Operators 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

H+

H2

pH <7

H
H

2-

Fe 2+

S HS
FeS Film
Metal Matrix

Applied Stress

No Applied Stress

Higher Strength Steels YS > 500 MPa

Low Strength Steels YS < 550 MPa

H2
H H
H H
H

H2

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
additions)

(ksi)

Resistant

Min. Yield

Max. Yield

Min. Tensile

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)

13-0-0*

(e.g. L80 13Cr) 90

13-4-1*

110

13-5-2

110

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

21-42-3

125

22-50-7

140

25-50-6

140

20-54-9+17Fe

140

15-60-16 +4W

140

Martensitic Stainless Steel

Duplex Stainless Steel

Austenitic Ni Alloys

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

pH

Decrease chloride,
temperature?

Increase chloride,
temperature?

Partial Pressure
H2S

Crackin
g

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

pH

Acceptable

0.5 bara

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