CO2 Preferential Weld Corrosion of Longitudinally Welded Linepipe - Effect of Microstructure, Corrosion Product Layers, and The Environment

Dissertation
CO2 Preferential Weld Corrosion of

Longitudinally Welded Linepipe: Effect of
Microstructure, Corrosion Product
Layers, and the Environment
carried out for the purpose of obtaining the degree of Doctor technicae (Dr. techn.),
submitted at TU Wien, Faculty of Mechanical and Industrial Engineering, by
Robert Muggleton, MEngSc, BE
Mat.Nr.: 1429784
under the supervision of

Ao.Univ.Prof. Dipl.-Ing.Dr.techn. Paul Linhardt
Institute of Chemical Technologies and Analytics, E164
Reviewed by
Univ. Prof. Dra. Maria Victoria Biezma
Dept. of Materials Science and Engineering
Universidad de Cantabria
Univ. Prof. Dipl.-Ing. Dr. Ernst Kozeschnik

Institute of Materials Science and Technology
Technische Universität Wien
Affidavit
I declare in lieu of oath, that I wrote this thesis and performed the associated
research myself, using only literature cited in this volume. If text passages from
sources are used literally, they are marked as such. I confirm that this work is
original and has not been submitted elsewhere for any examination, nor is it
currently under consideration for a thesis elsewhere.
Vienna, August, 2018

Signature
CO2 Preferential Weld Corrosion of Longitudinally Welded Linepipe: Effect of Microstructure,
Corrosion Product Layers, and the Environment
Robert Muggleton
Dedicated to my sister, Sharyn
Acknowledgements
A sincere thank you to my advisor Prof. Paul Linhardt, a very knowledgeable, patient man,
who is also excellent at explaining complicated things. It’s hard to imagine how one could
have had a better advisor.
Getting an oil and gas company to pay for a PhD while the oil price was free-falling through
the $30 a barrel mark was challenging to say the least. A very special thank you is in order
to the head of the OMV Upstream Materials and Corrosion Department, Dr. Gerald
Zehethofer. Not only did you reply to a random e-mail from the other side of the world, from
a stranger asking to do a PhD in your lab, but you fought relentlessly to secure funding
during a very brutal oil crisis.
Building my experimental test rig through up many technical challenges, all which were
solved after many discussions with three very helpful guys. A kind thank you to Dr. Stefan
Hönig, Günther Ball, and Christian Pripfl.
As many metallurgists know, discussions about bainitic microstructures can go on for days if
not months, and for that, a special thank you to Prof. Victoria Biezma.
While not providing much in the way of technical support, work bestie Emilia Tulan provided
the daily and very important motivational support.
My parents, who endured many phone calls from an annoying time zone, just to keep me
entertained while I was tinkering away in the lab, and my sister who always pushed me
academically.
Last but not least, Ami, not only for your constant support, but without you I never would
have entertained the idea of finishing my Masters’, let alone starting a PhD.
Publications
Work from this thesis was presented at the NACE International CORROSION 2018
conference with the following publication:
R. Muggleton, P. Linhardt, G. Zehethofer, “Role of Microstructure in the Susceptibility of X42

ERW Linepipe to CO2 Preferential Weld Corrosion,” Paper No. 10522, CORROSION 2018
(Houston, TX: NACE International, 2018).
Abstract
Academic publications on the CO2 corrosion of carbon steel linepipes in oil and gas
production environments date back as far as the 1940s. Despite considerable research, CO2
corrosion and preferential weld corrosion still account for approximately 46% of material
failures within the oil and gas industry, and present a serious risk to asset integrity and
reliability. The problem of preferential CO2 weld corrosion is complicated by the formation of
siderite based corrosion product layers, which can either inhibit or accelerate localized
corrosion.
Longitudinally welded ERW (electric resistance welded) linepipes are a commonly used
material for oil and gas pipelines, due to their lower cost and shorter lead times over
seamless. However, the longitudinal ERW weld introduces a region of microstructural
heterogeneity, which sometimes is susceptible to localized CO2 preferential weld corrosion.
Pipelines are often made from ERW linepipes of the same material grade (e.g. API grade
X42), however, sourced from several manufactures. Despite having nearly identical
mechanical and chemical properties, after a relatively short period of operation (several
months to a couple of years), some manufacturers appear to have a significantly higher
susceptibility to CO2 preferential weld corrosion than others. The reason for this difference in
susceptibility is unclear. Furthermore, unlike for H2S environments, there is no standard
regarding material selection to avoid preferential weld corrosion in CO2 environments.
The oil and gas industry therefore requires:
1. An explanation as to why relatively similar ERW carbon steel linepipes can have
significantly different susceptibilities to CO2 preferential weld corrosion.
2. An experimental test method that can quantitatively identify a particular linepipe’s

susceptibility to CO2 preferential weld corrosion, so various manufacturers can be
compared during the material selection process of a project.
This thesis developed a new methodology for assessing an ERW linepipe’s susceptibility to
CO2 preferential weld corrosion. The new approach is referred to as multi-channel zero
resistance ammetry. The developed technology allowed the ERW materials to corrode in a
natural and unforced way in various CO2 environments inside a stirring autoclave, however,
the galvanic coupling currents flowing between different microstructural zones present in the
ERW material could be monitored in real time. This allowed the direct identification of
microstructural zones (and therefore specific linepipes) that were susceptible to CO2
preferential weld corrosion. Scanning electron microscopy was able to correlate localized
corrosion susceptibility to corrosion product layer morphology around the weld region, which
was dependent on the cementite morphology in the steel. From this, a model was developed
explaining how ERW welds corrode, and why some ERW linepipes are more susceptible to
CO2 preferential weld corrosion than others, despite being the same material grade.
The information from these experiments provides oil and gas companies with material
selection guidelines for avoiding preferential weld corrosion of ERW linepipes in CO2
production environments. The developed technology also has the potential for field
deployment, where the effects of changes in operating conditions (i.e. inhibitor
concentration, pH, flow rate) to weld corrosion behaviour can be viewed immediately.
Fundamentally, results from this thesis can be used as a guide to increase asset
integrity and reliability.
Kurzfassung
Wissenschaftliche Veröffentlichungen zu CO2-Korrosion von Kohlenstoffstahl-

Rohrleitungen im Bereich der Öl- und Gasproduktion reichen zurück bis in die 1940er Jahre.
Trotz angestrengter Forschung beträgt der Anteil an Schäden durch CO2-Korrosion aber
immer noch 46% der Werkstoffschäden in diesem Bereich und stellt damit noch immer ein
hohes Risiko für Anlagenintegrität und -zuverlässigkeit dar. Das Problem der selektiven
Korrosion an Schweißnähten durch CO2 wird durch die Bildung siderit-basierter Schichten
aus Korrosionsprodukten verkompliziert, welche Lokalkorrosion sowohl inhibieren als auch
beschleunigen können.
Längsnahtgeschweißtes ERW-(elektrisch widerstandsgeschweißtes) Rohrmaterial

wird allgemein für Öl- und Gasleitungen eingesetzt, da es kostengünstiger und rascher
verfügbar ist als nahtlose Rohre. Allerdings bedingt die ERW-Schweißnaht eine Zone mit
heterogener Mikrostruktur, die manchmal gegenüber der selektiven Korrosion der
Schweißnaht durch CO2 empfindlich ist. Rohrleitungen werden oft aus ERW-Rohrmaterial
derselben Werkstoffspezifikation (z.B. API, X42) gefertigt, das aber von unterschiedlichen
Herstellern stammt. Trotz nahezu identischer mechanischer und chemischer Eigenschaften
ist aber fallweise nach relativ kurzer Einsatzdauer (einige Monate bis Jahre) zu beobachten,
dass manche Fabrikate deutlich höhere Empfindlichkeit gegenüber selektiver CO2-
Schweißnahtkorrosion aufweisen als andere. Der Grund für diesen Unterschied ist bislang
unklar. Im Gegensatz zur Werkstoffwahl für H2S-hältige Medien gibt es darüber hinaus
derzeit auch keinen technischen Standard für die Werkstoffauswahl zur Vermeidung von
selektiver CO2-Schweißnahtkorrosion.
Die Öl- und Gasindustrie benötigt daher:
1. Eine Erklärung für stark unterschiedliche Empfindlichkeit von relativ ähnlichem

ERW-Rohrmaterial gegenüber selektiver CO2-Schweißnahtkorrosion.
2. Ein experimentelles Prüfverfahren, das die Empfindlichkeit von Rohrmaterial
gegenüber selektiver CO2-Schweißnahtkorrosion quantitativ bestimmen lässt,
sodass unterschiedliche Fabrikate im Zuge der Werkstoffauswahl eines
Projekts verglichen werden können.
Im Rahmen der vorliegenden Dissertation wurde eine neue Methodik für die
Bestimmung der Empfindlichkeit von Rohrmaterial gegenüber selektiver CO2-
Schweißnahtkorrosion entwickelt. Dieser neue Ansatz wird als multichannel zero resistance
ammetry (vielkanal-null-Innenwiderstands-Strommessung) bezeichnet. Das entwickelte
Messverfahren gestattet es, dass ERW-Rohrmaterial auf natürliche, unbeeinflusste Weise in
interschiedlichen CO2-hältigen Medien in einem Autoklaven mit Rührwerk frei korrodieren
kann. Allerdings werden die galvanischen Kopplungsströme zwischen den Zonen
unterschiedlicher Mikrostruktur der ERW-Schweißnaht gleichzeitig mitgemessen. Diese
Vorgehensweise hat es erlaubt, unmittelbar jene Zonen (und damit jene Rohrmaterialien) zu
identifizieren, die empfindlich gegenüber selektiver CO2-Schweißnahtkorrosion sind. Im
Rasterelektronenmikroskop konnte die Empfindlichkeit für selektive Korrosion mit der
Morphologie der Schichten aus Korrosionsprodukten im Bereich der Schweißnaht korreliert
werden, was wiederum von der Morphologie des Zementits im Stahl abhängig ist. Basierend
auf diesen Befunden wurde ein Modell entwickelt, das erklärt wie ERW-Schweißnähte
korrodieren und warum manches ERW-Rohrmaterial empfindlicher gegenüber selektiver
CO2-Schweißnahtkorrosion ist als anderes, obwohl sie der gleichen Werkstoffspezifikation
entsprechen.
Die aus diesen Experimenten gewonnenen Daten geben öl- und gasfördernden
Unternehmen Anhaltspunkte für die Materialwahl zur Vermeidung von selektiver ERW-
Schweißnahtkorrosion in CO2-hältigen Medien. Die entwickelte Prüftechnologie hat auch das
Potential für Feldanwendung, wo die Effekte von Änderungen der Betriebsbedingungen (z.B.
Inhibitorkonzentration, pH, Strömungsgeschwindigkeit) auf das Korrosionsverhalten von
Schweißnähten unmittelbar verfolgt werden kann.
Im Grunde können die Ergebnisse dieser Dissertation als Richtlinie zur Verbesserung
der Integrität und Zuverlässigkeit der Anlagen verwendet werden.
Table of Contents
List of Figures i
List of Tables x
Nomenclature xi
Chapter 1 Introduction 1
1.1 Background 1
1.2 Hypothesis of dissertation 2
Chapter 2 Literature review 3

2.1 Fundamentals of CO2 corrosion 3
2.1.1 The carbon dioxide system 3
2.1.2 Siderite (FeCO3) precipitation 4
2.2 Preferential weld corrosion in CO2 environments 7
2.2.1 Effect of nickel and copper 8
2.2.2 Autogenous and matched filler welds 10
2.2.3 Influence of weld preheat 11
2.2.4 Effect of microstructure 11
2.3 Electric resistance welding (ERW) of linepipe 12
Chapter 3 Experimental methodology for investigating CO2

preferential weld corrosion 14
3.1 Introduction 14
3.2 Galvanic corrosion 15
3.2.1 Fundamentals of galvanic corrosion 15
3.2.2 Relevance to ERW linepipe 16
3.2.3 Zero resistance ammetry (ZRA) 16
3.2.3.1 Multi-channel zero resistance ammetry design 17
3.3 Experimental setup 19
3.3.1 Electrode design 19
3.3.2 Stirring autoclave 20
3.3.2.1 Operating procedure 20
3.3.3 Data evaluation 21
3.3.3.1 Average galvanic current density (AGCD) 21
3.4 Investigated materials 21
3.4.1.1 X42 linepipes 22
3.4.1.2 X52 linepipes 22
3.4.1.3 OCTG materials 22
3.4.2 Chemical analysis 23
3.4.3 Metallographic analysis 23
3.4.3.1 X42 linepipe 28
3.4.3.2 X52 linepipe 36
3.4.3.3 Oil Country Tubular Goods (OCTGs) 44
Chapter 4 Effect of ERW X42 linepipe microstructure on CO2

4.1 Introduction 49
4.2 Experimental methodology 49
4.2.1 Investigated materials 49
4.2.2 Multi-channel zero resistance ammetry 50
4.2.3 Experimental procedure 50
4.3 Results and discussion 52
4.3.1 Multi-channel zero resistance ammetry (ZRA) 52
4.3.1.1 The time dependence of galvanic interactions leading to PWC 52
4.3.1.2 Average galvanic current density (AGCD168hrs) 57
4.3.1.2.1 1 bar CO2 57
4.3.1.2.2 10 bar CO2 58
4.3.1.2.3 Mesa attack 59
4.3.1.2.4 Galvanic passivation 59
4.3.1.2.5 Coupling ferritic pearlitic linepipe to quenched
and tempered 61
4.3.2 Scanning electron microscopy (SEM) 65
4.3.2.1 X42-A and X42-B 65
4.3.2.1 X42-C 67
4.3.2.2 X42-S 67
4.3.2.3 Galvanic Passivation 81
4.3.2.3.1 X42-A 81
4.3.2.3.2 X42-B 81
4.3.2.3.3 X42-C 82
4.3.2.3.4 X42-S 82
4.3.2.4 Comparison with coupon tests 91
4.3.2.5 Location of siderite precipitation 92
4.3.2.5.1 Macro and micro-galvanic couples 92
4.3.2.5.2 Electro-migration of chlorides 93
4.3.2.5.3 Influencing factors in siderite precipitation 95
4.3.3 Effect of surface area and response to pressure changes 97
4.3.3.1 X42-A 97
4.3.3.2 X42-B 98
4.3.4 Effect of microstructure on preferential weld corrosion 102
4.3.4.1 Microstructural zones susceptible to PWC 102
4.3.4.1.1 Localized absence of pearlite banding 103
4.3.4.1.2 Localized regions of low temperature transformation
microstructures in a ferritic-pearlitic linepipe 103
4.3.4.1.3 Coupling ferritic pearlitic and quenched and tempered
linepipes 104
4.3.4.2 The effect of temperature 104
4.3.4.3 Avoiding localized CO2 corrosion in ERW linepipe 105
4.4 Conclusions 107
Chapter 5 Effect of normalization heat treatments and flow velocity on

CO2 preferential weld corrosion 108
5.1 Introduction 108
5.3.1.1 As-welded linepipe 111
5.3.1.2 Heat treated linepipe 111
5.3.1.3 Effect of flow velocity 117
5.3.1.3.1 Relationship to grain size 118
5.4 Conclusions 119
Chapter 6 Effect of quenched and tempered heat treatment on CO2

6.3.1 Normalized heat treatment (J55-A) 125
6.3.2 Quenched and tempered heat treatment (L80-A) 126
6.4 Conclusions 129
Chapter 7 Effect of acetic acid on CO2 preferential weld corrosion 130

7.3.1 X42 linepipes 132
7.3.1.1 X42-A 133
7.3.1.2 X42-B 134
7.3.1.3 X42-C 135
7.3.1.4 X42-S 138
7.3.2 X-52 linepipe 142
7.3.2.1 X52-AW 142
7.3.2.2 X52-SH 145
7.3.2.3 X52-450 145
7.3.2.4 X52-650 146
7.3.3 OCTGs 147
7.3.3.1 J55-A 148
7.3.3.2 L80-A 148
7.4 Conclusions 149
Chapter 8 Corrosion inhibitors and CO2 preferential weld corrosion 151

8.3.1 Effect of inhibitor on ERW X42 linepipe PWC 153
8.3.1.1 Multi-channel zero resistance ammetry 153
8.3.1.2 Scanning electron microscopy (SEM) 153
8.3.2 Effect of corrosion inhibitor on ERW OCTGs 154
8.4 Conclusions 162
Chapter 9 Conclusions and recommendations for avoiding CO2

preferential weld corrosion in ERW linepipes and OCTGs 163
9.1 A new methodology for assessing CO2 preferential weld
corrosion susceptibility 163
9.2 Mechanism of CO2 preferential weld corrosion in ERW linepipe 164
9.3 Correlation with base metal (strip material) microstructure and
chemical composition 165
9.3.1 Ferritic pearlitic ERW linepipes 165
9.3.2 Ferritic bainitic ERW linepipes 166
9.3.3 Quenched and tempered ERW OCTGs 166
9.4 Avoiding CO2 preferential weld corrosion in ERW linepipe 167
9.5 Conclusion 167
References 170
Curriculum Vitae 173

List of Figures
Figure 2.1: Effect of pCO2 and temperature on pH for 3% NaCl solution. ..................... 5
Figure 2.2: Effect of temperature and salinity on siderite solubility for various NaCl
concentrations17. ..................................................................................................................... 6
Figure 2.3: Effect of temperature, pCO2, and pH on siderite precipitation in 3% NaCl

solution. Vertical axis shows Fe2+ concentration required to reach siderite saturation. .......... 7
Figure 2.4: Effect of solution conductivity (NaCl concentration) on preferential weld

corrosion of GTAW and SMAW welds made using a 1% Ni filler material4. ......................... 10
Figure 2.5: Illustration of the high frequency ERW welding process used to make
longitudinally welded linepipe. .............................................................................................. 13
Figure 3.1: Common ZRA setup that fails to capture galvanic effects between the
CGHAZ and the FGHAZ as they are on the same electrode ................................................ 15
Figure 3.2: Example circuitry for multi-channel ZRA, allowing the measurement of
galvanic coupling currents between the different microstructural zones present in the welded
linepipes/OCTGs. .................................................................................................................. 18
Figure 3.3: A polished weld cross section showing the location of different
microstructural zones (left), and the corresponding five-segment ZRA electrode (‘hockey
puck’). Each electrode corresponds to a different microstructural zone present in the ERW
linepipe. The BM electrode was taken 180º from the weld. WM refers to the weld centreline,
where the two faying surfaces of the strip material meet. ..................................................... 20
Figure 3.4: Experimental setup, showing stirring autoclave, multi-channel ZRA

circuitry, temperature control unit, and data recorder. .......................................................... 21
Figure 3.5: Optical micrographs of X42-A microstructural zones. Etched 3% Nital,

500X...................................................................................................................................... 28
Figure 3.6: SEM SE micrographs of X42-A microstructural zones. Etched 3% Nital. . 29
Figure 3.7: Optical micrographs of X42-B. Etched 3% Nital, 500X. ............................. 30
Figure 3.8: SEM SE pictures of X42-B microstructural zones. Etched 3% Nital. ......... 31
i
Figure 3.9: Optical micrographs of X42-C microstructural zones. Etched 3% Nital,
500X...................................................................................................................................... 32
Figure 3.10: SEM SE micrographs of X42-C microstructural zones. Etched 3% Nital,

500X...................................................................................................................................... 33
Figure 3.11: EDX element mapping of X42-C weld centreline showing Mn, Si, O rich
inclusions. ............................................................................................................................. 34
Figure 3.12: Optical micrograph of nominal seamless X42-S microstructure used for
ZRA electrodes E1, E2, E3, E4, and E5. Etched 3% Nital, 500X. ........................................ 35
Figure 3.13: SEM SE micrograph of nominal seamless X42-S microstructure used for
ZRA electrodes E1, E2, E3, E4, and E5. .............................................................................. 35
Figure 3.14: Optical micrographs of X52-AW microstructural zones. Etched 3% Nital,

500X...................................................................................................................................... 36
Figure 3.15: SEM SE micrographs of X52-AW microstructural zones. Etched 3% Nital.

.............................................................................................................................................. 37
Figure 3.16: Optical micrographs of X52-SH microstructural zones. Etched 3% Nital,

500X...................................................................................................................................... 38
Figure 3.17: SEM SE micrographs of X52-SH microstructural zones. Etched 3% Nital.

