CANMETMTL

Metallurgical Factors in Stress

Corrosion Cracking (SCC) and
Hydrogen-Induced Cracking (HIC)
Metallo-2007
Indian Institute of Technology, Kanpur
in Honour of Professor T. R. Anantharaman
Winston Revie and Mimoun Elboujdaini
CANMET Materials Technology Laboratory
Natural Resources Canada, Ottawa, Canada
December 10, 2007
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Outside

Inside

Outline

Overview of Underground Oil and Gas Pipelines

Hydrogen-Induced Cracking (HIC)
- Metallurgical and Environmental Variables
- Inclusions
Stress Corrosion Cracking (SCC)
- Metallurgical, Mechanical, Environmental,
and Electrochemical Variables
- Inclusions
Conclusions
What Does the Future Hold?
Collaboration/A World without Borders
Acknowledgements
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Underground Pipeline
2 Sides to Every Pipe

Steel, Coating

Soil,
Microorganisms,
Unstable Terrain
Flowing
Flowing
Oil,
Oil, Brine
Gas,
Gas,
Brine

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HIC in Steel Exposed

to Sour Gas

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Hydrogen-Induced
Cracking (HIC)
Internal cracks caused by
trapped hydrogen atoms.
- Cracks parallel to
rolling plane.
- Residual or applied
tensile stress not
necessary for HIC.
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Prediction of HIC

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1. Immersion, 4 days, in H2S-satd buffer

solution, pH varied from 1.1 to 5.9
2. Diffusible hydrogen measured, glycerol
displacement at 45oC
3. Coupons examined for cracking, ultrasonic
C-scan, metallographic examination

pHth and

CHth

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Environment
pHth
Lowest pH at which no HIC was
detected
Material
CHth
Highest hydrogen concentration in
the steel at which no HIC was
detected
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Criterion for HIC

Steel
cH0

H2S/H2O

HIC
H
c th

Air

cH0
0

No HIC

H
c H0
cHth

Concentration of H at the inner pipe surface

Threshold H Concentration
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Criterion for HIC

HIC occurs if:
H
c 0>

Environmental
Variable

H
c

th

Material
Variable
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2.5
2
1.5

Threshold
Hydrogen Concentration,
mL
.
T h r e s h o ld h y d r o g e n c o n c e n t r a t io n ( m L )

HIC and Title

Inclusions

1
0.5
0
0

0.1

0.2

0.3

Volume fraction of inclusions (%)

Volume Fraction
of Inclusions, %
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0.4

0.5

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Inclusions
Inclusions in cracks are MnS, by EDX
Provide sites for H to accumulate

Steel Crack
A
Yes
B
Yes
C
Yes
D
Yes
E
No
F
No

Ca/S
0.15
0.50
0.96
1.31
2.62
2.50

Optimum Ca/S Ratio

2<Ca/S<5

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Microstructures

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Stress Corrosion Cracking Is

A cracking process that requires

the simultaneous action of a
corrosive and a sustained tensile
stress.

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Requirements

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1.Steel susceptible to SCC

2.Tensile stress
3.Potent environment
- Coating failure provides access of
aqueous environment to pipe
surface.

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Stress
Hoop stress
- from internal pipe pressure

Axial stress
- from soil movement or localized pipe bending

Residual stress
- from pipe forming or steel making operations

Cyclic stress
- Fluctuations in operating pressure
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Stresses in Pipelines

From: N.E.B Report on SCC, MH-2-96 (1996)

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Types of SCC
Near-Neutral-pH SCC
- Transgranular

High-pH SCC
- Intergranular

Orientation:
- Longitudinal
- Circumferential

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Stages of SCC

1. Generation of Environment
2. Initiation of SCC
3. Propagation of SCC

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a
c

b
c

d
e

20 m

Total Exposure Time

309 h

e
300 m

469 h
747 h

1025 h

Development of 5 cracks, a, b, c, d and e, after the total exposure

time shown, in X-65, max = 70% YS, R = 0.4 and f = 1 Hz in NS4
solution saturated with CO2, showing the correlation of crack
initiation, pits and non-metallic inclusions and the interaction and
coalescence of cracks. (Observations were made on replicas.)
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(a)

(b)

b
b

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c
d

e
e

200 m

N = 1.69 x 106 Cycles

N = 2.69 x 106 Cycles

469 h

747 h
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Al-oxide
Al
Al

(a)

Ca
Ca

Al
Al

S Ca
Ca

(b)

S
O
20 m

CaAlO3

CaS

dark

CaS

Ca

Al S Ca
(c)

EDX Spectrum

All dissolved
Before Test

After Test

EDS spectra and the morphologies associated with three

inclusions in a X-65 steel sample before and after test at max=
90%YS, R=0.6 and f=0.1Hz in NS-4 solution saturated with
N2/5%CO2. Note: Effect of S on corrosion around inclusions.
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Schematic of Inclusion

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Sulfide,
(soluble)

Oxide
(insoluble)

In some cases, CaS envelopes oxide/aluminate inclusion.

