S Cracking)

• Definition:-
− ISO 15156
‘Exposure to oilfield environments that contain H2S
and can cause cracking of materials by the
mechanisms addressed by ISO 15156 Part 1’
• Mechanisms in ISO 15156
− SSC, HIC, SOHIC, SZC, SCC, GHSC
Generation of Hydrogen by Corrosion Processes

Fe2+
. .
2H++2e =H +H =H2
.
H
Fe – 2e
. .
H +H =H2
Hydrogen Entry Mechanism

• Atomic Hydrogen is generated by the corrosion

process
• Generally H• + H• = H2
• However HS- poisons the combination.
• H• enters the steel matrix
Cracking in sour service

pH 2S H2 H+ Fe 2+
2-
S -
HS
pH <7 H
FeS Film

Metal Matrix
H

Applied Stress No Applied Stress

Higher Strength Steels YS > 500 MPa Low Strength Steels YS < 550 MPa

H2
H H
H H H2
H
Sulphide Stress Cracking (SSC)

• Cracking involving corrosion and tensile stress in the

presence of water and H2S
• Hydrogen embrittlement mechanism in carbon steel
Low Alloy Steel Grades (API 5CT/ISO11960)
Grade Strength H 2S
(ISO 11960 (ksi) Resistant
except *) Min. Yield Max. Yield Min. Tensile

H40 40 80 60 Yes
J55 55 80 75 Yes
K55 55 80 95 Yes
M65 65 85 85 Yes
N80 80 110 100 No (?)
L80 80 95 95 Yes
C90 90 105 100 No (?)
C95 95 110 105 No (?)
T95 95 110 105 Yes
P110 110 140 125 No (?)
C110* 110 120 115 Mild Only
Q125 125 150 135 No (Type 1 (?))

C125* 125 140 130 Very Mild Only

Domain Diagram for C110
Low Alloy Steel Grades (API 5L/ISO3183)
Grade Strength H2S
(* new (ksi) Resistant
additions)
Min. Yield Max. Yield Min. Tensile

B 35 65 60 Yes
X42 42 72 60 Yes
X46 46 76 63 Yes
X52 52 77 67 Yes
X56 56 79 71 Yes
X60 60 82 75 Yes
X65 65 87 78 Yes
X70 70 92 83 Yes
X80 80 140 125 No (?)
X90* 90 112 101 No (?)
X100* 100 122 110 No (?)
X120* 120 152 133 No (?)
Hydrogen Induced Cracking (HIC)

• Cracking that occurs when atomic hydrogen diffuses into steel and
combines to form molecular hydrogen at discontinuities
• Also called Hydrogen Pressure Induced Cracking (HPIC); Blister
cracking; Stepwise cracking (SWC)
30” seam welded API 5LX 60 sour
crude oil pipeline, failed 1972 during
commissioning. Abu Dhabi

Also called “step-wise

cracking”
HIC and Related Mechanisms in ISO15156/NACE
MR-0175

“The equipment user shall consider HIC/SWC

as defined in ISO 15156-1/NACE MR-0175
when evaluating flat-rolled carbon steel
products for sour service environments
containing even trace amounts of H2S”
Preliminary proposal for HIC severity regions
CRA Grades (ISO 13680 except *)
Type Category Maximum Available SMYS
(Cr-Ni-Mo) (ksi)

Martensitic Stainless Steel 13-0-0* (e.g. L80 13Cr) 90

13-4-1* 110
13-5-2 110
Duplex Stainless Steel 22-5-3+N 125
25-7-3+N 125
Super Duplex Stainless Steel 25-7-4 + 2W +N 125

Austenitic Stainless Steel 27-31-4 140

25-32-3 140
Austenitic Ni Alloys 21-42-3 125
22-50-7 140
25-50-6 140
20-54-9+17Fe 140
15-60-16 +4W 140
13Cr/4Ni/1Mo alloy – SSC Failure
SSC Failure of Downhole Tubular String

• HP/HT Gas Producer – 45mmscf/d, 50ppm H2S and 8.7mol%CO2.

(0.5psia H2S, pH 3.5).
• Completed with a mixture of L80-13Cr & CR13 95ksi 13/4/1 tubing.
• Packerless completion allowed produced fluid to contact tubing OD.
• Tubing failed via SSC at localised sites of cold work on the OD (slip and
tong marks).
• Gas, water and sand flowed from the tubing bore to the annulus,
resulting in significant erosion of both the tubing and casing.
Domain Diagram for Super 13Cr

ACCEPTABLE

5.5
0.03bara

pH 4.5
FURTHER ASSESSMENT REQUIRED

3.5
UNACCEPTABLE

0.001 0.01 0.1 1.0

pH 2 S (bara)
Domain Diagram For The Sulphide Stress Cracking Limits
Of 95ksi Super 13Cr Alloys In High Chloride (120,000 ppm Cl-) Waters
Stress Corrosion Cracking (SCC)

• In the context of this talk relates to the SCC

mechanisms that are associated with ‘active path
dissolution’ mechanisms (e.g. chloride SCC) and not
hydrogen-related mechanisms already covered (SSC,
HIC, etc.)
• As such the focus is mainly corrosion-resistant alloys
such as austenitic stainless steels (e.g. AISI 316),
duplex stainless steels (mixed mode mechanism or
CSC) and some nickel alloys (e.g. alloy 825)
• Developing domain diagrams for welded constructions
(flowlines, manifolds, piping,vessels, etc.) similar to
those already developed for OCTG
Domain diagrams for CRA flowlines and risers

No cracking

Decrease chloride,
temperature?
pH

Increase chloride,
temperature?
Crackin
g

Partial Pressure
H2S
Effect of welding?

pH

Partial Pressure
H2S
Cracking of duplex stainless steel
SSC Domain for 25Cr Duplex Stainless Steel (125ksi SMYS)
<120,000 ppm Cl

Acceptable 0.5 bara

pH

Unacceptable
0.25
bara

Partial pressure of H2S (bara)

Areas of active research

• Effect of environmental conditions on cracking of CRAs

− Chloride
− Temperature
− pH
− H 2S
• Effect of material processing on cracking
− Welding
− Plastic strain
H2S Cracking (SSC, SCC and HIC)

Thank You
For
Your
Attention!
SOHIC

3.5
mm
SOHIC

• Current Test Methods

− NACE TM0103 – Plate steels
− OTI 95 635 – Linepipe
• No universally accepted test method available
• Bodycote/TWI/Force JIP
− Aim – To develop a simple go/no go SOHIC test
method for pressure vessel steels and line pipe
SOHIC

• SOHIC testing requires further development

− JIP Test Method (Test Method imposes simultaneous
twisting and bending on a flat specimen to generate
triaxial stress)
− Methods for assessing fittings
• Appropriate test methods need to be applied
• Test techniques need to be realistic such that good
materials are accepted and poor ones rejected