.............................................................................................................................................. 39
Figure 3.18: Optical micrographs of X52-450 microstructural zones. Etched 3% Nital,

500X...................................................................................................................................... 40
Figure 3.19: SEM SE micrographs of X52-450 microstructural zones. Etched 3% Nital.

.............................................................................................................................................. 41
Figure 3.20: Optical micrographs of X52-650 microstructural zones. Etched 3% Nital,

500X...................................................................................................................................... 42

.............................................................................................................................................. 43
Figure 3.22: Optical micrographs of L80-A microstructural zones. Etched 3% Nital,

500X...................................................................................................................................... 44
Figure 3.23: SEM SE micrographs of L80-A microstructural zones. Etched 3% Nital. 45
Figure 3.24: Optical micrographs of J55-A microstructural zones. Etched 3% Nital,

500X...................................................................................................................................... 46
Figure 3.25: SEM SE micrographs of J55-A microstructural zones. Etched 3% Nital. 47
ii
Figure 3.26: Optical micrograph of nominal seamless L80-S microstructure. Etched 3%
Nital, 500X. ........................................................................................................................... 48
Figure 3.27: SEM SE micrographs of nominal seamless L80-S microstructure. ......... 48
Figure 4.1: Relative flow direction inside stirring autoclave. ........................................ 51
Figure 4.2: ZRA curves for 1 bar CO2, 90 ºC, showing how some microstructural zones
in ERW linepipe (X42-A, X42-B) develop strong galvanic couples during the corrosion
process. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive
values are anodic. ................................................................................................................. 54
Figure 4.3: Average galvanic current densities over 168 hours (AGCD168hrs) for X42
ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe. Conditions: 1 bar CO2, 3%
NaCl, 150 RPM (approx. 0.5 m/s), surface area ratios 1:1. Positive values are anodic. ...... 55
ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe. Conditions: 10 bar CO2, 3%
NaCl, 150 RPM (approx. 0.5 m/s), surface area ratios 1:1. Positive values are anodic. ...... 56
Figure 4.5: ZRA curves showing galvanic density for X42-A HAZ 2 and X42-B HAZ 3
for all test conditions. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Positive values are
anodic. .................................................................................................................................. 57
Figure 4.6: ZRA curves for 10 bar CO2, 60 ºC, showing galvanic current densities for
ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe. Electrolyte 3% NaCl, 150 RPM
(approx. 0.5 m/s). Surface area ratio 1:1. Positive values are anodic. ................................. 62
Figure 4.7: Current density curves for 10 bar CO2, 90 ºC, showing galvanic passivation
for X42-A, X42-B, and X42-S. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface
area ratio 1:1. Positive values are anodic. ............................................................................ 63
Figure 4.8: Etched cross section (3% Nital) of girth weld joining a quenched and
tempered linepipe to a normalized ferritic pearlitic linepipe. ................................................. 64
Figure 4.9: ZRA curves for 1 bar CO2, 60 ºC for X42-B (left), and the coupling of
normalized ferritic pearlitic seamless linepipe (X42-S) to a quenched and tempered
seamless linepipe (L80-S) (right). Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface
area ratio 1:1. Positive values are anodic. ............................................................................ 64
Figure 4.10: SEM BSD cross sections of X42-B, for 1 bar CO2, 90 ºC showing different
corrosion product layers forming on each microstructural zone. HAZ 2, HAZ 3, BM were
dominant anodes. ................................................................................................................. 69
iii
Figure 4.11: SEM BSD cross sections of X42-S for 1 bar CO2, 90 ºC showing all
seamless electrodes having similar corrosion product layers which resulted in no localized
attack. ................................................................................................................................... 70
Figure 4.12: SEM BSD cross sections of X42-A for 10 bar CO2, 60 ºC showing different
corrosion product layers forming on each microstructural zone. HAZ 2 was dominant anode.
.............................................................................................................................................. 71
Figure 4.13: EDX element mapping of X42-A for 10 bar CO2, 60 ºC, showing chloride
concentrations (bright colour) in corrosion product layers. ................................................... 72
Figure 4.14: SEM BSD cross sections of X42-B for 10 bar CO2, 60 ºC, showing
different corrosion product layers formed on each microstructural zone. HAZ 3 was the
dominant anode. ................................................................................................................... 73
Figure 4.15: EDX element mapping of X42-B for 10 bar CO2, 60 ºC, showing chloride
Figure 4.16: SEM BSD image of X42-B WM, showing siderite (bright area)
precipitating on cementite (remnants of pearlite banding) for 1 bar CO2, 90 ºC. Electrolyte
3% NaCl, 150 RPM (approx. 0.5 m/s). .................................................................................. 75
Figure 4.17: SEM BSD image of X42-B HAZ 3, showing siderite (bright area)
precipitating on cementite (dark area) for 1 bar CO2, 90 ºC. Image also shows the remnants
Al, Mn, Ca, S rich inclusion. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). ................... 75
Figure 4.18: SEM BSD cross sections of X42-B for 1 bar CO2, 60 ºC, showing different
corrosion product layers formed on each microstructural zone. HAZ 2 and HAZ 3 were
dominant anodes. ................................................................................................................. 76
Figure 4.19: SEM BSD cross sections of X42-C for 10 bar CO2, 60 ºC, showing
different corrosion product layers formed on each microstructural zone. ............................. 77
Figure 4.20: EDX element mapping of X42-C for 10 bar CO2, 60 ºC, showing chloride
Figure 4.21: SEM BSD cross sections of seamless X42-S for 10 bar CO2, 60 ºC,
showing corrosion product layers formed on each electrode of nominally identical
microstructure. ...................................................................................................................... 79
Figure 4.22: EDX element mapping of X42-S for 10 bar CO2, 60 ºC, showing chloride
Figure 4.23: SEM BSD cross sections of X42-A for 10 bar CO2, 90 ºC, showing
corrosion product layers after galvanic passivation had occurred. ....................................... 83
iv
Figure 4.24: SEM BSD cross sections of X42-B for 10 bar CO2, 90 ºC, showing
Figure 4.25: SEM BSD cross sections of X42-C for 10 bar CO2, 90 ºC, showing
corrosion product layers. ....................................................................................................... 85
Figure 4.26: SEM BSD cross sections of X42-S for 10 bar CO2, 90 ºC, showing
Figure 4.27: Photomicrograph of X42-B coupon after 168 hours at 10 bar CO2, 90 ºC.
Red line indicates cross section location. Cross section insert etched in 3% Nital, revealing
localized attack of HAZ 3. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). ...................... 87
Figure 4.28: Optical micrograph of X42-B coupon after 168 hours at 10 bar CO2, 90 ºC,
showing localized attack at HAZ 3. Etched 3% Nital. Electrolyte 3% NaCl, 150 RPM (0.5
m/s). ...................................................................................................................................... 88
Figure 4.29: SEM BSD images of corrosion product layers formed on the X42-B
coupon at 10 bar CO2, 90 ºC after 168 hours in as-polished condition (top), and optical
micrograph etched in 3% Nital (bottom). Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). 89
Figure 4.30: EDX element mapping of X42-B coupon for 10 bar CO2, 90 ºC, showing
chlorine, oxygen, and iron concentrations (bright colours). .................................................. 90
Figure 4.31: Cross section of the multi-channel “hockey puck” style five-segment ZRA
electrode shown in Figure 3.3, illustrating macro-galvanic couples between different
microstructural zones (black arrows, electron current), and micro-galvanic couples between
each microstructural zone and its corrosion product layer (blue arrows, electron current)
couples.................................................................................................................................. 93
Figure 4.32: Chloride ions from the bulk solution attracted by the accumulation of Fe2+
ions at the steel/cementite interface. .................................................................................... 96
Figure 4.33: Acidification at the steel/cementite interface from the production of

hydrochloric acid, and alkalinisation at the bulk solution/cementite interface from bicarbonate
production. ............................................................................................................................ 96
Figure 4.34: The combined effects of Fe2+ accumulation, chloride migration (internal
acidification), and bicarbonate production on the siderite saturation factor. ......................... 97
Figure 4.35: X42-A ZRA curves for 1 bar CO2, 60 ºC showing effect of BM surface
area and response to an increase pCO2 from 1 bar to 2 bar. ............................................. 100
Figure 4.36: X42-B ZRA curves for 1 bar CO2, 60 ºC showing effect of BM surface
area and response to an increase pCO2 from 1 bar to 2 bar. ............................................. 101
v
Figure 5.1: SEM SE image of X52-AW base metal (BM 2), 180º from the weld
centreline. Rough grains are granular bainite (GB), smooth grains are polygonal ferrite (PF),
grain boundaries mostly MA constituent. Etched 3% Nital. ................................................ 109
Figure 5.2: Average galvanic current densities (AGCD168hrs) for X52 ERW linepipe with
different heat treatments, and a comparison to X42-C and seamless X42-S. Conditions: 1
bar CO2, 3% NaCl, 150 RPM, area ratios 1:1. Positive values are anodic. Note: AGCD128hrs
values shown for 1 bar CO2, 60 ºC. .................................................................................... 113
Figure 5.3: Average galvanic current densities over 168 hours (AGCD168hr) for X52
ERW linepipe with different heat treatments, and a comparison to X42-C and seamless X42-
S. Conditions: 10 bar CO2, 60 ºC, 3% NaCl, 150 RPM, area ratios 1:1. Positive values are
anodic. ................................................................................................................................ 114
Figure 5.4: SEM BSD cross sections of X52-AW, for 1 bar CO2, 90 ºC, 150 RPM
showing different corrosion product layers forming on each microstructural zone. Base
electrolyte 3% NaCl. ........................................................................................................... 115
Figure 5.5: SEM BSD cross sections of X52-650, for 1 bar CO2, 90 ºC, 150 RPM
showing different corrosion product layers forming on each microstructural zone. Base
electrolyte 3% NaCl. ........................................................................................................... 116
Figure 5.6: ZRA curves showing the effect of flow velocity on galvanic interactions for
X52 ERW linepipe in the as-welded (X52-AW) and seam heat treated with 650 ºC full body
stress relief (X52-650) condition. Experimental conditions: 1 bar CO2, 90 ºC, 3% NaCl, area
ratios 1:1. Positive values are anodic. ................................................................................ 120
Figure 5.7: SEM BSD cross sections of X52-AW, for 1 bar CO2, 90 ºC, 0 RPM showing
different corrosion product layers forming on each microstructural zone............................ 121
Figure 5.8: SEM BSD cross sections of X52-650, for 1 bar CO2, 90 ºC, 0 RPM showing
different corrosion product layers forming on each microstructural zone............................ 122
Figure 6.1: Average galvanic current densities over 168 hours (AGCD168hrs) for
normalized (J55-A) and quenched and tempered (L80-A) ERW OCTGs. Conditions: 3%
NaCl, 150 RPM (approx. 0.5 m/s), surface area ratios 1:1. Positive values are anodic. .... 127
Figure 6.2: Current density curves for 10 bar CO2, 90 ºC, showing galvanic passivation
of ERW OCTG microstructural zones as corrosion product layers form. Experimental ID 10-
90-C. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive
values are anodic. ............................................................................................................... 128
vi
Figure 6.3: Current density curves for the repeated 10 bar CO2, 90 ºC experiment,
showing that the anodic microstructural zones for the quenched and tempered OCTG (L80-
A) are selected at random, similar to a seamless linepipe. Experimental ID 10-90-D.
Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive values are
anodic. ................................................................................................................................ 128
Figure 7.1: X42-A ZRA current density curves showing the effect of 60 ppm HAc on
galvanic interactions for 1 bar CO2, 60 ºC. Electrolyte 3% NaCl, 150 RPM, area ratios 1:1.
Positive values are anodic. ................................................................................................. 133
Figure 7.2: EDX element mapping showing chlorides (bright colour) for X42-A HAZ 2
corrosion product layer, for 1 bar CO2, 60 ºC, with and without 60 ppm HAc. .................... 134
Figure 7.3: X42-B current density curves showing the effect of various acetic acid
(HAc) additions on galvanic interactions for 1 bar CO2, 60 ºC. Electrolyte 3% NaCl, 150
RPM, area ratios 1:1. Positive values are anodic. .............................................................. 136
Figure 7.4: SEM BSD images of X42-B HAZ 3 corrosion product layer at 1 bar CO2,
60 ºC. The addition of 60 ppm (60 ppm) HAc to the initial electrolyte caused the corrosion
product layer to become more broken. ............................................................................... 137
Figure 7.5: Corrosion potential of samples for 1 bar CO2, 60 ºC with HAc injections at
0, 71, and 143 hours. Experiment ID: 1-60-H. Electrolyte 3% NaCl, 150 RPM, area ratios
1:1. ...................................................................................................................................... 137
Figure 7.6: X42-C current density curves showing the effect of 60 ppm HAc on
galvanic interactions for 1 bar CO2, 60 ºC. Electrolyte 3% NaCl, 150 RPM, area ratios 1:1.
Figure 7.7: Seamless X42-S current density curves showing the effect of 60 ppm HAc
on galvanic interactions for 1 bar CO2, 60 ºC. Electrolyte 3% NaCl, 150 RPM, area ratios 1:1.
ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe, showing effect of 60 ppm HAc.
Conditions: 1 bar CO2, 60 ºC, 3% NaCl, 150 RPM, area ratios 1:1. Positive values are
anodic. ................................................................................................................................ 140
ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe, showing effect of 60 ppm HAc.
Conditions: 10 bar CO2, 60 ºC, 3% NaCl, 150 RPM, area ratios 1:1. Positive values are
anodic. ................................................................................................................................ 141
vii
Figure 7.10: ZRA curves for X52-AW showing the effect of acetic acid (HAc) and flow
rate on the susceptibility of the WM to localized attack. Test condition 1 bar CO2, 60 ºC, 3%
NaCl. Positive values are anodic. ....................................................................................... 144
Figure 7.11: ZRA curves for X52-SH showing the effect of acetic acid (HAc) and flow
rate on galvanic interactions. Test condition 1 bar CO2, 60 ºC, 3% NaCl. Positive values are
anodic. ................................................................................................................................ 145
Figure 7.12: ZRA curves for X52-450 showing the effect of acetic acid (HAc) and flow
anodic. ................................................................................................................................ 146
Figure 7.13: ZRA curves for X52-650 showing the effect of acetic acid (HAc) and flow
anodic. ................................................................................................................................ 147
Figure 7.14: ZRA curves for J55-A showing the effect of acetic acid (HAc) and flow
rate on galvanic interactions. Test condition 1 bar CO2, 60 ºC, 3% NaCl, 150 RPM (approx.
0.5 m/s). Positive values are anodic. .................................................................................. 148
Figure 7.15: ZRA curves for L80-A showing the effect of acetic acid (HAc) and flow
rate on galvanic interactions. Test condition 1 bar CO2, 60 ºC, 3% NaCl, 150 RPM (approx.
0.5 m/s). Positive values are anodic. .................................................................................. 149
ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe, showing effect of 500 ppm
CRW85579 corrosion inhibitor. Conditions: 10 bar CO2, 60 ºC, 3% NaCl, 150 RPM (approx.
0.5 m/s), surface area ratios 1:1. Positive values are anodic. ............................................ 155
Figure 8.2: Average galvanic current densities over 168 hours (AGCD168hrs) for ERW
OCTGs, showing effect of 500 ppm CRW85579 corrosion inhibitor. Conditions: 10 bar CO2,
60 ºC, 3% NaCl, 150 RPM (approx. 0.5 m/s), surface area ratios 1:1. Positive values are
anodic. ................................................................................................................................ 156
Figure 8.3: Current density curves for 10 bar CO2, 60 ºC, with 500 ppm CRW85579
corrosion inhibitor, showing galvanic interactions between different microstructural zones
present in ERW linepipe (X42-A, X42-B, X42-C) compared to a seamless linepipe (X42-S)
linepipe. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive
values are anodic. Experiment ID CRW-A. ......................................................................... 157
Figure 8.4: Current density curves for 10 bar CO2, 60 ºC, showing galvanic interactions
between different microstructural zones present in ERW linepipe (X42-A, X42-B, X42-C)
viii
compared to a seamless linepipe (X42-S) linepipe. Electrolyte 3% NaCl, 150 RPM (approx.
0.5 m/s). Surface area ratio 1:1. Positive values are anodic. Experiment ID 10-60-A. ....... 158
Figure 8.5: SEM BSD cross sections of X42-B for uninhibited 10 bar CO2, 60 ºC,
showing different corrosion product layers formed on each microstructural zone. HAZ 3 was
the dominant anode. ........................................................................................................... 159
Figure 8.6: SEM BSD cross sections of X42-B, for 10 bar CO2, 60 ºC, with the addition
of 500 ppm CRW85579 corrosion inhibitor, showing the absence of any significant corrosion
product layers. .................................................................................................................... 160
Figure 8.7: Current density curves for 10 bar CO2, 60 ºC, with 500 ppm CRW85579
corrosion inhibitor, showing galvanic interactions between different microstructural zones
present in ERW OCTGs. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area
ratio 1:1. Positive values are anodic. Experiment ID CRW-B. ............................................ 161
Figure 8.8: Current density curves for 10 bar CO2, 60 ºC, showing galvanic interactions
between different microstructural zones present in ERW OCTGs. Electrolyte 3% NaCl, 150
RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive values are anodic. Experiment ID 10-
60-C. ................................................................................................................................... 161
Figure 9.1: Susceptibility of various linepipes/OCTGs to CO2 preferential weld

corrosion. Plot shows the effect of pCO2 and temperature on the galvanic corrosion rates
measured for weld seam and heat affected zone microstructures (AGCD168hrs values). Base
electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). .............................................................. 169
ix
List of Tables
Table 2.1: Relevant equation values for (2.5)5, 10. .......................................................... 4
Table 2.2: Dissociation constants for the carbonic acid system in 3% NaCl8. ............... 4
Table 2.3: Base metal composition of linepipe investigated by Joosten, et al.26 and
Alawadhi and Robinson39. ..................................................................................................... 10
Table 2.4: Weld metal root composition of linepipe investigated by Joosten, et al.26 and
Alawadhi and Robinson39. ..................................................................................................... 10
Table 3.1: Heat treatment and welding information of investigated materials. ............ 23
Table 3.2: Chemical composition (wt%) of investigated steel linepipes/OCTGs,

measured using optical emission spectroscopy. Remainder concentration is iron (Fe). ...... 23
Table 3.3: Description of X42 linepipe microstructural zones / ZRA electrodes. ......... 24
Table 3.4: Description of X52 linepipe microstructural zones / ZRA electrodes. ......... 25
Table 3.5: Description of OCTG microstructural zones / ZRA electrodes. .................. 27
Table 4.1: Experimental test matrix with pH and Fe2+ measurements. Electrolyte 3%
NaCl, purged with CO2 for 2 hours, 150 RPM (approx. 0.5 m/s). ......................................... 51
Table 4.2: Chemical composition (wt%) of flowlines from CO2 containing oil field. ..... 64
NaCl, purged with CO2 for 2 hours, 150 RPM (approx. 0.5 m/s). ....................................... 110
NaCl, purged with CO2 for 2 hours, 150 RPM (approx. 0.5 m/s). ....................................... 125
Table 7.1: Investigated materials with corresponding experimental ID and HAc

concentration information. ................................................................................................... 131
Table 7.2: Experimental test conditions. .................................................................... 132
Table 8.1: Investigated materials for inhibitor experiments. ...................................... 152
Table 8.2: Experimental test matrix. All experiments performed at 10 bar CO2, 60 ºC.
Electrolyte 3% NaCl, purged with CO2 for 2 hours, 150 RPM (approx. 0.5 m/s). Corrosion
inhibitor injected at start of experiment after CO2 purging. ................................................. 152
x
Nomenclature
AGCD Average Galvanic Current Density