Aluminate inclusions have poor deformability, remain spherical.
In polishing to 1 m diamond finish, use non-aqueous lubricant, oilbased diamond.
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(a)

X 25 m

Y 25 m

Focused ion beam images of crack in X-65 specimen after 4.15 x 106
cycles, max = 70% YS, R = 0.4, f = 1 Hz, NS-4 solution, CO2 satd.
(a) Plan view of crack, FIB secondary electron image, tilt 0 deg. (b)
Enlargement of crack tip area in ion-milled cross-sectioned region,
tilt 30 deg. (b) image in secondary ion mode,
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Not Wrapped

Wrapped

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1025 h

747 h

X-65 steel, max = 70% YS, R = 0.4, f = 1 Hz, in NS4 solution saturated with CO2.
Right part of specimen in (a) was coated with PTFE film during the test interval
between 469 and 747 h. No coating between the exposure of 747 and 1025 h (b).
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Pipe Fatigue Precracking

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Full-Scale Pipe Test for SCC

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Conclusions - 1
1.

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SCC promoted by:

1. Decreasing R (min./max. stress)

2. Increasing frequency
2.

3.
4.
5.

Environment that leads to SCC is generated by the

balance between:
CO2
CP current
Inclusions provide initiation sites for pitting
Pits provide initiation sites for SCC
Proximity of several small cracks can lead to
linkage
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Conclusions 2
6. SCC Initiation Sites
Pits
Inclusions
Surface geometric discontinuities
Coating Disbondments

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Conclusions 3

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7. Elongated inclusions provide H trap sites for HIC

initiation
1. Good correlation between inclusion measurements
and HIC
2. Lower volume fraction of inclusions ~ increased
HIC resistance
3. Banded microstructure decreases HIC resistance

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What is the Main Question

about Corrosion?

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1. Will there be another failure?

If?

2. When will the next failure occur?

When?

3. Where will the next failure occur? Where?

What do YOU think?

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Building on Success

Information on
Data & Decisions

Cellular Network/Satellite Communications

Software for Data Analysis
and Decision-making
Instrumentation for Data Collection
Sensors for Field Measurements
100 Years of Corrosion R&D The Foundation
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Intelligent Systems
Are Built on
1.
2.
3.
4.
5.

Knowledge of Corrosion
Sensors
Instrumentation
Software
Remote Communications

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Convergence of
technologies provides
new opportunities to
manage corrosion.

1960s: Design Corrosion Out

2000s: Design Smart Systems for Corrosion Monitoring and
Decision-making
Monitoring online, in real time, all the time

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Corrosion
Control
Wagon
$$$

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Corrosion
Control
Wagon
$$$

A Strategy
Meeting
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Team
Leader

Corrosion
Control $$$
Wagon 45

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Acknowledgements
Jenny Been
Jenny Jackman
Dave Kiff
Yves Lafrenire
Ruel Ramsingh

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Mahmoud Shehata
Yong-zhi Wang
Glenn Williams
Wenyue Zheng

GRI
PRCI
Canadian Federal Interdepartmental
Program of Energy R&D (PERD)
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Last Thought

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Managing corrosion is an investment in

asset protection that should result in cost
savings because, when corrosion is
managed, the cost of failure by corrosion
is saved.

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Failure Prevention
Knowing is not enough;
we must apply.
Willing is not enough;
we must do.
Goethe
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NS-4 Solution

483 mg/L NaHCO3

122 mg/L KCl
Trang Web
nay 2coi cung hay, vao coi thu di
137 mg/L
CaCl
http://gaigoibaucat.xlphp.net
131 mg/L
7H
unTrangMgSO
Web nay 4coi
cung
hay, vao coi thu di
2O
http://gaigoibaucat.xlphp.net

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CANMETMTL

Trang Web nay coi cung hay, vao coi thu di

http://gaigoibaucat.xlphp.net
C:\WINDOWS\hinhem.scr

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