BM Base Metal
CGHAZ Coarse Grain Heat Affected Zone
Ecorr Corrosion Potential
EDX Energy Dispersive X-Ray
EIS Electrochemical Impedance Spectroscopy
ERW Electric Resistance Welding
FCAW Flux Cored Arc Welding
FGHAZ Fine Grain Heat Affected Zone
GTAW Gas Tungsten Arc Welding
HAc Acetic acid
HAZ Heat Affected Zone
MA Martensite Austenite
OCTG Oil Country Tubular Goods
PWC Preferential Weld Corrosion
SAW Submerged Arc Welding
SEM Scanning Electron Microscopy
SMAW Shielded Metal Arc Welding
WM Weld Metal
ZRA Zero Resistance Ammetry
xi
Chapter 1 Introduction
1.1 Background
The presence of dissolved carbon dioxide in production fluids poses a serious risk to
oil and gas asset integrity. Literature suggests approximately 46% of material failures in oil
and gas are related to CO2 or preferential weld corrosion (PWC)1-3.
Within oil and gas companies, the performance of longitudinally welded linepipe
relative to seamless linepipe is always a topic of discussion. Longitudinally welded linepipes
are preferred from a project management point of view, as they have lower costs and shorter
lead times over seamless. However, the introduction of a longitudinal weld seam is an
inhomogeneity that can be susceptible to CO2 preferential weld corrosion (PWC). While
NACE MR0175/ISO 15156 can be used to assess the suitability of longitudinally welded
linepipe for sour service applications (H2S environments), no equivalent standard exists for
CO2 containing environments. The suitability of longitudinally welded linepipe, along with
material grade and heat treatment, is therefore left to the experience of the oil and gas
company.
Furthermore, the construction of a pipeline often uses longitudinally welded linepipe

from several different manufacturers. While these linepipes are all of the same material
grade (i.e. API grade X42), with similar mechanical test values, many oil and gas companies
have experienced that the longitudinal weld from certain manufacturers can be more
susceptible to preferential weld corrosion than others. The reason for this is unclear, and the
development of a laboratory test method to identify this susceptibility before the procurement
stage would be extremely valuable.
Traditionally, longitudinally welded linepipes are known to be more susceptible to

localized CO2 corrosion than seamless linepipes due to chemical composition gradients
between the weld and base metal. A large investigation of several welding procedures and
their susceptibility to localized CO2 corrosion was performed by Lee and Woollin4. The
findings showed that welds made using matched fillers, or autogenous welding processes
(i.e. no filler material) provided the best resistance to PWC in CO2 environments.
Modern longitudinally welded linepipes are fabricated by electric resistance welding

(ERW), which is an autogenous process that eliminates chemical composition gradients and
therefore should be resistant to PWC. Despite using this process, some ERW linepipes still
appear susceptible to preferential weld corrosion in CO2 environments, while others do not.
1
1.2 Hypothesis of dissertation
Austrian oil and gas company OMV has experienced PWC in longitudinally ERW
welded X42 linepipe operating in saline CO2 production environments. The reason for this is
unclear, as often other linepipes of the same material grade but different manufacturer,
operating in identical environments, seem immune to this form of localized attack.
The author is not aware of any study that has used a thorough microstructural analysis
as the basis for studying galvanic coupling currents in ERW welds. This thesis poses the
hypothesis that ERW weld and heat affected zone microstructure play a role in CO2
preferential weld corrosion. The effect of microstructure on localized attack should be visible
in electrochemical quantities, in particular galvanic coupling currents.
2
Chapter 2 Literature review
2.1 Fundamentals of CO2 corrosion
2.1.1 The carbon dioxide system
When carbon dioxide is in contact with water, a complex two-step equilibrium takes
place resulting in an overall acidification of the fluid. Depending on temperature and salinity,
a percentage of the CO2 gas will dissolve into the liquid (2.1)5, 6. Some of this dissolved CO2
will then react with water to form carbonic acid (H2CO3) (2.2), which then dissociates into
- 2-
bicarbonate (HCO3 ) (2.3) and then carbonate (CO3 ) (2.4)7, 8. Each dissociation step
produces H+ ions, lowering solution pH.
The amount of dissolved CO2 (in mol/l) is a function of pCO2, temperature, and salinity,
and can be calculated by (2.5)6 using the values shown in Table 2.1. The equilibrium
between carbonic acid, bicarbonate, and carbonate, depends on the dissociation constants
K1 (2.6) and K2 (2.7). K1 and K2 also depend on temperature and salinity; values are shown
in Table 2.2. From these values, it is possible to calculate the pH of a solution as a function
of temperature and pCO2. Figure 2.1 shows pH – pCO2 curves for a 3% NaCl solution at 30,
60, and 90 ⁰C. The values are in agreement with those presented by Dugstad9 for similar
conditions.
CO2(g) ⟷ CO2(l) (2.1)

CO2(l) + H2 O(l) ⟷ H2 CO3(l) (2.2)
+ -
H2 CO3 ⟷ H + HCO3 (2.3)
- + 2-
HCO3 ⟷H + CO3 (2.4)
pCO2
[CO2 ] = c (2.5)
H
+ -
[H ][HCO3 ]
K1 = (2.6)
[H2 CO3 ]
2-
[H+ ][CO3 ]
K2 = - (2.7)
[HCO3 ]
3
Table 2.1: Relevant equation values for (2.5)5, 10.
Temperature H, Henry’s Constant for 3% NaCl c, Water Molar Density
⁰C (MPa) (mol/l)
30 229 55.2
60 403 54.5
90 622 53.6
Table 2.2: Dissociation constants for the carbonic acid system in 3% NaCl8.
Temperature K1 K2
⁰C
30 1.1242 x 10-6 3.0083 x 10-10
60 1.3537 x 10-6 4.6592 x 10-10
90 1.3055 x 10-6 5.8363 x 10-10
2.1.2 Siderite (FeCO3) precipitation
The anodic dissolution of iron produces Fe2+ ions and electrons by Equation (2.8)9, 11,
12. The liberated electrons then participate in the cathodic reaction, typically either by
reducing H+ ions by (2.9), or the direct reduction of carbonic acid by (2.10)9, 11, 13-15. In acidic
solutions (pH < 4) H+ concentration is high, and hydrogen evolution (2.12) is the dominant
cathodic reaction. However, as pH increases to intermediate values (4 < pH < 6), the
reduction of carbonic acid becomes dominant. Therefore the presence of carbonic acid
accelerates corrosion by not only acting as a source of H+ ions by (2.3) and (2.4), but also by
being directly reducible (2.10). This is often used to explain why CO2 brines are more
corrosive than a brine of the same pH with a fully dissociated acid (strong acid)14, 16. As the
reduction of carbonic acid produces bicarbonate (2.10), the total corrosion process produces
alkalinity (2.11)9.
Siderite (FeCO3) will precipitate by (2.12) when the fluid becomes locally saturated,
that is, when the concentration product [Fe2+][CO3-] exceeds the solubility product, Ksp (2.13).
Several authors have investigated the effect of ionic strength (salinity) and temperature on
Ksp17-20, and a unified equation was proposed by Sun, et al.17 (2.14), where Tk is temperature
in K, and I is ionic strength in mol/L. Equation (2.14) is plotted as a function of temperature
and salinity in Figure 2.2, showing how siderite precipitation is more difficult at lower
temperatures and higher salinity levels. From these expressions, the Fe2+ concentration
required for a solution to become saturated and precipitate siderite can be calculated as a
function of pH, temperature, salinity, and pCO2, as shown by Figure 2.3.
4
Fe → Fe2+ +2e- (2.8)
2H+ + 2e- → H2 (2.9)

-
2H2 CO3 + 2e- → H2 + 2HCO3 (2.10)
-
Fe + 2H2 CO3 → Fe2+ + 2HCO3 + H2 (2.11)
2-
Fe2+ + CO3 → FeCO3 (2.12)
2-
[CO3 ] Fe2+ > Ksp (2.13)
2.1963 0.5
log(Ksp )= -59.3498-0.041377(Tk ) - + 24.5724log(Tk ) + 2.518 I - 0.657(I) (2.14)
Tk
30 °C
5.0
60 °C
90 °C
4.5
pH
4.0
3.5
3.0
0 1 2 3 4 5 6 7 8 9 10 11 12
pCO2 (bar)
Figure 2.1: Effect of pCO2 and temperature on pH for 3% NaCl solution.
5
1E-9
Siderite Solubility, Ksp (mol2/L2)
1E-10
1E-11
3% NaCl
2% NaCl
1% NaCl
0% NaCl
1E-12
20 30 40 50 60 70 80 90
Temperature (⁰C)
Figure 2.2: Effect of temperature and salinity on siderite solubility for various NaCl concentrations17.
6
100000
1 bar, 30 °C
1 bar, 60 °C
10000
1 bar, 90 °C
10 bar, 30 °C
10 bar, 60 °C
1000 10 bar, 90 °C
100
Fe2+ (ppm)
10
0.1
0.01
3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
pH
Figure 2.3: Effect of temperature, pCO2, and pH on siderite precipitation in 3% NaCl solution. Vertical axis
shows Fe2+ concentration required to reach siderite saturation.
2.2 Preferential weld corrosion in CO2 environments
Oil and gas pipelines are often hundreds of kilometres long, and made by butt welding
individual stock lengths of linepipe end-to-end. The typical linepipe stock-length is 11 m,
therefore a pipeline can consist of thousands of girth welds. In addition to the girth welds, if
longitudinally welded linepipe is used, there is weld running the entire length of the pipeline.
Preferential weld corrosion of carbon steel linepipes in CO2 environments is a serious

problem faced by oil and gas companies, and can occur in either the girth or longitudinal
weld. There is a strong consensus in the literature that CO2 preferential weld corrosion is
caused by galvanic interactions between the weld metal, heat-affected zone, and the base
7
metal4, 21-28. It is well known that carbon steels with different micro-alloying compositions
have slightly different corrosion potentials, and when electrically connected to each other this
difference is compensated by the flow of galvanic currents. Electrons will leave the less
noble (anodic) material and flow to the more noble (cathodic) material. The anodic material
is therefore galvanically attacked, and the cathodic material is cathodically protected.
Pipelines typically operate under severe conditions, with temperature ranges of -20 to
100 ºC, and pressures ranges of 0.5 to 60 bar. The weld seam is a location of
microstructural inhomogeneity, and often seen as a location where mechanical properties
such as toughness and hardness are compromised compared to the base material. Because
of this, the filler material used during welding has a careful mix of micro-alloying elements to
optimise mechanical properties after welding. This results in the weld filler material typically
having a different chemical composition to the base metal and HAZ. The literature often
focuses on this difference in chemical composition as the source of preferential weld
corrosion in CO2 environments4, 24, 26-34. While this clearly has an important effect on PWC, it
does not explain why autogenous welds (i.e. welds made without a filler material) can also
experience PWC.
2.2.1 Effect of nickel and copper
The addition of nickel and copper increase the nobility of steel, therefore these
elements are discussed together. Also, nickel filler materials are often specified when
increased mechanical properties are required, primarily in terms of toughness.
A Ni containing filler material has two effects on the WM. Firstly it makes the WM more
noble, meaning it behaves cathodically relative to the BM. Secondly, it increases the intrinsic
corrosion rate (self-corrosion rate, or un-coupled corrosion rate) of the WM4, 30, 35, 36. In other
words, if the electrolyte is not sufficiently conductive (e.g. wet gas or very low salinity water),
the WM will corrode at a higher rate than the BM, as its intrinsic corrosion rate is higher from
the Ni addition. However, if the electrolyte is sufficiently conductive (e.g. saline formation
water), a galvanic couple is established where the BM cathodically protects the WM,
lowering its corrosion rate to much less than its intrinsic value. If the WM contains too much
nickel, typically greater than 1 wt%, the WM becomes so cathodic that the HAZ can be
preferentially attacked26, 29.
The effect of solution conductivity (i.e. NaCl concentration) on the effect of Ni on PWC
was clearly shown by Lee and Woollin4. Results are summarised by Figure 2.4, and show
the welds made using a Ni filler were only preferentially attacked in low conductivity
solutions.
8
Cu and Ni can be added simultaneously to increase WM nobility, and literature shows
that when added to a bainitic steel the WM was cathodic if Equation (2.15) was satisfied37, 38.
Equation (2.16) has also been used by some29, where a positive ∆ value indicates an anodic
weld configuration.
Cu+Ni WM - Cu+Ni BM >0.5% (2.15)
∆ = 3.8 CuBM - CuWM + 1.1 NiBM - NiWM + 0.3 (2.16)
A series of girth welds made with different filler materials on X60 and X65 linepipe
were investigated in 0.5% NaCl at 1 bar CO2, 75 ºC by Joosten, et al.26. Base metal and
weld root compositions are given in Table 2.3 and Table 2.4.
Low heat input (0.4 - 1.0 kJ/mm) gas metal arc welding (GMAW) of a Cu-Ni steel
(Steel 3) using 1.4% Ni solid wire (Union K 5 Ni) resulted in a 1% Ni root composition, and
preferential corrosion of the HAZ resulted. Zero resistance ammetry measurements
confirmed the HAZ was anodic relative to the BM and WM. Higher heat input (1.0 - 3.5
kJ/mm) shielded metal arc welding (SMAW) of the same steel using a 1% Ni electrode
(Lincoln SA 70+) gave a 0.39% Ni weld root composition, and PWC was completely avoided.
SMAW of another Cu-Ni steel (Steel 4) with a nickel free, 0.3% Mo electrode (Lincoln
HYP) resulted in preferential attack of the weld. The weld root composition was 0.19% Mo,
0.13% Cu, and 0.15% Ni. Ni and Cu were found in the weld root as there is a mixing with the
base metal during welding. As the base metal of Steel 4 contained 0.22% Ni and 0.20% Cu,
the WM was under-alloyed and was galvanically attacked.
SMAW of an unalloyed C-Mn X65 steel (Steel 1) welded with a 1% Ni electrode

(Lincoln SA 70+) gave a 0.34% Ni root composition and no preferential attack was observed.
Joosten, et al.26 noted that submerged arc welding (SAW), which has an even higher
heat input (2.0 – 4.0 kJ/mm), was also able to avoid preferential weld corrosion, however,
filler material and weld root compositions were not given. Alawadhi and Robinson39 had a
similar finding, that SAW welding of a C-Mn X65 steel (Steel 2) giving a root composition of
0.68% Ni prevented preferential weld corrosion.
Bretherton, et al.40 investigated preferential weld corrosion experienced in an inhibited

process line downstream of a second stage separator after 24 months of operation. The line
was used to pass degassed process water from the second stage separator to the first stage
separator. Acetic acid was injected into the line (500 - 1000 ppm) to prevent pH rise during
the degassing. It was discovered that only the Ni free welds suffered preferential weld
corrosion. Welds in the same line welded with a Ni filler were not attacked.
9
Table 2.3: Base metal composition of linepipe investigated by Joosten, et al.26 and Alawadhi and
Robinson39.
Steel 1 Steel 2 Steel 3 Steel 4
API Grade X65 X65 X65 X60
C 0.11 0.02 0.09 0.09
Mn 1.35 1.60 1.37 1.32
Si 0.23 0.30 0.36 0.22
Ni 0.03 0.04 0.19 0.22
Cu 0.02 0.02 0.19 0.20
Cr 0.04 0.02 0.01 0.03
Mo 0.19 0.01 0.01 0.01
Table 2.4: Weld metal root composition of linepipe investigated by Joosten, et al.26 and Alawadhi and
Robinson39.
Steel 1 Steel 2 Steel 3 Steel 4
API Grade X65 X65 X65 X60
C 0.11 0.08 0.10 0.088
Mn 1.09 1.40 0.99 0.79
Si 0.27 0.30 0.28 0.29
Ni 0.34 0.68 0.39 0.15
Cu 0.01 0.02 0.11 0.13
Cr 0.03 0.03 0.01 0.03
Mo 0.14 0.33 0.01 0.19
BM 1
12 HAZ 1
WM
Corrosion Rate (mm/y)
10 HAZ 2
BM 2
8
0
X52 GTAW X52 SMAW X52 GTAW X52 SMAW
0.35 g/L NaCl 0.35 g/L NaCl 35 g/L NaCl 35 g/L NaCl
Figure 2.4: Effect of solution conductivity (NaCl concentration) on preferential weld corrosion of GTAW
and SMAW welds made using a 1% Ni filler material4.
2.2.2 Autogenous and matched filler welds
Work by Lee and Woollin4 showed that welds made using a filler material of similar
composition to the base metal, or by an autogenous process (i.e. no filler material), were
less susceptible to PWC, regardless of electrolyte conductivity. This makes sense as by
10
removing chemical composition gradients, the driving force for galvanic corrosion should
reduce. It was noted that autogenous or matched filler welds with larger grains and higher
hardness were more susceptible to PWC.
2.2.3 Influence of weld preheat
Weld nobility can also be affected by the level of preheat applied before welding.
SMAW welds on a Cu-Ni X60 linepipe (Steel 4, Table 2.4) with an unalloyed filler metal were
made with preheats of 22, 100, and 180 ºC. The welds were then exposed to 0.5% NaCl
saturated with 1 bar CO2 at 75 ºC for two weeks26. Zero resistance ammetry measurements
showed the WM was strongly anodic for the 22 and 100 ºC preheat cases. The attack depth
of the WM, HAZ, and BM was measured after two weeks, and for both the 22 and 100 ºC
preheat condition, the WM had a corrosion rate of 23 mm/yr. The HAZ and BM were
measured at only 2 mm/y. By contrast, the use of 180 ºC preheat dramatically reduced the
weld anodic current density in the zero resistance ammetry experiments, and the WM
corrosion rate reduced to 9 mm/y, and the HAZ and BM corrosion rates increased to 6 mm/y.
As the base metal contained Cu and Ni additions, an unalloyed filler metal being anodic is
not surprising. Nevertheless, the increased preheat and subsequent slower cooling rate
clearly affected the anodic/cathodic behaviour of the weld. The effect of increased weld
preheat on reducing PWC is in agreement with Section 2.2.1, where welding processes with
a higher heat input (e.g. SMAW and SAW) were more resistant to PWC than lower heat
input processes (GMAW).
2.2.4 Effect of microstructure
Carbon steel is thermodynamically unstable in CO2 oil and gas production

environments and experiences a high rate of corrosion41. The wide spread use of this
economical material largely depends on its ability to form a protective siderite (FeCO3)
corrosion product layer. The protectiveness of this siderite corrosion product largely depends
on its density and adherence strength to the steel surface, which is dependent upon the
steel's microstructure42-47. Cementite (Fe3C) networks present in the steel strongly influence
the formation rate and adherence strength of siderite. Cementite is cathodic relative to
ferrite45, 48, therefore cementite accelerates the dissolution of iron from the ferrite phase
through galvanic coupling. This forms flow-sheltered cavities between the cementite platelets
that become locally saturated with Fe2+ ions. As discussed in Section 2.1.2, siderite
precipitates once the solubility product is exceeded.
Early work by Ueda and Takabe44 showed that a J55 steel with a normalized banded
pearlite microstructure experienced a significantly lower corrosion rate than an N80 steel,
11
which had similar composition and a martensitic microstructure. This was attributed to the
morphology of the siderite corrosion product layer. The J55 steel corroded away to leave a
lamellar cementite network, locally increasing Fe2+ ion concentration in the formed corrosion
cavities. This led to siderite precipitating within the cavities and anchoring itself to the
lamellar, interconnected cementite structure of the J55. The homogeneous distribution of
globular cementite particles in the N80 steel also acted as cathodic sites, only they fell out of
the ferrite matrix as the steel corroded, and the siderite was unable to anchor itself to the
surface. It was proposed that once the non-conductive siderite covered the lamellar
cementite J55 structure, the galvanic coupling effect reduces and the corrosion rate slows.
Ueda and Takabe44 concluded normalized banded steels where therefore superior to
quenched and tempered ones, due to the interconnected cementite networks. However, as
summarised in a recent literature review by Kermani and Morshed45, the formation of
cementite layers have a contrasting role. While a strong, well-adhered, and interconnected
cementite layer can prevent Fe2+ diffusion to the bulk solution, promoting siderite
precipitation, it can also lead to internal acidification. The cathodic reaction preferentially
occurs at the cementite surface, therefore a thick cementite layer can physically separate the
location of the anodic and cathodic reactions. This can cause significant water chemistry
variations, where the outer cementite layer becomes alkaline and the inner region becomes
acidic. Such a regime can accelerate corrosion.
Therefore, cementite morphology essentially affects corrosion product layer stability,

however, it is a complex relationship and cannot be reliably predicted.
The main limitation of the current literature, with regards to siderite corrosion product
layer formation, and its relationship to steel microstructure, is that it only focuses on a
uniform material42-47. In the weld region, especially with ERW seam heat treated linepipe,
there can be significant variations in cementite morphology across the weld and HAZs. The
effect of having these different microstructures coupled to each other is unclear, and is the
main focus of this thesis.
2.3 Electric resistance welding (ERW) of linepipe
From a fabrication point of view, linepipe falls into two categories, seamless or
longitudinally welded. Seamless linepipe involves heating an ingot of steel and essentially
ramming a die through it to create a hollow tube. Longitudinally welded linepipe, which is the
more common method, essentially hot rolls a flat steel sheet into a tube and welds the
longitudinal axis to create a pipe (Figure 2.5).
12
High frequency electric resistance welding (ERW) is the most common way to produce
longitudinally welded linepipe, as the process is highly automated, has a high production
rate, and is energy efficient. The process concentrates high frequency electrical current to
heat a small volume of metal near the faying surfaces to be welded, as illustrated in Figure
2.5. Heat is generated by the high frequency electricity and the electrical resistance of the
carbon steel sheet. When a high frequency current is applied to steel, the current
preferentially resides near the surface of the metal, known as the skin effect. As the
electrical frequency of the welding process is increased, the current depth becomes
shallower (closer to the surface). As the heat input can be carefully controlled and
concentrated, the resulting weld is very narrow (approx. 1 mm) with a small HAZ49, 50.
The resulting ERW weld has an as-cast microstructure. To improve mechanical

properties, welding is followed by a local seam heat treatment procedure, as this is more
economical than full body normalization. The localized seam heat treatment introduces a
steep temperature gradient between the austenitized weld region and the much cooler base
material. Depending on the carbon and manganese concentration of the steel, this cooling
gradient can produce a wide HAZ with several different microstructures present.
Despite the high prevalence of ERW linepipe in the oil and gas industry, there is little
work investigating the susceptibility of these autogenous welds to CO2 PWC.
Figure 2.5: Illustration of the high frequency ERW welding process used to make longitudinally welded
linepipe.
13
Chapter 3 Experimental methodology for investigating
CO2 preferential weld corrosion
3.1 Introduction
As discussed in the literature review, the mechanisms surrounding preferential weld

corrosion (PWC) in CO2 oil and gas environments are unclear. Previous research has shown
the greatest resistance to CO2 PWC occurs when matched fillers or autogenous welding
processes (i.e. no welding consumable) are used, as this minimizes chemical composition
gradients and galvanic couples4, 28. By this reasoning, longitudinally welded linepipe
manufactured by the autogenous electric resistance welding (ERW) process should have
good PWC resistance. The use of ERW linepipe is also more economical compared to
seamless, with lower costs and shorter lead times. Unfortunately, the oil and gas industry
still experiences many random PWC failures every year with ERW linepipe.
The ERW welding process is the most common way of producing longitudinally welded
linepipe. As discussed in Section 2.3, the localized seam heat treatment can produce a wide
heat affected zone with several different microstructures present.
As the ERW welding process eliminates chemical composition gradients, the author
suggests CO2 PWC must be related to the different microstructures present in the weld and
heat affected zone of the ERW linepipe.
This section introduces an electrochemical method called multi-channel zero

resistance ammetry (ZRA) (Section 3.2.3), that allows the measuring of galvanic currents
between the different microstructural zones present in ERW linepipe. The method has been
modified so experiments can be performed inside a stirring autoclave to simulate oil and gas
field conditions.
There is little work investigating the susceptibility of autogenous welds to PWC. While
there are several papers investigating the galvanic behaviour of welds in CO2 environments,
the weld is always divided into the conventional three categories of WM, HAZ, and BM24, 27,
30, 40, 51-53. This approach, where the HAZ is only represented by one electrode in the ZRA
setup, is over-simplistic and problematic. It is quite rare for the HAZ of any weld, not just
autogenous welds, to be one discrete microstructure. As a minimum there is usually a
coarse grain HAZ (CGHAZ) followed by a fine grain HAZ (FGHAZ). If these two
microstructures are simply grouped together on the same ZRA electrode, galvanic
interactions between these two microstructural zones will go undetected. For example, if the
14
FGHAZ is strongly anodic relative to the CGHAZ as illustrated in Figure 3.1, the FGHAZ will
be attacked. However, the ZRA will not capture this behaviour as both the FGHAZ and
CGHAZ are on the same electrode. In the case of seam heat treated ERW linepipe where
typically three HAZ microstructures are present (Section 3.4.3), accurate results require
each ZRA electrode to be strictly one microstructure.
The new multi-channel ZRA approach described here, aims to investigate ERW
linepipe galvanic interactions in CO2 environments strictly on a microstructural basis. That is,
to perform multi-channel ZRA experiments where every different microstructural zone
present in a particular manufacturer’s ERW linepipe is represented by a separate electrode
in the ZRA setup. This approach will allow for the explicit identification ERW microstructural
zones susceptible to localized attack in CO2 environments.
Figure 3.1: Common ZRA setup that fails to capture galvanic effects between the CGHAZ and the FGHAZ
as they are on the same electrode
3.2 Galvanic corrosion
3.2.1 Fundamentals of galvanic corrosion
When a metal is in contact with an electrolyte, electrochemical reactions occurring on

the surface result in the metal acquiring a specific corrosion potential (Ecorr). The acquired
corrosion potential primarily depends on metal’s chemical composition and the electrolyte,
however, it also depends on the surface condition of the metal. For example, steel with a
corrosion product layer will acquire a different corrosion potential than the same piece of
steel with a freshly ground surface. Metals with a more positive corrosion potential are
referred to as being more noble. When two dissimilar metals are brought into contact in an
electrolyte, each metal can no longer maintain its natural corrosion potential, and the two
corrosion potentials are polarized to a common, intermediate potential. This is the coupling
potential. Due to this polarization, electrons will flow from the less noble metal to the more
noble one. Electrochemically speaking, corrosion is simply the loss of electrons. Therefore
15
the less noble metal loosing electrons has its corrosion rate increased, and the more noble
metal receiving the electrons is cathodically protected. This forms a galvanic cell, and is
essentially how sacrificial anodes work on ships, for example. The zinc mounted on the hull
of the ship will preferentially corrode instead of the steel hull. When there is no more zinc left
to corrode, the steel hull then starts to corrode.
3.2.2 Relevance to ERW linepipe
The longitudinal weld present in ERW linepipe is a region of microstructural

inhomogeneity. In CO2 containing environments, corrosion product layers consisting of
cementite (Fe3C) and siderite (FeCO3) readily form on the surface of the steel. As several
different microstructural zones are present around the ERW weld region, it can be expected
that corrosion product layer morphology will vary throughout this region. As corrosion
product layers affect the corrosion potential, it is reasonable to expect that each
microstructural zone will naturally want to acquire a different corrosion potential. However,
these different microstructural zones are touching each other, and steel is conductive, and
there cannot be different potentials across a single conductor. Therefore, the different
microstructural zones will be polarized to a common intermediate potential. To compensate
for this polarization, an electron current is forced to flow from the less noble microstructures
to the more noble ones. This phenomenon could then result in the highly localized galvanic
attack of a particular microstructural zone in the ERW linepipe.
3.2.3 Zero resistance ammetry (ZRA)
A zero resistance ammeter (ZRA) is an arrangement of operational amplifiers that

allows different electrodes to be virtually short circuited (i.e. connected with zero resistance),
and for the galvanic coupling currents flowing between the electrodes to be measured. This
method is well suited for studying the effect of microstructure on the preferential weld
corrosion of ERW linepipe. Each of the different microstructural zones present in the ERW
linepipe can be segmented (i.e. cut out) and made into a separate electrode. The segmented
electrodes can then be short circuited together via the ZRA, which electrically recreates the
original weld configuration. The advantage of this approach is that the complete weld
structure can corrode in a natural and un-forced way, however, the galvanic currents flowing
between the different microstructural zones can be measured in real time.
The ERW process is an autogenous welding process (i.e. does not use a filler metal),
therefore the weld seam has the same chemical composition as the HAZs and the BM. This
would suggest that the galvanic currents measured by the ZRA should be minimal. However,
as the welding and seam heat treatment processes can cause several localized
16
microstructural variations (Section 3.4.3), it is possible that after being exposed to various
CO2 environments for several days, different corrosion product layers will form on different
microstructural zones. Once this occurs, significant galvanic couples could then develop
between certain microstructural zones present in the ERW linepipe. A multi-channel ZRA
would capture this behaviour, and would allow for microstructural zones susceptible to
localized corrosion to be identified. Several ERW linepipes and OCTGs could be
investigated, in a range of CO2 environments (i.e. pCO2, temperature, acetic acid, corrosion
inhibitors), and relationships between microstructure and susceptibility to localized attack
could be developed. This information can be used in the material selection process to avoid
the preferential weld corrosion of ERW linepipes in CO2 environments. Of course, the
developed experimental setup can also be used to directly asses a particular linepipe’s
susceptibility to localized CO2 corrosion.
3.2.3.1 Multi-channel zero resistance ammetry design
Figure 3.2 illustrates the basis of how a multi-channel ZRA was created using a series
of operational amplifiers. A total of four ZRA blocks were built (Blocks A, B, C, and D),
allowing four hockey puck electrodes (Figure 3.3) to be tested simultaneously in the same
electrolyte pool in the stirring autoclave. Each ZRA block consisted of five inputs (designated
I1 to I5), five outputs (designated U1 to U5), and its own power supply. The different ERW
microstructural zones were connected to inputs I1 to I5, which electronically short circuited
the microstructural zones and re-created the original weld. The potential that needed to be
applied (U1 to U5) by the operational amplifiers to keep all the microstructural zones (I1 to
I5) at the same natural corrosion potential was measured against a common ground (i.e
GND A for Block A), and recorded using a Keysight model 34972A DAQ, which was a 6 ½
digit voltmeter. The signals were switched by a model 34901A relay multiplexer module in
two-wire configuration (i.e. truly differential), and the input impedance was greater than
10 GΩ for all channels.
The applied potential to each microstructural zone (i.e. the value recorded by the DAQ)
causes a galvanic current to flow according to Equation (3.1), where I is in amperes, U is in
volts, R is the value of the resistor (10,000 Ω), and a positive I value indicates the
microstructural zone is anodic (i.e. is losing electrons and being locally attacked).
I = U/R (3.1)
17
For the configuration shown, the ZRA can deliver a maximum current density of
approximately 4500 µA/cm2, for an electrode surface area of 0.10 cm2. Several operational
amplifiers were tested. LT1013CP and LT1014CN operational amplifiers were selected as
calibration testing showed they had an offset voltage tolerance of ±0.0005 V, equating to a
current density tolerance of 0.5 µA/cm2. The sum of the currents measured by the ZRA were
continuously checked to ensure they summed to zero.
Figure 3.2: Example circuitry for multi-channel ZRA, allowing the measurement of galvanic coupling
currents between the different microstructural zones present in the welded linepipes/OCTGs.
18
3.3 Experimental setup
3.3.1 Electrode design
Metallographic cross sections were taken of the entire weld and heat affected zone
region of each of the investigated ERW linepipes and OCTGs given in Section 3.4. Optical
microscopy was used to identify the ERW weld centreline, and then closely examine the
heat affected zone region until the microstructure had fully transformed into the nominal
base metal microstructure. A micro-hardness indenter fitted to the microscope was then
used to mark the boundaries where one microstructure transformed into another. The weld
centreline was designated as WM (i.e. where the two faying surfaces of the strip material
meet during the ERW welding process), and each different heat affected zone microstructure
was designated HAZ 1, HAZ 2, HAZ 3, etc… After marking the microstructural zone
boundaries, a Struers Accutom-5 precision water cooled cutting machine was used to slowly
(0.01 mm/s) segment the different microstructural zones. This technique ensured precise
and deformation free cutting. A base metal segment (BM) was taken approx. 180º from the
weld. The segmented pieces were then ground to a 2400 grit finish on all surfaces, and
polished on a Struers MD-Nap polishing disc, giving a mirror finish. The segments were then
embedded in non-conductive Bakelite at 180 ºC under 300 bar pressure. The combination of
mirror polishing the sides of the segments and embedding under pressure ensured a crevice
free ‘hockey puck’ style five-segment electrode.
The ‘hockey puck’ was then polished, etched in 3% Nital for approx. 7 seconds, and
examined under optical microscope to ensure the microstructural zones were segmented
successfully. A completed five-segment ZRA electrode is shown by Figure 3.3, where each
electrode corresponds to a different microstructural zone present in the ERW linepipe. A
five-segment electrode was made for every ERW linepipe and OCTG. A five-segment ZRA
electrode was also made for the seamless linepipes and OCTGs, where each electrode was
the nominal seamless microstructure. Electrode surface area ratios were as close to 1:1 as
practicable, with each electrode being approximately 0.10 cm2.
Precision holes were drilled on the back side of the hockey puck so electrical wires
could be joined to each electrode using silver paint. Once joined, the holes were sealed shut
with high-strength resin. The surface of the five-segment ZRA electrodes were ground to a
2400 grit finish and rinsed with ethanol before each experiment.
19
Figure 3.3: A polished weld cross section showing the location of different microstructural zones (left),
and the corresponding five-segment ZRA electrode (‘hockey puck’). Each electrode corresponds to a
different microstructural zone present in the ERW linepipe. The BM electrode was taken 180º from the
weld. WM refers to the weld centreline, where the two faying surfaces of the strip material meet.
3.3.2 Stirring autoclave
The multi-channel ZRA experiments were performed inside a 5 litre stirring autoclave
modified for in-situ electrochemistry, which could hold four ‘hockey puck’ electrodes at once.
This allowed the ZRA measurements to be made at various CO2 partial pressures and
temperatures, with a flow rate representative of field conditions (150 RPM, approx. 0.5 m/s).
The experimental setup is shown in Figure 3.4.
3.3.2.1 Operating procedure
A 4 litre beaker filled with 30 g/L NaCl was purged with CO2 for 2 hours to remove
oxygen and ensure CO2 saturation. Meanwhile, the five-segment ZRA electrodes were
placed inside the empty stirring autoclave in a specially designed cradle. The autoclave was
purged with CO2 to remove any oxygen from the chamber and then closed and brought to
vacuum pressure. The pressure differential was used to draw in approximately 3.3 litres of
electrolyte, which completely submerged the five-segment ZRA electrodes. A back pressure
valve was used to slowly purge the autoclave atmosphere with CO2 during the experiment
(no bubbling of the electrolyte, only CO2 blanketing). The stirrer was operating at 150 RPM,
which gave an approx. flow velocity of 0.5 m/s at the electrode surfaces.
The stirring autoclave was equipped with several valves, which allowed for the
injection of additional fluids (e.g. corrosion inhibitor, acetic acid) and for the extraction of fluid
samples for water analysis (e.g. Fe2+ concentration).
20
Figure 3.4: Experimental setup, showing stirring autoclave, multi-channel ZRA circuitry, temperature
control unit, and data recorder.
3.3.3 Data evaluation
3.3.3.1 Average galvanic current density (AGCD)
Five-segment ‘hockey puck’ ZRA electrodes were made for each investigated linepipe
and OCTG. The galvanic currents flowing between the ZRA electrodes were measured for
168 hours inside the stirring autoclave, producing current density curves for each electrode
(microstructural zone) such as those shown by Figure 4.2. Positive current densities in this
thesis are anodic, negative currents are cathodic. The sum of the galvanic coupling currents
were checked to ensure they equalled zero.
Galvanic interactions for a particular microstructural zone were summarised by an
average galvanic current density (AGCD168hrs) value, as it was impractical to present all ZRA
curves for every investigated material and test condition. AGCD168hrs values were calculated
by separately integrating the positive (anodic) and negative (cathodic) parts of each
microstructural zone’s current density curve. The results were then summarised in bar
charts, such as those shown by Figure 4.4.
3.4 Investigated materials
Investigated linepipes and OCTGs are summarised in Table 3.1. In total 11 different
materials were investigated, sourced from several commercial manufacturers, and included
21
API grades X42, X52, J55, and L80. Chemical compositions measured by optical emission
spectroscopy are given in Table 3.2.
3.4.1.1 X42 linepipes
Four API grade X42 linepipes with different chemical compositions were investigated.
Three were ERW linepipes and one was seamless. The seamless linepipe was included in
these experiments to provide a base-line measurement, to essentially indicate what level of
galvanic interactions can be expected if the microstructure is nominally uniform.
Two X42 ERW linepipes (X42-A and X42-B) were hot rolled from normalized strip
material and ERW welded. After welding the weld seam was locally normalized by induction.
One X42 ERW linepipe (X42-C) was made via thermo-mechanical controlled
processing (TMCP). The weld seam was also locally normalized after welding.
The X42 seamless linepipe (X42-S) was full body normalized.
3.4.1.2 X52 linepipes
Four API grade X52 linepipes were investigated. The four linepipes were all made via
TMCP in the same production run from the same strip material. Therefore all four X52
samples had the same chemical composition. After ERW welding, each linepipe received a
different heat treatment by the manufacturer, as follows:
► One was left in the as-welded condition (X52-AW), and did not receive any
heat treatment.
► One had the weld seam locally normalized at 930 ºC (X52-SH).
► One had the weld seam locally normalized at 930 ºC, followed by a full body
stress relief at 450 ºC (X52-450).
► One had the weld seam locally normalized at 930 ºC, followed by a full body
stress relief at 650 ºC (X52-650).
The full body stress relief was via induction, and lasted for approximately 5 seconds.
3.4.1.3 OCTG materials
Three Oil Country Tubular Goods (OCTGs) were investigated, consisting of two ERW
OCTGs and one seamless. The ERW OCTGs were a quenched and tempered API grade
L80 (L80-A) and an API grade J55 with localized weld seam normalization (J55-A). The
seamless OCTG was a quenched and tempered API grade L80 (L80-S).
22
Table 3.1: Heat treatment and welding information of investigated materials.
Sample ID Grade Type Heat treatment
X42-A X42 ERW Hot rolled + local seam normalization
X42-B X42 ERW Hot rolled + local seam normalization
X42-C X42 ERW TMCP + local seam normalization
X42-S X42 Seamless Full body normalization
L80-A L80 ERW Quenched and tempered
L80-S L80 Seamless Quenched and tempered
J55-A J55 ERW Hot rolled + local seam normalization
X52-AW TMCP, as-welded condition
X52-SH TMCP + local seam normalization
X52 ERW
X52-450 TMCP + local seam normalization + 450 ºC stress relief
X52-650 TMCP + local seam normalization + 650 ºC stress relief
3.4.2 Chemical analysis
Chemical analysis of the investigated samples is given in Table 3.2.
Table 3.2: Chemical composition (wt%) of investigated steel linepipes/OCTGs, measured using optical
emission spectroscopy. Remainder concentration is iron (Fe).
Sample ID C Mn Si S Cr Mo Cu Ti P
X42-A 0.115 0.950 0.180 0.001 0.060 0.006 0.044 0.003 0.013
X42-B 0.130 0.960 0.180 0.003 0.076 0.028 0.053 0.002 0.015
X42-C 0.071 0.570 0.310 0.009 0.026 0.002 0.032 0.002 0.009
X42-S 0.090 1.220 0.220 0.001 0.150 0.054 0.150 0.002 0.015
L80-A 0.280 1.492 0.242 0.001 0.027 0.001 0.013 0.001 0.013
L80-S 0.302 1.342 0.203 0.0118 0.247 0.011 0.035 0.002 0.014
J55-A 0.159 1.104 0.187 0.001 0.353 0.001 0.020 0.017 0.012
X52-AW
X52-SH
0.058 0.820 0.211 0.001 0.040 0.009 0.113 0.014 0.010
X52-450
X52-650
3.4.3 Metallographic analysis
Metallographic cross sections were made of all investigated materials to identify the
different microstructural zones present. Optical and SEM micrographs showing the different
microstructural zones present in each investigated materials are given in Section 3.4.3.1 for
the X42 linepipes, Section 3.4.3.2 for the X52 linepipes, and Section 3.4.3.3 for the OCTGs.
An overall description of the different microstructural zones present in the X42, X52,
and OCTG materials is provided in Table 3.3, Table 3.4, and Table 3.5, respectively.
23
Table 3.3: Description of X42 linepipe microstructural zones / ZRA electrodes.
Microstructural zones /
Description Relevant figures
ZRA electrodes
X42-A
WM Weld centreline, normalized ferrite, isolated pearlite colonies
HAZ 1 Normalized ferrite, banded pearlite
HAZ 2 Grain refined, no banding Figure 3.5, Figure 3.6
HAZ 3 Grain refined, fine banded pearlite
BM Ferrite, banded pearlite, taken 180º from WM
X42-B
HAZ 1 Normalized ferrite, banded pearlite
HAZ 2 Coarse, heavily sub-grained, quasi-polygonal ferrite, banded pearlite Figure 3.7, Figure 3.8
HAZ 3 Granular bainite, upper bainite, quasi-polygonal ferrite
BM Ferrite, banded pearlite, taken 180º from WM
X42-C
HAZ 1 Normalized ferrite, isolated pearlite colonies
HAZ 2 Normalized ferrite, isolated pearlite colonies, slight segregation band Figure 3.9, Figure 3.10
BM 1
Ferrite, isolated pearlite colonies, both taken 180º from WM
BM 2
X42-S
E1, E2, E3, E4, E5 Nominal seamless microstructure of normalized ferrite, banded pearlite Figure 3.12, Figure 3.13
24
Table 3.4: Description of X52 linepipe microstructural zones / ZRA electrodes.
ZRA electrodes
X52-AW
Weld centreline in as-welded condition, acicular ferrite, quasi-polygonal ferrite, MA constituent, minor
WM
amounts of granular bainite
HAZ 1 Quasi-polygonal ferrite, polygonal ferrite, granular bainite, MA constituent
HAZ 2 Coarse, heavily subgrained, quasi-polygonal ferrite, polygonal ferrite, granular bainite, MA constituent Figure 3.14, Figure 3.15,
BM microstructure taken near the weld region, quasi polygonal ferrite, polygonal ferrite, granular bainite, Figure 5.1
BM 1
MA constituent
BM microstructure taken 180º from the weld region, quasi polygonal ferrite, polygonal ferrite, granular
BM 2
bainite, MA constituent
X52-SH
WM Weld centreline, fine equiaxed polygonal ferrite, granular bainite, MA constituent
HAZ 1 Fine equiaxed polygonal ferrite, granular bainite, MA constituent
HAZ 2 Large grain size distribution, polygonal ferrite, granular bainite, MA constituent
BM microstructure taken near the weld region, quasi polygonal ferrite, polygonal ferrite, granular bainite, Figure 3.16, Figure 3.17
BM 1
MA constituent
BM 2
X52-450
HAZ 2 Large grain size distribution, polygonal ferrite, granular bainite, MA constituent
BM 1
MA constituent
BM 2
…Table continued on next page
25
ZRA electrodes
X52-650
HAZ 2 Moderate grain size distribution, polygonal ferrite, granular bainite, MA constituent
BM 1
MA constituent
BM 2
26
Table 3.5: Description of OCTG microstructural zones / ZRA electrodes.
ZRA electrodes
L80-A
WM Weld centreline, quenched and tempered morphology
HAZ 1 Quenched and tempered morphology with residual pearlite bands visible
HAZ 2 Quenched and tempered morphology, no pronounced residual pearlite bands visible Figure 3.22, Figure 3.23
HAZ 3 Quenched and tempered morphology with fine residual pearlite bands visible
BM Quenched and tempered morphology with residual pearlite bands visible
J55-A
WM Weld centreline, normalized ferrite and mostly isolated pearlite
HAZ 1 Normalized ferrite and mostly isolated pearlite
HAZ 2 Grain refined, normalized ferrite and pearlite with some banding Figure 3.24, Figure 3.25
HAZ 3 Ferrite and finely banded pearlite
BM Ferrite and banded pearlite
L80-S
E1, E2, E3, E4, E5 Nominal seamless quenched and tempered microstructure Figure 3.26, Figure 3.27
27
3.4.3.1 X42 linepipe
Sample ID: X42-A

Type: X42 ERW linepipe
Method: Normalized strip material, hot rolled, with seam heat treatment
WM HAZ 1
HAZ 2 HAZ 3
Macrograph
BM (180º from WM)
Figure 3.5: Optical micrographs of X42-A microstructural zones. Etched 3% Nital, 500X.
28
Sample ID: X42-A
WM HAZ 1
HAZ 2 HAZ 3
BM (180º from WM) Macrograph

Figure 3.6: SEM SE micrographs of X42-A microstructural zones. Etched 3% Nital.
29
Sample ID: X42-B
WM HAZ 1
HAZ 2 HAZ 3
Macrograph
BM (180º from WM)
Figure 3.7: Optical micrographs of X42-B. Etched 3% Nital, 500X.
30
Sample ID: X42-B
WM HAZ 1
HAZ 2 HAZ 3

Figure 3.8: SEM SE pictures of X42-B microstructural zones. Etched 3% Nital.
31
Sample ID: X42-C
Method: Thermo-mechanically controlled processed, with seam heat treatment
WM HAZ 1
HAZ 2 BM 1, BM 2 (180º from WM)
Macrograph
Figure 3.9: Optical micrographs of X42-C microstructural zones. Etched 3% Nital, 500X.
32
Sample ID: X42-C
Method: TMCP, with seam heat treatment
WM HAZ 1
HAZ 2 BM 1, BM 2 (180º from WM)
Macrograph
Figure 3.10: SEM SE micrographs of X42-C microstructural zones. Etched 3% Nital, 500X.
33
Sample ID: X42-C
Description: EDX element mapping of WM
SEM SE image
Figure 3.11: EDX element mapping of X42-C weld centreline showing Mn, Si, O rich inclusions.
34
Sample ID: X42-S
Type: X42 seamless linepipe, full body normalized
Nominal
Figure 3.12: Optical micrograph of nominal seamless X42-S microstructure used for ZRA electrodes E1,
E2, E3, E4, and E5. Etched 3% Nital, 500X.
Sample ID: X42-S

Type: X42 seamless linepipe, full body normalized
Nominal
Figure 3.13: SEM SE micrograph of nominal seamless X42-S microstructure used for ZRA electrodes E1,
E2, E3, E4, and E5.
35
3.4.3.2 X52 linepipe
Sample ID: X52-AW

Method: TMCP, as-welded condition, no seam heat treatment
WM HAZ 1
HAZ 2 BM 1
Macrograph
BM 2 (180º from WM)
Figure 3.14: Optical micrographs of X52-AW microstructural zones. Etched 3% Nital, 500X.
36
Sample ID: X52-AW
Method: TMCP, as-welded condition, no seam heat treatment
WM HAZ 1
HAZ 2 BM 1
BM 2 (180º from WM) Macrograph

Figure 3.15: SEM SE micrographs of X52-AW microstructural zones. Etched 3% Nital.
37
Sample ID: X52-SH
Method: TMCP, seam heat treatment
WM HAZ 1
HAZ 2 BM 1
Macrograph
Figure 3.16: Optical micrographs of X52-SH microstructural zones. Etched 3% Nital, 500X.
38
Sample ID: X52-SH
Method: TMCP, seam heat treatment
WM HAZ 1
HAZ 2 BM 1
Figure 3.17: SEM SE micrographs of X52-SH microstructural zones. Etched 3% Nital.
39
Sample ID: X52-450
Method: TMCP, seam heat treatment with 450 ºC full body stress releif
WM HAZ 1
HAZ 2 BM 1
Macrograph
Figure 3.18: Optical micrographs of X52-450 microstructural zones. Etched 3% Nital, 500X.
40
Sample ID: X52-450
WM HAZ 1
HAZ 2 BM 1
41
Sample ID: X52-650
WM HAZ 1
HAZ 2 BM 1
Macrograph
Figure 3.20: Optical micrographs of X52-650 microstructural zones. Etched 3% Nital, 500X.
42
Sample ID: X52-650
WM HAZ 1
HAZ 2 BM 1
43
3.4.3.3 Oil Country Tubular Goods (OCTGs)
Sample ID: L80-A

Type: L80 ERW OCTG
Method: Quenched and tempered OCTG
WM HAZ 1
HAZ 2 HAZ 3
Macrograph
BM (180º from WM)
Figure 3.22: Optical micrographs of L80-A microstructural zones. Etched 3% Nital, 500X.
44
Sample ID: L80-A
Type: L80 ERW OCTG
Method: Quenched and tempered OCTG
WM HAZ 1
HAZ 2 HAZ 3

Figure 3.23: SEM SE micrographs of L80-A microstructural zones. Etched 3% Nital.
45
Sample ID: J55-A
Type: J55 ERW OCTG
WM HAZ 1
HAZ 2 HAZ 3
Macrograph
BM (180º from WM)
Figure 3.24: Optical micrographs of J55-A microstructural zones. Etched 3% Nital, 500X.
46
Sample ID: J55-A
Type: J55 ERW OCTG
WM HAZ 1
HAZ 2 HAZ 3
Figure 3.25: SEM SE micrographs of J55-A microstructural zones. Etched 3% Nital.
47
Sample ID: L80-S
Type: L80 seamless OCTG
Method: Quenched and tempered seamless OCTG
Nominal
Figure 3.26: Optical micrograph of nominal seamless L80-S microstructure. Etched 3% Nital, 500X.
Sample ID: L80-S

Type: L80 seamless OCTG
Method: Quenched and tempered seamless OCTG
Nominal
Figure 3.27: SEM SE micrographs of nominal seamless L80-S microstructure.
48
Chapter 4 Effect of ERW X42 linepipe microstructure
on CO2 preferential weld corrosion
4.1 Introduction
Longitudinally welded linepipes are known to be more susceptible to localized

corrosion than seamless linepipe due to chemical composition gradients between the weld
and base metal. As discussed in Section 2.2, LPR and EIS measurements from literature4
showed that welds made using a matched filler material, or made using an autogenous
welding process (e.g. ERW), have the best resistance to preferential weld corrosion in CO2
environments. These welding methods eliminate chemical composition gradients between
the WM, HAZ, and BM, and therefore prevent the formation of galvanic couples. Despite
using this approach, in certain CO2 containing oil and gas fields OMV has experienced
preferential weld corrosion in longitudinally welded ERW linepipes. Furthermore, despite all
flowlines having similar operating conditions and being made from the same material grade
(e.g. X42), certain manufacturers are more susceptible to PWC than others. The reason for
this is unclear, however, may be related to the different microstructural zones that form
around the ERW weld after the seam heat treatment process. If certain microstructures were
found to readily form strong galvanic couples due to different siderite precipitation kinetics,
these combinations could simply be avoided.
This chapter uses multi-channel zero resistance ammetry to investigate three ERW
X42 linepipes, and compares their performance to an X42 seamless linepipe.
4.2 Experimental methodology
4.2.1 Investigated materials
Four X42 linepipe were investigated, consisting of three longitudinally welded ERW
samples (X42-A, X42-B, X42-C) and one seamless (X42-S). Chemical compositions are
given in Table 3.2. A detailed micrographic analysis of these samples is given in Section
3.4.3.1, however, for convenience a quick summary is provided here.
X42-A and X42-B were welded by ERW from normalized strip material (0.115 and
0.130 wt% C, respectively), and the weld seam was locally normalized by induction after
welding. X42-C had a much lower carbon content (0.071 wt% C) and was made via thermo-
49
mechanically controlled processing (TMCP). X42-S was a full-body normalized seamless
linepipe.
As shown by Figure 3.5 and Figure 3.7, X42-A and X42-B had significant
microstructural heterogeneities around their longitudinal weld. Both had three distinct HAZ
regions, referred to as HAZ 1, HAZ 2, and HAZ 3, in addition to their WM and BM
microstructures. Note that ‘WM’ refers to the ERW weld centreline.
Figure 3.9 shows how X42-C had a much more uniform microstructure. HAZ 1 and
HAZ 2 are the heat-affected zones on the left and right side of the weld centreline. They are
essentially the same, however, it was noticed on a low-magnification photomicrograph that
HAZ 2 had a small segregation band running though the centre that was absent for HAZ 1.
Figure 3.12 shows the nominal seamless microstructure of X42-S, which was uniform
throughout the entire cross section.
Description of the different microstructural zones are summarised by Table 3.3.
4.2.2 Multi-channel zero resistance ammetry
Multi-channel zero resistance ammetry was used to investigate the galvanic

interactions between the different microstructural zones present in each linepipe. As
described in Section 3.3.1, a five-segment ZRA ‘hockey puck’ style electrode was made for
each linepipe. This recreated the original weld with each different microstructural zone
becoming an electrode on the ZRA (Figure 3.3). A five-segment ZRA electrode was also
made by taking five random cross sections from the seamless linepipe (X42-S), defined as
E1 to E5. All electrodes had approximately the same surface area of 0.10 cm2.
This approach allows the weld to corrode in a natural and un-forced way, and for the
galvanic currents flowing between each microstructural zone to be measured. Positive
currents are anodic.
4.2.3 Experimental procedure
The five-segment ZRA electrodes for each linepipe were placed inside the stirring
autoclave. The detailed experimental procedure is described in Section 3.3.2, however a
brief summary is provided here. The autoclave was brought to vacuum pressure, and the
pressure differential was equalized by drawing in approximately 3.3 litres of electrolyte, fully
submerging the samples. The electrolyte was 3% NaCl, purged with CO2 for 2 hours. The
stirring autoclave was then configured to one of the test conditions shown in Table 4.1 and
ran for approximately 168 hours. A back pressure valve was used to slowly purge the stirring
autoclave with CO2 for the entire duration of the experiment. The stirring speed was set to
50
150 RPM, which gave a flow velocity of approximately 0.5 m/s at the electrode surface; the
relative flow direction is shown by Figure 4.1. The pH and Fe2+ concentrations were
measured throughout each experiment; the results are also shown in Table 4.1.
Figure 4.1: Relative flow direction inside stirring autoclave.
Table 4.1: Experimental test matrix with pH and Fe2+ measurements. Electrolyte 3% NaCl, purged with
CO2 for 2 hours, 150 RPM (approx. 0.5 m/s).
Experimental Electrolyte RPM Temperature pCO2 pHinitial pH168hrs Bulk
ID (ºC) (bar) Fe2+168hrs
(ppm)
1-30-A 30 1 3.74 5.11 48
1-60-A 60 1 3.81 5.53 75
1-60-B 60 1 3.79 5.56 152
1-60-C 60 1 3.82 5.62 201
1-90-A 3% NaCl 150 90 1 3.95 5.79 49
10-30-A 30 10 3.28 5.01 1 86
10-60-A 60 10 3.36 5.75 1 275
10-90-A 90 10 3.45 6.16 1 224
10-90-B 90 10 3.48 6.21 1 195
1… final pH measurements were made at 1 bar CO
2
51
4.3 Results and discussion
4.3.1 Multi-channel zero resistance ammetry (ZRA)
4.3.1.1 The time dependence of galvanic interactions leading to PWC
Multi-channel zero resistance ammetry provided insight into the time dependence of
galvanic interactions for the ERW linepipes. The ZRA curves for 1 bar CO2, 90 ºC, are
shown by Figure 4.2 and illustrate how galvanic couples develop with time. For the first few
hours of the experiment, all samples had small galvanic interactions (low current densities).
This was expected, as the ERW welding process is autogenous (no filler material), therefore
chemical composition gradients are negligible, and the driving forces for galvanic
interactions are small. However, as the experiment progressed, the galvanic current
densities for X42-A and X42-B started to increase for particular microstructural zones. The
microstructural zones present in X42-A and X42-B had significant morphological differences,
especially with regard to cementite morphology. It was therefore expected that each
microstructural zone would slowly corrode in a different way, develop different corrosion
product layers, and that this localized surface modification would then slowly develop strong
galvanic couples. This is indeed the behaviour shown by Figure 4.2.
X42-A HAZ 2 after approx. 48 hours became a dominant anode (i.e. large positive
current density), meaning this microstructural zone in the ERW linepipe was being locally
attacked, essentially acting as a sacrificial anode trying to protect the rest of the linepipe.
Similarly with X42-B, HAZ 2 and HAZ 3 became dominant anodes, meaning these
microstructural zones are also susceptible to localized attack.
By comparison, the galvanic current densities measured between the X42-C

microstructural zones were significantly lower, and approached the performance of the
seamless X42-S linepipe. This was also expected, as the different microstructural zones
present in X42-C were quite similar to each other. Therefore they should corrode in a similar
way, and no significant surface variations should develop. This then lowers the driving force
for galvanic attack or a particular microstructural zone. It should be noted that the two BM
electrodes behaved cathodically, and the WM, HAZ 1, and HAZ 2 anodically. This is
undesirable as in reality the BM of the linepipe has a larger surface area and would
accelerate the anodic dissolution rate of the WM, HAZ 1, and HAZ 2. Nevertheless, the more
uniform microstructure of X42-C resulted in galvanic current densities approximately one
order of magnitude lower than X42-A and X42-B.
52
The seamless X42-S ZRA electrode, which was made from five random cross-sections
of the seamless linepipe, had almost negligible galvanic interactions for the entire duration of
the experiment. All X42-S electrodes had nominally identical microstructure, therefore all
electrodes were modified in the same way by the corrosion process, and galvanic
interactions were minimal.
The ZRA curves shown by Figure 4.2 provide insight into how different microstructures
present around the weld region can slowly establish galvanic couples that lead to PWC. If
the presence of different microstructural zones were sufficient to form galvanic couples, the
measured current densities at time zero would already be significant, however, this is not the
case here. The shape of these current density curves clearly indicate that galvanic couples
are established by a growth process, such as the development of different corrosion product
layers.
53
400
X42-A X42-B X42-C X42-S
4.6
Galvanic Current Density (µA/cm2)
Equivalent Corrosion Rate (mm/y)

300 3.5
200 2.3
100 1.2
0 0
-100
-200 WM E1
WM WM
HAZ 1 E2
-300 HAZ 1 HAZ 1
HAZ 2 E3
HAZ 2 HAZ 2
HAZ 3 E4
-400 HAZ 3 BM 1
E5
BM BM BM 2
-500
0 48 96 144 0 48 96 144 0 48 96 144 0 48 96 144
Time (Hrs) Time (Hrs) Time (Hrs) Time (Hrs)
Figure 4.2: ZRA curves for 1 bar CO2, 90 ºC, showing how some microstructural zones in ERW linepipe (X42-A, X42-B) develop strong galvanic couples during the
corrosion process. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive values are anodic.
54
1 bar CO2
200 2.3
X42-A X42-B X42-C X42-S

Average Galvanic Current Density (µA/cm2)
150 1.7

100 1.2
50 0.6
0 0
-50
WM WM WM E1
-100 HAZ 1 HAZ 1 HAZ 1 E2
HAZ 2 HAZ 2 HAZ 2 E3
HAZ 3 HAZ 3 BM 1 E4
-150 BM BM BM 2 E5
-200
30 ºC 60 ºC 90 ºC 30 ºC 60 ºC 90 ºC 30 ºC 60 ºC 90 ºC 30 ºC 60 ºC 90 ºC
Temperature
Figure 4.3: Average galvanic current densities over 168 hours (AGCD168hrs) for X42 ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe. Conditions: 1 bar
CO2, 3% NaCl, 150 RPM (approx. 0.5 m/s), surface area ratios 1:1. Positive values are anodic.
55
10 bar CO2
1400 16.2
1200 X42-A X42-B X42-C X42-S 13.9


1000 WM WM WM E1 11.6
800 HAZ 2 HAZ 2 HAZ 2 E3 9.3
HAZ 3 HAZ 3 BM 1 E4
600 BM BM BM 2 E5 7.0
400 4.6
200 2.3
0 0
-200
-400
-600
-800
Temperature
Figure 4.4: Average galvanic current densities over 168 hours (AGCD168hrs) for X42 ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe. Conditions: 10 bar
CO2, 3% NaCl, 150 RPM (approx. 0.5 m/s), surface area ratios 1:1. Positive values are anodic.
56
X42-A HAZ 2 X42-B HAZ 3
10000
1000
100
10
±1
0.1
-10
0.01
-100
0.001
-1000
0 24 48 72 96 120 144 168 0 24 48 72 96 120 144 168
Time (Hrs) Time (Hrs)
1 bar, 30 ºC 10 bar, 30 ºC 1 bar, 30 ºC 10 bar, 30 ºC
Figure 4.5: ZRA curves showing galvanic density for X42-A HAZ 2 and X42-B HAZ 3 for all test
conditions. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Positive values are anodic.
4.3.1.2 Average galvanic current density (AGCD168hrs)
It is not practical to present ZRA curves similar to Figure 4.2 for each linepipe for all
the test conditions shown in Table 4.1. A more convenient approach is to compare the
average anodic and cathodic current densities for each microstructural zone over the 168
hour test period (AGCD168hrs). This method was described in Section 3.3.3.1.
The AGCD168hrs values for each microstructural zone for 30, 60, and 90 ºC are shown
in Figure 4.3 for 1 bar CO2 and Figure 4.4 for 10 bar CO2. Overall, X42-A and X42-B had a
higher susceptibility to localized corrosion than X42-C and the seamless X42-S. X42-C
approached the performance of seamless for 30 and 60 ºC, at both 1 and 10 bar CO2,
however, the WM was attacked at 90 ºC. The seamless X42-S was the least susceptible to
localized corrosion overall.
4.3.1.2.1 1 bar CO2
For X42-A, the grain refined region free of pearlite banding (HAZ 2), was consistently
attacked. This microstructural zone was constantly the dominant anode at 30, 60, and 90 ºC,
with anodic AGCD168hrs values of 18, 29, and 107 µA/cm2 (0.21, 0.34, and 1.2 mm/y),
respectively.
57
HAZ 2, HAZ 3, and the BM for X42-B were consistently anodic, however, HAZ 3 was
clearly the dominant anode. At 30, 60, and 90 ºC HAZ 3 had anodic AGCD168hrs values of 19,
87, and 164 µA/cm2 (0.22, 1.0, and 1.9 mm/y), respectively. These were the highest values
recorded for the 1 bar CO2 experiments, and suggests that quenched and tempered (Q&T)
microstructures behave anodically to normalized ones. This is an interesting point, as often
normalized and Q&T linepipes are welded together. HAZ 2, the heavily subgrained quasi-
polygonal ferritic region, was also a strong anode at 1 bar CO2, with AGCD168hrs values of 18,
48, and 140 µA/cm2 (0.21, 0.56, and 1.6 mm/y), respectively.
X42-C had the lowest AGCD168hrs values for the ERW linepipe. No significant localized
corrosion behaviour was observed at 30 and 60 ºC; the maximum anodic AGCD168hrs value
was only 9.5 µA/cm2 (0.11 mm/y). Although the WM was preferentially attacked at 90 ºC,
with an AGCD168hrs of 32 µA/cm2 (0.37 mm/y), the attack rate was an order of magnitude
lower than that experienced by X42-A HAZ 2 and X42-B HAZ 3.
The seamless X42-S linepipe showed no susceptibility to localized corrosion at 1 bar

CO2 for 30, 60, and 90 ºC. All the anodic X42-S AGCD168hrs values were less than 5 µA/cm2
(0.06 mm/y), up to two orders of magnitude smaller than the ERW linepipes.
4.3.1.2.2 10 bar CO2
At 10 bar CO2 X42-A HAZ 2 and X42-B HAZ 3 were again dominant anodes, and the
higher CO2 partial pressure magnified the level of attack.
The anodic AGCD168hrs values for X42-A HAZ 2 had approximately doubled to 175 and
331 µA/cm2 (2.0 and 3.8 mm/y) for 60 and 90 ºC, respectively. Interestingly at 30 ºC, there
was no localized attack of any microstructure for X42-A, with the AGCD168hrs values
comparable to the seamless linepipe.
X42-B HAZ 3 experienced a dramatic increase in localized attack for the 10 bar CO2
experiments, with AGCD168hrs values of 1013 and 664 µA/cm2 (11.8 and 7.7 mm/y) for 60,
and 90 ºC, respectively. Interestingly HAZ 2 was strongly anodic at 1 bar, yet behaved
cathodically at 10 bar.
X42-C again had the lowest susceptibility to localized corrosion for the ERW linepipes.
Similar to 1 bar CO2, X42-C showed no localized corrosion behaviour at 30 and 60 ºC, with
AGCD168hrs values comparable to seamless. Also similar to 1 bar CO2, the WM was again
attacked at 90 ºC, with an AGCD168hrs of 204 µA/cm2 (2.3 mm/y).
The galvanic interactions for X42-S were again consistently low. At 30 ºC X42-S had
similar galvanic interactions to the ERW linepipes, although these values were low anyway.
58
X42-S galvanic interactions remained low at 60 and 90 ºC, between 1 to 2 orders of
magnitude lower than the ERW linepipes. Having a uniform microstructure therefore lowers
the susceptibility to localized attack.
4.3.1.2.3 Mesa attack
10 bar CO2, 60 ºC was a severe test condition, and while the AGCD168hrs values for the
seamless X42-S sample were significantly lower than X42-A and X42-B (Figure 4.4), X42-S
experienced a case of mesa attack. Mesa attack is a form of localized CO2 corrosion that
causes random localized attack of seamless linepipe. Current literature debates the
mechanism behind mesa attack. Some authors suggest mesa attack occurs from the
competitive formation of siderite (FeCO3) and magnetite (Fe3O4), and that the co-deposition
of both corrosion product layers prevents a protective siderite film form forming, initiating
mesa attack54. One problem with this theory is that in actual field conditions where mesa
attack has occured, magnetite is not always detected55. Other authors have shown that
mesa attack occurs at regions on the steel surface where flow conditions prevent siderite
precipitation, even if the fluid is saturated56-58. Dugstad has discussed the possibility of a
galvanic cell establishing, where the siderite covered surface is cathodic and the mesa
attacked region is anodic20, 59.
Evidence supporting Dugstad’s theory was recorded by the multi-channel ZRA

experiments for the seamless X42-S linepipe. The ZRA curves for all four samples are
shown by Figure 4.6 for 10 bar CO2, 60 ºC. The curves show the galvanic currents between
the five nominally uniform X42-S electrodes (E1 to E5) to be negligible for the first 130
hours, until E1 suddenly spikes in the anodic direction. This sudden spike suggests
something quickly changed on the surface of E1, such as a break in the corrosion product
layer, making it suddenly anodic. Post experiment SEM cross section analysis revealed the
corrosion product layer of E1 had experienced a breakage (Figure 4.21). Electrodes E2 to
E5 were covered with morphologically similar, dense siderite corrosion product layers;
however, E1 was mostly bare. The E1 corrosion product layer may have broken from
intrinsic film growth stresses 60, as discussed in Section 4.3.2.2. Therefore mesa attack is
indeed related to the sudden localized breakage of the corrosion product layer.
4.3.1.2.4 Galvanic passivation
The ZRA current density curves for the susceptible ERW microstructures (X42-A
HAZ 2 and X42-B HAZ 3) are shown in Figure 4.5 for all test conditions. With the exception
of 10 bar, 90 ºC, the current densities were normally maximum at the end of the experiment
(168 hrs). This should be expected if galvanic interactions occur from different
59
microstructural zones forming different corrosion product layers. The more time these
different layers have to grow, the greater their differences become, and stronger galvanic
interactions result. It is possible however, that if one of the susceptible microstructural zones
experiences sufficiently rapid attack, the change in local precipitation kinetics could produce
a protective corrosion product layer. Galvanic passivation, where all the current densities fall
to near-zero, was frequently observed for the seamless linepipe, but only once for the ERW
linepipes.
Figure 4.7 shows the ZRA curves for 10 bar CO2, 90 ºC, for all samples. X42-A HAZ 2
and X42-B HAZ 3 experienced rapid anodic attack, with current densities peaking at 2140
and 2900 µA/cm2, equating to an instantaneous corrosion rate of 24.8 and 33.6 mm/y,
respectively. After the peak, the current densities decayed to zero and a state of galvanic
passivation occurred. This would imply that from the point of view of the electrolyte, all
corrosion product layers became similar, and the intrinsic corrosion potentials of each
microstructural zone became equal.
A similar type of galvanic passivation was also observed for the seamless X42-S
sample. Three of the seamless electrodes (E2, E3, and E4) randomly became dominate
anodes, with E2 peaking at 483 µA/cm2, equivalent to an instantaneous corrosion rate of
5.1 mm/y (Figure 4.7). After this peak the current densities decayed to zero and a state of
galvanic passivation was reached. This is a good example of how localized corrosion can
occur in a seamless linepipe. Despite all the X42-S electrodes being nominally identical,
there are always subtle differences between one location on the linepipe and another. When
a corrosion product layer, for some reason, precipitates faster at one location and slower at
another, there is a constant variation of intrinsic corrosion potentials all over the steel
surface. This slight variation in intrinsic corrosion potentials is then balanced by current flow,
and some areas are attacked. It should be noted that the current density peaks for the
seamless X42-S were still considerably less than X42-A and X42-B, due to its more uniform
microstructure. It is also important to note that localized attack in a seamless linepipe is
constantly randomized, unlike X42-A and X42-B, where the same region was always
attacked.
It is interesting that X42-C did not quite reach galvanic passivation like the other
samples, although its current densities were still comparatively low (Figure 4.7). The WM
was attacked, peaking at 648 µA/cm2, equivalent to an instantaneous corrosion rate of
7.5 mm/y (Figure 4.7). The current densities then started to decay, although were not able to
reach near-zero levels by the end of the experiment. It is possible that due to the lower
carbon content of X42-C, and weaker interconnected cementite network, siderite
60
precipitation may have been more difficult than the other samples. This is discussed in more
detail in Section 4.3.4.
4.3.1.2.5 Coupling ferritic pearlitic linepipe to quenched

and tempered
The majority of the X42-B linepipe was ferritic pearlitic, with the notable exception of
HAZ 3, which resembled a quenched and tempered microstructure. HAZ 3 was consistently
a strong anode and was locally attacked in all experiments. This is somewhat concerning as
often in the field normalized ferritic pearlitic linepipes may be welded to quenched and
tempered linepipes. In fact, the author was recently involved in a case of CO2 preferential
weld corrosion where a 1 m section of a normalized ferritic pearlitic linepipe was replaced
with a quenched and tempered linepipe of similar chemical composition (Table 4.2). While
both linepipes had almost identical chemical composition, the quenched and tempered side
of the girth weld had experienced a large wall thickness reduction (Figure 4.8).
The 1 bar CO2, 60 ºC experiment was repeated (experiment ID: 1-60-C) using a
special five-segment ZRA electrode. Three of the electrodes were taken from the seamless
X42-S linepipe which had a normalized ferritic pearlitic microstructure (Figure 3.12). The
remaining two electrodes were taken from the seamless L80-S quenched and tempered
linepipe, with chemical composition given in Table 3.2 and nominal microstructure by Figure
3.26. All electrodes had the same surface area of approx. 0.60 cm2. If quenched and
tempered microstructures such as X42-B HAZ 3 are strongly anodic relative to normalized
ferritic pearlitic ones, as indicated by the multi-channel ZRA experiments (Figure 4.4 and
Figure 4.5), then the L80-S electrodes should become dominant anodes.
The ZRA curves for X42-B and the special coupled X42-S/L80-S electrodes are shown
by Figure 4.9. The X42-S/L80-S curves clearly show that quenched and tempered linepipe
behaves anodically relative to normalized ferritic pearlitic linepipe. This is in agreement with
the X42-B HAZ 3 microstructural zone being strongly anodic. This serves as a warning that
coupling similar carbon steels with different heat treatments can causes localized galvanic
attack in CO2 environments.
61
4000
X42-A X42-B X42-C X42-S
46

WM WM WM E1
3000 HAZ 2 HAZ 2 HAZ 2 E3 35
HAZ 3 HAZ 3 BM 1 E4
BM BM BM 2 E5
2000 23
1000 12
0 0
-1000
0 48 96 144 0 48 96 144 0 48 96 144 0 48 96 144

Figure 4.6: ZRA curves for 10 bar CO2, 60 ºC, showing galvanic current densities for ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe. Electrolyte 3%
NaCl, 150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive values are anodic.
62
X42-A X42-B X42-C X42-S
3500
40
Equivilent Corrosion Rate (mm/y)

3000 35
2500 E1 29
WM WM WM
2000 HAZ 1 HAZ 1 HAZ 1 E2 23
1500 HAZ 3 HAZ 3 BM 1 E4 17
BM BM BM 2 E5
1000 11
500 6
0 0
-500
-1000
-1500
0 48 96 144 0 48 96 144 0 48 96 144 0 48 96 144
Figure 4.7: Current density curves for 10 bar CO2, 90 ºC, showing galvanic passivation for X42-A, X42-B, and X42-S. Electrolyte 3% NaCl, 150 RPM (approx. 0.5
m/s). Surface area ratio 1:1. Positive values are anodic.
63
Table 4.2: Chemical composition (wt%) of flowlines from CO2 containing oil field.
C Si S P Mn Ni Cr Mo V Cu Ti Nb
Normalized ferritic pearlitic linepipe
0.21 0.25 0.002 0.008 0.51 0.14 0.09 0.02 0.002 0.20 0.004 0.002
Quenched and tempered linepipe
0.21 0.19 0.001 0.005 0.46 0.13 0.07 0.02 0.002 0.16 0.005 0.002
Figure 4.8: Etched cross section (3% Nital) of girth weld joining a quenched and tempered linepipe to a
normalized ferritic pearlitic linepipe.
X42-B X42-B
400 4.6
Glavanic Current Density (µA/cm2)
1-60-A 1-60-C
300 3.5
200 2.3
100 1.2
0 0
-100
WM
-200 HAZ 1
HAZ 2 X42-S L80-S
-300 HAZ 3 X42-S L80-S
BM X42-S
-400
0 48 96 144 0 48 96 144
Figure 4.9: ZRA curves for 1 bar CO2, 60 ºC for X42-B (left), and the coupling of normalized ferritic
pearlitic seamless linepipe (X42-S) to a quenched and tempered seamless linepipe (L80-S) (right).
Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive values are anodic.
64
4.3.2 Scanning electron microscopy (SEM)
The multi-channel ZRA results (Section 4.3.1) clearly showed localized attack of ERW
linepipe was time dependent, suggesting a reliance on corrosion product layer growth. The
performance of the four linepipes can be broadly summarised as follows:
► X42-A and X42-B had significant microstructural variations across the ERW
weld region, and both showed the highest susceptibility to localized corrosion.
► X42-C had very uniform microstructure across the ERW weld region, and
showed a significantly lower susceptibility to localized corrosion than X42-A
and X42-B.
► X42-S, which being a seamless linepipe had nominally uniform microstructure
throughout, consistently showed the lowest susceptibility to localized corrosion
in all test conditions.
SEM examination revealed the different ERW microstructural zones of X42-A and
X42-B grew significantly morphologically different corrosion product layers, whereas X42-C
and the seamless X42-S, for the most part, did not.
4.3.2.1 X42-A and X42-B
At 1 bar CO2, 90 ºC, X42-B had strong galvanic interactions, with HAZ 2, HAZ 3, and
the BM being strong anodes, and the WM and HAZ 1 being strong cathodes. However, for
the same test condition, the seamless linepipe had negligible galvanic interactions (Figure
4.3). Cross sections of the corrosion product layers gave insight into why this occurred.
Shown in Figure 4.10, the anodic microstructural zones for X42-B preferentially precipitated
siderite at the centre of the cementite film, whereas the cathodic microstructures precipitated
siderite directly at the steel/cementite interface. This was a significant modification to the
surface, and set up strong galvanic couples (Figure 4.2). By comparison, all of the seamless
electrodes precipitated siderite at the same location (Figure 4.11). Therefore while the
seamless electrodes were modified by the corrosion process, they were all modified at the
same rate and in the same way, making the relative differences negligible.
SEM cross sections were made for all linepipe samples for the 10 bar CO2, 60 ºC test
condition, and again, galvanic interactions could be related to differences in corrosion
product layer morphology. This was a severe test condition and X42-A HAZ 2 and X42-B
HAZ 3 were strongly attacked.
Figure 4.12 shows the corrosion product layer on X42-A HAZ 2 was an order of
magnitude thinner than the other films. As HAZ 2 was a region where cementite was present
as isolated particles, rather than the interconnected bands seen in the other X42-A
65
microstructural zones, this observation was not surprising. If present as discrete particles,
rather than an interconnected network, as the ferrite corrodes there is no mechanical
strength holding the cementite layer together. The particles are simply washed away, and
the cementite sponge-like layer does not form, making local saturation and siderite
precipitation more difficult. The other microstructures all formed thick cementite layers with
siderite precipitating at the centre. This results in the HAZ 2 surface being considerably
different than the other microstructural zones, and strong galvanic couples develop.
X42-B HAZ 3 was also severely attacked at 10 bar CO2, 60 ºC, and Figure 4.14 shows
its corrosion product layer was also significantly thinner than the others. The cathodic
microstructures (WM, HAZ 1, HAZ 2) formed dense siderite layers at the steel/cementite
interface, and not in the middle of the cementite layer, as was seen for X42-A. The notable
difference is that the cathodic current densities for X42-B were typically twice that of X42-A,
meaning the production of bicarbonate on the X42-B cathodes occurred twice as fast,
magnifying the local alkalinisation effect. Also, the larger cathodic current densities would
decrease the production rate of Fe2+ at the cathodes, lowering the driving force for chloride
electro-migration and internal acidification (Section 4.3.2.5.2).
X42-B HAZ 3’s corrosion product layer was considerably thicker at 1 bar CO2, 90 ºC
compared to 10 bar CO2, 60 ºC (Figure 4.10 and Figure 4.14). This could be related to
siderite being able to precipitate more easily at 1 bar CO2, 90 ºC, increasing the mechanical
strength of the corrosion product layer. As the ferrite corrodes, a porous cementite mesh is
left behind. For the case of HAZ 3, most of the cementite is present as poorly interconnected
particles at the grain boundaries (Figure 3.8), making the mesh brittle. As Figure 4.16 and
Figure 4.17 show, siderite has a tendency to precipitate directly on the cementite in this
porous mesh. This is most likely because the cathodic reaction occurs on the cementite
substrate, which causes local alkalinisation. Also, heterogeneous nucleation (i.e. on a
surface) is thermodynamically easier than homogenous nucleation. The combination of the
bulk solution being less acidic at 1 bar CO2, and the higher temperature of 90 ºC, makes
siderite precipitation generally easier. Therefore, as the ferrite in HAZ 3 corrodes, leaving
behind a fragile cementite network, the faster precipitation of siderite on the freshly exposed
cementite may somewhat act as a ‘glue’ holding the corrosion product layer together. A
thicker layer therefore results for 1 bar CO2, 90 ºC compared to 10 bar CO2, 60 ºC. This
theory was further confirmed by SEM analysis of X42-B at 1 bar CO2, 60 ºC (Figure 4.18),
where siderite precipitation is considerably more difficult than at 1 bar CO2, 90 ºC. It can be
seen under the more difficult siderite precipitation conditions, HAZ 3’s corrosion product
layer was again significantly thinner than the other microstructural zones.
66
4.3.2.1 X42-C
While X42A and X42-B showed a strong susceptibility to localized corrosion at 10 bar
CO2, 60 ºC, X42-C showed almost none. In fact, the galvanic interactions for X42-C at
10 bar CO2, 60 ºC were essentially equal to the seamless X42-S sample (Figure 4.4). The
low level of galvanic interactions between the different microstructural zones for X42-C at
such a severe test condition were reflected in its SEM cross sections. Figure 4.19 shows all
the different microstructural zones (WM, HAZ 1, HAZ 2, BM 1, BM 2) formed morphologically
similar empty cementite corrosion product layers. The layers were the remnants of an
interconnected cementite network. The corrosion product layer on the WM was more broken
than the rest, due to the cementite phase been less interconnected at the weld seam from
the upsetting process. The cementite layer was also considerably more broken for the BM 1
and BM 2 electrodes compared to the HAZ 1 and HAZ 2 electrodes. This makes sense, as
HAZ 1 and HAZ 2 were normalized with equiaxed grains, therefore the cementite phase
would be more interconnected than the worked BM 1 and BM 2 microstructures.
Nevertheless, the overall morphology of the corrosion product layers were similar, so while
there were modifications to the surface of the material, each microstructural zone was
modified in a similar way, and no significant galvanic couples developed.
4.3.2.2 X42-S
Overall the X42-S showed a low susceptibility to localized corrosion, which was
expected as its five-segment ZRA electrode was made from five random cross sections of
the nominally uniform seamless linepipe.
The three ERW linepipes had significant galvanic interactions for 1 bar CO2, 90 ºC,
however, the seamless sample was negligible (Figure 4.2). SEM cross sections of X42-S
(Figure 4.11) showed each electrode had formed similar corrosion product layers, and
therefore no significant galvanic couples were established.
The test condition of 10 bar CO2, 60 ºC was severe for X42-A and X42-B, as some
microstructural zones had greater difficulty than others with regards to siderite precipitation.
As Figure 4.6 shows, the galvanic interactions for X42-S were almost negligible for the first
130 hours, until E1 experienced a sudden anodic current spike. This suggests all seamless
electrodes had similar corrosion product layers, and then suddenly E1 experienced a break
in its film. The SEM cross sections shown by Figure 4.21 confirm this was indeed the case.
The E1 electrode is almost completely bare, while all other electrodes have morphologically
similar corrosion product layers. The break on E1 would have suddenly exposed fresh steel,
forcing E1’s intrinsic corrosion potential into the active (negative) direction, and immediately
67
establishing a galvanic couple. This is an example of mesa attack in a seamless linepipe.
The corrosion product layer may have broken due to flow stresses, or perhaps intrinsic
growth stresses within the layer starting to exceed the layer’s yield strength, causing a
sudden breakage60. The positive aspect of seamless linepipe is that while this area would be
locally attacked for the short term, it would naturally develop a corrosion product layer similar
to the others, as its microstructure is the same, and the galvanic couple would decay. With
X42-A and X42-B, however, whether the films occasionally break or not, the different
microstructural zones present will always want to form different corrosion product layers, and
the same regions will always be attacked.
It should also be noted from Figure 4.6 that the galvanic currents for X42-S after the
establishment of mesa attack were still significantly less than X42-A and X42-B. This is
explained by the significant levels of siderite present in the corrosion product layers of the
other electrodes (E2 to E5, Figure 4.21). Remember, the galvanic couples form due to the
formation of different corrosion product layers, however, cementite is cathodic relative to
ferrite, and siderite has poor conductivity61. Therefore the precipitation of siderite in the
cementite mesh essentially reduces the cathodic area. This ‘blocking’ effect of the cathodic
reaction means when there is a localized breakage, even though it exposes a large area of
fresh steel, the galvanic driving forces are reduced due to the cathodic area restriction. This
will also help minimise the local acidification effect at anode, assisting with faster siderite
formation.
68
Sample ID: X42-B
Test Condition: 1 bar CO2, 90 ºC, 3% NaCl, 150 RPM
Test Duration: 168 hours
WM HAZ 1
HAZ 2 HAZ 3
BM
Figure 4.10: SEM BSD cross sections of X42-B, for 1 bar CO2, 90 ºC showing different corrosion product
layers forming on each microstructural zone. HAZ 2, HAZ 3, BM were dominant anodes.
69
Sample ID: X42-S
E1 E2
E3 E4
E5
Figure 4.11: SEM BSD cross sections of X42-S for 1 bar CO2, 90 ºC showing all seamless electrodes
having similar corrosion product layers which resulted in no localized attack.
70
Sample ID: X42-A
WM HAZ 1
HAZ 2 HAZ 3
BM
Figure 4.12: SEM BSD cross sections of X42-A for 10 bar CO2, 60 ºC showing different corrosion product
layers forming on each microstructural zone. HAZ 2 was dominant anode.
71
Sample ID: X42-A
WM HAZ 1 HAZ 2 HAZ 3 BM

SEM BSD
EDX Element Mapping
Figure 4.13: EDX element mapping of X42-A for 10 bar CO2, 60 ºC, showing chloride concentrations (bright colour) in corrosion product layers.
72
Sample ID: X42-B
WM HAZ 1
HAZ 2 HAZ 3
BM
Figure 4.14: SEM BSD cross sections of X42-B for 10 bar CO2, 60 ºC, showing different corrosion product
layers formed on each microstructural zone. HAZ 3 was the dominant anode.
73
Sample ID: X42-B
WM HAZ 1 HAZ 2 HAZ 3 BM

SEM BSD
EDX Element Mapping
Figure 4.15: EDX element mapping of X42-B for 10 bar CO2, 60 ºC, showing chloride concentrations (bright colour) in corrosion product layers.
74
Figure 4.16: SEM BSD image of X42-B WM, showing siderite (bright area) precipitating on cementite
(remnants of pearlite banding) for 1 bar CO2, 90 ºC. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s).
Figure 4.17: SEM BSD image of X42-B HAZ 3, showing siderite (bright area) precipitating on cementite
(dark area) for 1 bar CO2, 90 ºC. Image also shows the remnants Al, Mn, Ca, S rich inclusion. Electrolyte
3% NaCl, 150 RPM (approx. 0.5 m/s).
75
Sample ID: X42-B
WM HAZ 1
HAZ 2 HAZ 3
BM
Figure 4.18: SEM BSD cross sections of X42-B for 1 bar CO2, 60 ºC, showing different corrosion product
layers formed on each microstructural zone. HAZ 2 and HAZ 3 were dominant anodes.
76
Sample ID: X42-C
WM HAZ 1
HAZ 2 BM 1
BM 2
Figure 4.19: SEM BSD cross sections of X42-C for 10 bar CO2, 60 ºC, showing different corrosion product
layers formed on each microstructural zone.
77
Sample ID: X42-C
WM HAZ 1 HAZ 2 BM 1 BM 2
SEM BSD
EDX Element Mapping
Figure 4.20: EDX element mapping of X42-C for 10 bar CO2, 60 ºC, showing chloride concentrations (bright colour) in corrosion product layers.
78
Sample ID: X42-S
E1 E2
E3 E4
E5
Figure 4.21: SEM BSD cross sections of seamless X42-S for 10 bar CO2, 60 ºC, showing corrosion product
layers formed on each electrode of nominally identical microstructure.
79
Sample ID: X42-S
E1 E2 E3 E4 E5
SEM BSD
EDX Element Mapping
Figure 4.22: EDX element mapping of X42-S for 10 bar CO2, 60 ºC, showing chloride concentrations (bright colour) in corrosion product layers.
80
4.3.2.3 Galvanic Passivation
The case of galvanic passivation seen at 10 bar CO2, 90 ºC for X42-A, X42-B, and
X42-S (Figure 4.7), would imply corrosion was sufficiently rapid enough to form
morphologically similar corrosion product layers. Figure 4.23 (X42-A), Figure 4.24 (X42-B),
and Figure 4.26 (X42-S) show this to be the case.
4.3.2.3.1 X42-A
X42-A HAZ 2 was constantly susceptible to PWC (Figure 4.3 and Figure 4.4). As
shown in Figure 4.12, this was attributed to HAZ 2 having different siderite precipitation
kinetics compared to the other microstructural zones, forming a significantly thinner and
morphologically different corrosion product layer. The 10 bar CO2, 90 ºC test condition was
severe, indicated by HAZ 2 reaching an instantaneous corrosion rate of 24.8 mm/y (Figure
4.7). However, in this particular situation the corrosion rate was so severe it allowed HAZ 2
to form a denser and thicker corrosion product layer filled with siderite, as shown by Figure
4.23. This resulted in, from the point of view from the electrolyte, all microstructural zones
being similar. It can be seen in Figure 4.23 that originally a thin corrosion product layer
existed on HAZ 2, however, eventually with the accelerated anodic dissolution of ferrous
ions from the strong galvanic attack, forming a dense outer siderite layer became
unavoidable. After the dense outer layer formed, the galvanic current densities decayed to
near-zero (Figure 4.7).
4.3.2.3.2 X42-B
The consistent localized attack of X42-B HAZ 3 was also attributed to it having
significantly different siderite precipitation kinetics and forming a considerably thinner
corrosion product layer (Figure 4.14). For the 10 bar CO2, 90 ºC test condition, the WM,
HAZ 1, HAZ 2, and the BM were strong cathodes (Figure 4.7), and Figure 4.24 shows they
all formed dense siderite layers at the steel/cementite interface. From these cross sections it
is obvious that the cementite layer formed first, then siderite precipitated later when local
saturation was achieved. HAZ 3 was strongly anodic and reached an instantaneous
corrosion rate of 33.6 mm/y. Its cross section suggests ferrite initially corroded and left
behind a poorly interconnected cementite network, prone to breaking away. At this stage
only a thin layer had formed, similar to Figure 4.14. However, when the corrosion rate
became sufficiently rapid, the massive production of ferrous ions made siderite precipitation
unavoidable, and a dense outer siderite layer formed. The hollow region in the middle of
HAZ 3’s film suggests internal acidification, and EDX element mapping confirmed high
81
chloride concentrations at the steel/cementite interface (Section 4.3.2.5.2). Similar to X42-A,
once this dense outer siderite layer formed on HAZ 3, the galvanic current densities started
to decay to near-zero.
4.3.2.3.3 X42-C
X42-C did not reach full galvanic passivation during the 10 bar CO2, 90 ºC
experiments, however, it was approaching galvanic passivation. Its ZRA curves show the
WM was preferentially attack, similar to the 1 bar CO2, 90 ºC experiments, and then the
galvanic current densities slowly started to decay (Figure 4.7). The magnitude of galvanic
attack for X42-C was significantly less than X42-A and X42-B, and was similar to the level
observed for the seamless X42-S linepipe. Corrosion product layers are shown by Figure
4.25, where the WM and BM 2 electrodes have a notable hollow section at the
steel/cementite interface. This was not surprising as the WM and BM 2 were the two anodic
electrodes during the experiment.
4.3.2.3.4 X42-S
The seamless X42-S sample experienced random localized attack on electrodes E2,
E3, and E4, with a peak instantaneous corrosion rate of 6 mm/y (Figure 4.7). However, the
currents quickly decayed to near-zero, and as Figure 4.26 shows, all electrodes have similar
corrosion product layers.
82
Sample ID: X42-A
WM HAZ 1
HAZ 2 HAZ 3
BM
Figure 4.23: SEM BSD cross sections of X42-A for 10 bar CO2, 90 ºC, showing corrosion product layers
after galvanic passivation had occurred.
83
Sample ID: X42-B
WM HAZ 1
HAZ 2 HAZ 3
BM
Figure 4.24: SEM BSD cross sections of X42-B for 10 bar CO2, 90 ºC, showing corrosion product layers
84
Sample ID: X42-C
WM HAZ 1
HAZ 2 BM 1
BM 2
Figure 4.25: SEM BSD cross sections of X42-C for 10 bar CO2, 90 ºC, showing corrosion product layers.
85
Sample ID: X42-S
E1 E2
E3 E4
E5
Figure 4.26: SEM BSD cross sections of X42-S for 10 bar CO2, 90 ºC, showing corrosion product layers
86
HAZ 3 HAZ 2 HAZ 1 HAZ 1
BM WM
Figure 4.27: Photomicrograph of X42-B coupon after 168 hours at 10 bar CO2, 90 ºC. Red line indicates cross section location. Cross section insert etched in 3% Nital, revealing localized
attack of HAZ 3. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s).
87
BM HAZ 2 WM
HAZ 3 / BM Transition HAZ 3 HAZ 1
Figure 4.28: Optical micrograph of X42-B coupon after 168 hours at 10 bar CO2, 90 ºC, showing localized attack at HAZ 3. Etched 3% Nital. Electrolyte 3% NaCl, 150 RPM (0.5 m/s).
88
Figure 4.29: SEM BSD images of corrosion product layers formed on the X42-B coupon at 10 bar CO2, 90 ºC after 168 hours in as-polished condition (top), and optical micrograph etched in
3% Nital (bottom). Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s).
89
Sample ID: X42-B Coupon
Test Condition: 10 bar CO2, 90 ºC,
Coupon
SEM BSD
HAZ 3 HAZ 2
EDX Element Mapping
Figure 4.30: EDX element mapping of X42-B coupon for 10 bar CO2, 90 ºC, showing chlorine, oxygen, and iron concentrations (bright colours).
90
4.3.2.4 Comparison with coupon tests
The multi-channel ZRA experiments showed some microstructural regions of ERW

linepipe were susceptible to localized galvanic attack as different corrosion products grew.
X42-B HAZ 3 was severely attacked at 10 bar CO2, 90 ºC, reaching a peak instantaneous
localized corrosion rate of 33.6 mm/y before galvanic passivation occurred (Figure 4.7). SEM
analysis of the multi-channel ZRA electrodes found all microstructural zones eventually
formed a dense siderite layer, with HAZ 3 having a hollow region in the centre (Figure 4.24).
To verify the multi-channel ZRA measurements, a coupon of X42-B that included the weld
seam, all of the HAZs, and part pf the BM was prepared and embedded under pressure in
Bakelite. The coupon was placed into the stirring autoclave and the 10 bar CO2, 90 ºC
experiment was repeated (experiment ID: 10-90-B, Table 4.1). If HAZ 3 was indeed attacked
to the extent indicated by the multi-channel ZRA measurements, one would expect to see
considerable mass loss at the HAZ 3 region of the coupon.
A photomicrograph of the X42-B coupon after repeating the 10 bar CO2, 90 ºC

experiment (168 hours) is shown by Figure 4.27. The corrosion product layer in the HAZ 3
region is considerably different than the rest, and an etched cross section (indicated by the
dashed red line) confirmed the HAZ 3 microstructural zone was preferentially attacked.
Although to a lesser extent, a small region just left of the HAZ 3 boundary was also attacked.
The larger optical micrographs shown by Figure 4.28 show this region still contained a
significant amount of the HAZ 3 microstructure, and was essentially a transition zone where
HAZ 3 turned into the nominal BM microstructure.
SEM BSD images of the corrosion product layer in the as-polished condition (before
3% Nital etching) are shown by Figure 4.29. Comparison to Figure 4.24 show the corrosion
product layer formed on the X42-B coupon and the multi-channel ZRA electrodes are in
agreement. In both cases the corrosion product layer of HAZ 3 contains a large hollow
section.
The coupon tests therefore verified the findings of the multi-channel ZRA
measurements, that HAZ 3 is severely attacked by galvanic currents. An interesting point is
that the AGCD168hrs value measured by the multi-channel ZRA for X42-B for this test
condition was 7.7 mm/y (Figure 4.4), therefore over a 168 hour test period the depth of
attack should be approx. 147 µm. The X42-B coupon SEM images (Figure 4.29) show an
attack depth closer to 500 µm. This is simply explained by differences in microstructural
zone surface area. The ZRA curves (Figure 4.7) showed the WM and HAZ 1 were extremely
cathodic, and after an initial period the BM also became cathodic. The cathode provides the
91
driving force for galvanic attack, and the microstructural zones on the multi-channel ZRA all
had 1:1 surface area ratios. This was clearly not the case for the X42-B coupon (Figure
4.27), where the surface area of HAZ 1 and the BM were significantly larger than the other
microstructural zones. This of course increases the driving force for the galvanic attack of
HAZ 3, and a greater attack depth results.
4.3.2.5 Location of siderite precipitation
As discussed above, different microstructural zones were able to form morphologically

different corrosion product layers, and this was able to establish significant galvanic couples
that led to localized attack. An interesting observation from the SEM cross-sections was that
sometimes siderite precipitated directly at the steel/cementite interface, and sometimes it
precipitated at the centre of the cementite film. As discussed in Section 4.3.2.5.2, EDX
element mapping of the corrosion product layers suggested this behaviour was due to the
preferential electro-migration of chloride ions leading to internal acidification.
4.3.2.5.1 Macro and micro-galvanic couples
As shown by Figure 3.3, the multi-channel ZRA consists of five electrodes, and each
electrode corresponds to a different microstructural zone that was present in the ERW weld.
The multi-channel ZRA measures macro-galvanic couples, i.e. the galvanic currents flowing
between the different microstructural zones (WM, HAZ 1, HAZ 2, HAZ 3, and the BM). In
addition to this, there are also micro-galvanic couples occurring on each electrode, and this
behaviour is not captured by the ZRA. A cross section of a typical five-segment electrode is
illustrated by Figure 4.31. As each electrode starts to corrode, ferrite dissolves and leaves
behind a thin cementite corrosion product layer with a unique morphology (shown in red).
Cementite is cathodic relative to the un-corroded steel electrode (shown in grey), and a
micro-galvanic couple forms where electron current flows from the anodic un-corroded steel
to the cathodic cementite (blue arrows). Therefore the formation of the cementite corrosion
product layer acually accelerates the corrosion process. However, as each electrode is a
different microstrucural zones, and it forms morphalogically different corrosion product
layers, macro-galvanic couples are also formed between each ZRA electrode. The
macro-galvanic coupling currents (electron current) are shown by the black arrows in Figure
4.31, and are drawn in the direction such that the WM, HAZ 1, and HAZ 2 are cathodic (i.e.
receiving electrons) and HAZ 3 and the BM are anodic (i.e. losing electrons).
If we define electron current flow leaving an electrode as postive (anodic electron

current), and entering as negative (cathodic electron current), then the net electron current
flow for a microstrucural zone can be calculated by (4.1). It is important to note that Imacro
92
may be positive or negative, however, Imicro is always positive. Therfore if a microstrucural
zone is macro-galvanically cathodic, this supply of electrons from the other electrodes on the
macro-galvanic level compensates for the electrons lost on the micro-galvanic level. If
sufficiently high macro-galvanic electron current is delivered, the accelerated corrosion
caused by the galvanic couple between the uncorroded steel and the cementite corrosion
product layer can be completey stopped.
I I I
(4.1)
Imicro
Imacro
Figure 4.31: Cross section of the multi-channel “hockey puck” style five-segment ZRA electrode shown
in Figure 3.3, illustrating macro-galvanic couples between different microstructural zones (black arrows,
electron current), and micro-galvanic couples between each microstructural zone and its corrosion
product layer (blue arrows, electron current) couples.
4.3.2.5.2 Electro-migration of chlorides
The cathodic microstructures of X42-A for the 10 bar CO2, 60 ºC condition (WM,
HAZ 1, HAZ 3, BM) all precipitated siderite at the centre of the cementite layer, not at the
steel/cementite interface (Figure 4.12). This is counter intuitive as the ferrous ion
concentration would be highest at the steel/cementite interface, and therefore siderite
precipitation should be easiest at this location. EDX element mapping of the corrosion
product layers showed chlorides had accumulated at the steel/cementite interface (Figure
4.13), which suggests a type of internal acidification had taken place61. Similar to pitting
corrosion, negatively charged chloride ions are attracted by the accumulation of positively
charged ferrous ions at the steel/cementite interface (Figure 4.32). They form iron chloride
and then hydrolyse to hydrochloric acid and ferrous hydroxide, resulting in local acidification
at the steel/cementite interface. The cathodic reaction occurring on the cementite layer
removes H+ ions, causing local alkalinisation. However, as the delivery of reducible species
from the bulk solution is fastest at the cementite/bulk solution interface, this region has a
higher pH (Figure 4.33). Therefore the location for siderite precipitation, which is determined
by the saturation factor (Section 2.1.2) is a compromise between the steel/cementite
93
interface with higher Fe2+ concentration and lower pH, and the cementite/bulk solution
interface with lower Fe2+ concentration and higher pH (Figure 4.34).
For the same test condition, the cathodic microstructures of X42-B (WM, HAZ 1, HAZ
2) formed dense siderite layers at the steel/cementite interface (Figure 4.14), and not in the
middle of the cementite layer, as was seen for X42-A. The notable difference is that the
cathodic current densities for X42-B were typically twice that of X42-A, meaning the
production of bicarbonate on the X42-B cathodes occurred twice as fast, magnifying the
local alkalinisation effect. Also, the larger cathodic current densities would decrease the
production rate of Fe2+ at the cathodes, lowering the driving force for chloride electro-
migration and internal acidification. This was supported by EDX element mapping of the
corrosion product layers, which could not find chloride concentrations at the steel/cementite
interface of the cathodic microstructures (Figure 4.15). Chlorides were found, however, at
the steel/cementite interface of HAZ 3 and the BM. This indicated internal acidification
occurred at HAZ 3 and the BM electrode, which was supported by the fact siderite
precipitated in the middle of the BM cementite layer and not at the steel/cementite interface.
SEM images of X42-B for the 10 bar CO2, 90 ºC condition, where galvanic passivation
occurred, showed all microstructural zones ultimately formed dense siderite layers (Figure
4.24). The notable difference was HAZ 3 had a large hollow section in the middle. The same
was observed on the X42-B coupon in the repeated experiment (Figure 4.29), and EDX
element mapping of the coupon revealed chlorides accumulated on the steel/cementite
interface only for HAZ 3 (Figure 4.30), and not at the other microstructural zones. This
further supports the theory of internal acidification by chloride migration to the surface of
strongly anodic microstructural zones.
X42-C did not precipitate siderite in any of its corrosion product layers at 10 bar CO2,
60 ºC (Figure 4.19). All the corrosion product layers were somewhat broken empty
cementite, and EDX mapping showed all had attracted chlorides to the steel/cementite
interface in approximately equal amounts (Figure 4.20). Most likely the porous cementite
layers on the electrode surfaces were sufficient to establish micro-galvanic couples (Section
4.3.2.5.1) causing Fe2+ production, which attracted chlorides and caused some acidification.
Siderite precipitated in the middle of the cementite layer for the seamless X42-S
sample at 10 bar CO2, 60 ºC (Figure 4.21) for electrode E2, E3, E4, and E5. As discussed in
Section 4.3.1.2.3, E1 suffered a film breakage after 130 hours, however, as galvanic
interactions were negligible beforehand, its corrosion product layer would have had similar
morphology. The precipitation of siderite away from the steel/cementite interface suggests
94
internal acidification occurred, and this was supported by EDX element mapping finding
chloride concentrations at the interface (Figure 4.22).
4.3.2.5.3 Influencing factors in siderite precipitation
Siderite precipitation is made easier as the local ferrous ion concentration increases,
and as the local pH becomes more alkaline. From the above observations, it appears the
precipitation of siderite is influenced by two main factors:
1. The micro-galvanic couple formed between the cementite corrosion product layer
and the un-corroded steel. This locally accelerates corrosion which increases the
local ferrous ion concentration at the steel/cementite surface. While this makes
siderite precipitation easier, it also attracts chloride ions leading to local
acidification, which hinders precipitation near the steel/cementite interface. This
situation results when a microstructural zone is anodic (e.g. X42-B BM), or when
the delivered cathodic current density is insufficient to compensate fully for the
micro-galvanic coupling effects (e.g. X42-A WM).
2. The macro-galvanic couples formed between different microstructural zones. The
delivery of macro-galvanic cathodic electron current reduces the magnitude of the
micro-galvanic couple between the cementite corrosion product layer and the
un-corroded steel. While this reduces the local ferrous ion concentration, it also
reduces the driving force for chloride electro-migration, preventing internal
acidification at the steel/cementite interface. Also, if the cathodic current density is
sufficiently high, it accelerates the cathodic reaction on the cementite surface,
increasing the production of bicarbonate ions, further increasing the local pH.
Therefore when very high cathodic current densities are delivered, such as with
X42-B WM, HAZ 1, and HAZ 2 (Figure 4.14), the combination of increased
bicarbonate ion production and reduced chloride electro-migration allows siderite to
precipitate directly at the steel/cementite interface.
95
Bulk solution/cementite Steel/cementite
interface interface
‐ 2+
Cl Fe
-
Cl Fe
2+
- 2+
Cl Fe
- 2+
Cl Fe
2+
Fe
2+
Fe
2+
Fe
Bulk NaCl solution Cementite layer Steel
Figure 4.32: Chloride ions from the bulk solution attracted by the accumulation of Fe2+ ions at the
steel/cementite interface.
Bulk solution/cementite Steel/cementite

interface interface
2+
H2CO3 Fe
HCl
2+
H2CO3 Fe
2+
Fe
HCl
Turbulent HCO3- 2+
flow Fe
HCO3-
HCl
2+
H2CO3 Fe
2+
Fe
2+
Fe
HCO3- HCl
Bulk NaCl solution Cementite layer Steel
Figure 4.33: Acidification at the steel/cementite interface from the production of hydrochloric acid, and
alkalinisation at the bulk solution/cementite interface from bicarbonate production.
96
Easiest location for
siderite precipitation
Saturation factor
Magnitude
pH
2+
Fe
Bulk solution Cementite Steel

layer
Figure 4.34: The combined effects of Fe2+ accumulation, chloride migration (internal acidification), and
bicarbonate production on the siderite saturation factor.
4.3.3 Effect of surface area and response to pressure changes
In the previous experiments, the different microstructural zones on the five-segment

ZRA electrode had surface area ratios of 1:1. This prevented distortion of the ZRA curves
due to an imbalance in driving forces. Nevertheless, in reality the BM surface area of an
ERW linepipe is significantly larger than the WM and HAZs. The 1 bar CO2, 60 ºC
experiments were repeated for the two most susceptible samples to localized corrosion,
X42-A and X42-B. The repeated experiment (experiment ID: 1-60-B, Table 4.1) consisted of
the normal five-segment electrodes with each microstructural zone having a surface area
ratio of 1:1, and a modified five-segment electrode where the BM surface area was
increased by a factor of 15. During the repeated experiment (experiment ID: 1-60-B) the CO2
partial pressure was increased from 1 bar to 2 bar to investigate the response of each
microstructural zone.
4.3.3.1 X42-A
Figure 4.35 compares the ZRA curves from the original 1 bar CO2, 60 ºC experiment
(experiment ID: 1-60-A) where all electrodes (microstructural zones) had 1:1 surface area
ratios, to the repeated experiment (experiment ID: 1-60-B) that included both the standard
97
1:1 electrodes and the specially modified electrodes where the BM surface area was
increased by a factor of 15. The ZRA curves show that:
1. There is excellent agreement between the 1-60-A and 1-60-B ZRA curves for the
1:1 electrodes, indicating excellent repeatability of the measurements.
2. Regardless of BM surface area, HAZ 2 remained the dominant anode, and was
subjected to localized attack.
3. When all microstructural zones had surface area ratios of 1:1, the WM and HAZ 2
were attacked. When the BM surface area was increased by a factor of 15, the WM
was strongly attacked for the first 12 hours, but then its anodic current density
started to decay and ultimately became cathodic. The larger BM surface area
increased the attack rate of HAZ 2.
4. Increasing the pCO2 from 1 bar to 2 bar at approximately 120 hours increased the
localized attack rate of HAZ 2 (Figure 4.35).
From the points above, the most significant is that by increasing the BM surface area,
which more accurately models real-word conditions, attack of HAZ 2 was increased. This
was expected because in the 1:1 experiments (1-60-A and 1-60-B) the BM was cathodic,
meaning it was somewhat of a driving force for the galvanic attack of the WM and HAZ 2. By
increasing the cathodic surface area, the driving force for galvanic attack is therefore
increased.
The switching of the WM from anodic to cathodic by increasing the surface area of the
BM electrode was not surprising. The WM for X42-A was only attacked for the 1 bar CO2,
60 ºC test condition (Figure 4.3 and Figure 4.4), probably due to the more difficult siderite
precipitation kinetics. In all other test conditions the WM became cathodic. Changing the
temperature or the pCO2 is also essentially changing the driving forces for galvanic
corrosion, just like varying the BM surface area. The larger BM makes the WM corrode
faster, which in this case assisted with siderite precipitation. Nevertheless, regardless of BM
surface area, HAZ 2 remained the susceptible location for localized attack.
Increasing the pCO2 from 1 bar to 2 bar increases the concentration of reducible
species in the electrolyte, which resulted in an increased attack rate of HAZ 2, further
highlighting its susceptibility to localized corrosion.
4.3.3.2 X42-B
Figure 4.36 compares the ZRA curves from the original 1 bar CO2, 60 ºC experiment
(experiment ID: 1-60-A) where all electrodes (microstructural zones) had 1:1 surface area
ratios, to the repeated experiment (experiment ID: 1-60-B) that included both the standard
98
1:1 electrodes and the specially modified electrodes where the BM surface area was
increased by a factor of 15. The ZRA curves show that:
1. There is excellent agreement between the 1-60-A and 1-60-B ZRA curves for the
1:1 electrodes, indicating excellent repeatability of the measurements.
2. Regardless of BM surface area, HAZ 3 was strongly anodic and locally attacked.
3. Increasing the BM surface area had no effect on the galvanic current densities
between the different microstructural zones.
4. Increasing the pCO2 from 1 bar to 2 bar increased the attack rate of HAZ 3.
Unlike X42-A, increasing the BM surface area did not affect the level of localized
attack. This was expected as in the 1:1 experiment (1-60-A and 1-60-B) the BM electrode
was relatively neutral, with current densities close to zero. This shows that the BM was not
really participating in the galvanic interactions, therefore increasing its surface area has no
significant effect.
Increasing the pCO2 from 1 bar to 2 bar increased the anodic current density of HAZ 3,
further showing its high susceptibility to localized corrosion.
99
100
X42-A X42-A X42-A
Galvanic Current Density (µA/cm2) 1.2

1:1 1:1 1:15
75 0.9
1 bar 1 bar 2 bar 1 bar 2 bar
50 0.6
25 0.3
0 0
-25
WM WM WM
-50 HAZ 1 HAZ 1 HAZ 1
HAZ 2 HAZ 2 HAZ 2
BM 1-60-A BM 1-60-B BM 1-60-B
-100
0 48 96 144 0 48 96 144 0 48 96 144
Time (Hrs) Time (Hrs) Time (Hrs)
Figure 4.35: X42-A ZRA curves for 1 bar CO2, 60 ºC showing effect of BM surface area and response to an increase pCO2 from 1 bar to 2 bar.
100
400
X42-B X42-B X42-B
Galvanic Current Density (µA/cm2) 4.6

1:1 1:1 1:15
300 3.5
1 bar 1 bar 2 bar 1 bar 2 bar
200 2.3
100 1.2
0 0
-100
WM WM WM
HAZ 2 HAZ 2 HAZ 2
BM 1-60-A BM 1-60-B BM 1-60-B
-400
0 48 96 144 0 48 96 144 0 48 96 144
Time (Hrs) Time (Hrs) Time (Hrs)
Figure 4.36: X42-B ZRA curves for 1 bar CO2, 60 ºC showing effect of BM surface area and response to an increase pCO2 from 1 bar to 2 bar.
101
4.3.4 Effect of microstructure on preferential weld corrosion
Steel is generally composed of two phases, ferrite and cementite (Fe3C). Ferrite is
anodic relative to cementite48, therefore as the steel corrodes the ferrite dissolves and leaves
behind an un-corroded cementite layer. If the steel has pearlite banding, which is essentially
a strong, interconnected network of cementite, then the corrosion product layer will be a
porous sponge-like network of cementite. In this case, the cementite film can be
considerably thick and well-adhered to the surface. In contrast, if the cementite phase is
present as poorly interconnected carbides, then the corrosion product layer can be quite
weak and may break away from flow turbulences. This explains how the local microstructure
can act as a footprint for the corrosion product layer.
The formation of the empty cementite layer is important because it creates a local
environment for siderite precipitation. If the cementite layer is thick and porous, i.e. the
remnants of pearlite banding, then the Fe2+ ions released by the corrosion reaction are
somewhat sheltered from flow turbulences (diffusion limited), and accumulate locally instead
of being washed away. Siderite will precipitate when the fluid becomes locally saturated, that
is, when the concentration product [Fe2+][CO3-] exceeds the solubility product, Ksp. The
solubility product decreases with increasing temperature (precipitation is easier at higher
temperatures) 17. The accumulation of Fe2+ ions in the cementite film allows local saturation
to be reached more easily, and siderite precipitates. If the cementite phase is poorly
interconnected and structurally weak, it constantly breaks away as the ferrite dissolves. In
this situation, a well adhered porous cementite film does not form. Fe2+ ions will not
accumulate as easily, and local siderite precipitation is difficult.
When seam heat treated ERW linepipe corrodes, different microstructural zones
create local variations in cementite film morphology. These variations then affect local
saturation factors within the various cementite films, which then affects siderite precipitation
kinetics. Once different corrosion product layers start to form on each microstructural zone,
the steel surface is locally modified and the intrinsic corrosion potential of each zone
changes. This then establishes galvanic couples, and localized corrosion results.
4.3.4.1 Microstructural zones susceptible to PWC
The ZRA and SEM results presented here support the above explanation for
preferential weld corrosion in CO2 environments. Two microstructural zones in the ERW
linepipe were identified as being highly susceptible to localized corrosion; X42-A HAZ 2 and
X42-B HAZ 3. Both of these microstructural zones were regions with significantly different
carbide morphology. In both cases, the carbide morphology was comparatively less
102
interconnected and more prone to breaking, which prevented siderite precipitation locally at
this region.
4.3.4.1.1 Localized absence of pearlite banding
X42-A was made from normalized strip material with local seam heat treatment, and
had five different microstructural zones (Figure 3.5 and Figure 3.6). The WM and HAZ 1
were typical normalized ferrite and banded pearlite. HAZ 2 was a region of grain refinement
where the pearlite banding completely disappeared. HAZ 3 was also a region of grain
refinement, however the pearlite re-appeared as fine bands. The BM microstructure was
typical worked ferrite with banded pearlite.
The region of grain refinement free of pearlite banding (HAZ 2) was constantly
attacked (Figure 4.3 and Figure 4.4). SEM analysis showed the WM, HAZ 1, HAZ 3, and the
BM were able to first form a well-adhered cementite layer that then later precipitated siderite
(Figure 4.12). By contrast, HAZ 2 was unable to form this well-adhered cementite layer, as
the cementite was mostly present as small particles and not inter-connected pearlite bands.
This resulted in HAZ 2 forming a considerably thinner corrosion product layer without
siderite. The multi-channel ZRA measurements showed once this occurred, strong galvanic
couples developed with HAZ 2 being anodic.
Therefore if the BM of an ERW linepipe has a banded ferritic pearlitic microstructure,

all of the HAZs should also have pearlite banding, as the local absence will locally prevent
siderite precipitation, and localized galvanic attack will result. It is not so much that HAZ 2
was a ‘bad’ microstructure, it just corroded differently than the other microstructural zones
present in the X42-A linepipe, and this resulted in a strong galvanic couple being
established.
4.3.4.1.2 Localized regions of low temperature transformation

microstructures in a ferritic-pearlitic linepipe
X42-B was made from normalized strip material with local seam heat treatment, and
had five microstructural zones (Figure 3.7 and Figure 3.8). The WM and HAZ 1 were typical
normalized ferrite and banded pearlite. HAZ 2 was a region that had an accelerated cooling
rate, and developed a somewhat coarse, heavily sub-grained, quasi-polygonal ferrite region
with coarse banded pearlite. HAZ 3 experienced an even faster cooling rate, and developed
an almost quenched and tempered looking microstructure, containing a mixture of granular
bainite, upper bainite, and quasi-polygonal ferrite. The BM was typical worked ferrite with
banded pearlite.
103
The quenched and tempered microstructural region (HAZ 3) was severely attacked in
all test conditions (Figure 4.3 and Figure 4.4). The coarse, heavily sub-grained, quasi-
polygonal ferrite region (HAZ 2) was also susceptible to localized attack, however,
susceptibility was only at 1 bar CO2. At higher CO2 partial pressures, attack became more
intense and localized at HAZ 3. SEM analysis showed HAZ 3 was unable to form a stable
cementite layer and could not precipitate siderite, whereas all the other microstructural
zones could (Figure 4.14 and Figure 4.18). As the different microstructural zones corroded,
strong galvanic couples then developed where HAZ 3 was the anode.
Therefore if an ERW linepipe has a ferrite and banded pearlite base metal metallurgy,
any regions of accelerated cooling that produce low temperature transformation products
(e.g. granular bainite, upper bainite, quasi-polygonal ferrite) will be galvanically attacked as
different corrosion product layers form.
4.3.4.1.3 Coupling ferritic pearlitic and quenched and tempered

linepipes
The multi-channel ZRA experiments clearly showed the quenched and tempered
region of X42-B to be highly susceptible to localized galvanic attack. A special multi-channel
ZRA experiment where a seamless normalized ferritic pearlitic linepipe (X42-S) was coupled
to a seamless quenched and tempered linepipe (L80-S) also resulted in the quenched and
tempered linepipe being strongly galvanically attacked (Figure 4.9).
Quenched and tempered linepipes have a lower corrosion rate in CO2 environments
than normalized ones. Therefore when leaks occur in flowlines for example, it is often
tempting to replace the leaking section with a quenched and tempered linepipe. These
measurements show that in doing so, strong galvanic couples can slowly develop leading to
attack of the quenched and tempered material. Again, it is not correct to say a quenched and
tempered microstructure is ‘bad’ for CO2 corrosion, it just should not be coupled to a ferritic
pearlitic microstructure in saline CO2 environment. This fits well with field experience by the
author, as discussed in Section 4.3.1.2.5.
4.3.4.2 The effect of temperature
While certain ERW microstructural zones were consistently preferentially attacked, the
magnitude of attack was clearly influenced by temperature. The localized corrosion rates
were significantly lower at 30 ⁰C compared to 60 or 90 ⁰C, as siderite does not precipitate
easily at lower temperatures. For example, siderite precipitation at 30 ⁰C was difficult for all
microstructural zones, not just the susceptible ones. As none of the microstructural zones
104
are precipitating siderite, no significant galvanic couples develop. This fits well with field
observations by the author that CO2 PWC is less common at lower temperatures (e.g.
30 ºC).
As the temperature was increased, siderite precipitation became easier, especially at

regions where the cementite film allowed for preferential siderite precipitation, and stronger
galvanic couples resulted. Generally, siderite did not precipitate at the steel/cementite
interface where the Fe2+ concentration was higher, but rather some distance away from the
surface in the cementite layer. This was due to the electro-migration of chloride ions, causing
internal acidification. If the galvanic couples were strong enough, as was seen with X42-B,
internal acidification could be reduced or avoided at the cathodic microstructural zones and
accelerated at the anodic zones.
If the localized corrosion rate was rapid enough to make siderite precipitation
unavoidable, as was seen at 10 bar CO2, 90 ºC, galvanic passivation could occur. This starts
with the rapid attack of the susceptible microstructural zones, releasing large amounts of
Fe2+ ions causing a locally high level of siderite supersaturation. This ultimately makes
siderite precipitation unavoidable, and dense siderite layers form on all microstructural
zones. This passive layer, however, is prone to breaking either by intrinsic growth stresses 60
or mechanical damage. Sand particles flowing through the linepipe for example could break
this passivating layer, resulting in the re-establishment of localized corrosion until
passivation is once again reached. Cycling between these two stages would ultimately lead
to premature failure.
4.3.4.3 Avoiding localized CO2 corrosion in ERW linepipe
The susceptibility of ERW linepipe to localized corrosion around the weld region can
be related to two primary factors:
1. The carbon and manganese content of the steel

2. The localized seam heat treatment of the ERW weld
The two ERW linepipes that showed a high susceptibility to preferential weld corrosion,
X42-A and X42-B, had a carbon content of 0.115 and 0.130 wt%, respectively. Both
linepipes also had a manganese content of approx. 0.950 wt%. This gives the steel
reasonable hardenability characteristics, i.e. increases the ease at which microstructural
transformations can occur. When the ERW weld seam is locally heat treated, there exists a
temperature gradient between the weld seam (approx. 930 ºC) and the much cooler base
metal. The base metal therefore acts as a large heatsink, extracting heat from the seam heat
treated region. If the steel has a reasonable carbon and manganese content, this cooling
105
gradient can be sufficient to cause several microstructural transformations at the edge of the
seam heat treatment region, where the cooling gradient is highest. This was most obviously
seen with X42-B, which had the highest hardenability of the ERW linepipes, and was able to
form low temperature transformation microstructures at the outer edge of the seam heat
treatment region. This then resulted in several microstructural zones being present around
the ERW weld, most notably associated with cementite morphology variations. These
different microstructural zones then corrode and the cementite morphology acts as a
footprint for the corrosion product layer morphology. Once different corrosion product layers
start to form, strong galvanic couples develop, and localized attack results.
If the ERW linepipe has a lower carbon and manganese value, as was the case for
X42-C (0.071 wt% C, 0.570 wt% Mn), microstructural transformations are more difficult.
Furthermore, X42-C was made via thermo-mechanical controlled processing, meaning there
was greater control over cooling gradients. There were still different microstructural zones
present in X42-C around the ERW weld region, however, they were very similar to each
other (Figure 3.9 and Figure 3.10). They only varied in the sense that the HAZs had
equiaxed grains, and the BM had a more worked morphology. The cementite morphology
between the different microstructural zones was more or less the same. This resulted in
X42-C’s corrosion product layers all having similar morphology (Figure 4.19), and its
galvanic couples were considerably weaker than X42-A and X42-B (Figure 4.3 and Figure
4.4). In fact, the performance of X42-C approached the performance of the seamless X42-S
linepipe.
Therefore with greater care of the seam heat treatment process and C/Mn content,
microstructural variations around the ERW weld can be avoided. This reduces the
susceptibility of the ERW linepipe to localized galvanic attack in CO2 environments. The key
focus is to ensure no significant cementite morphology variations exist, as this results in
different corrosion product layers and siderite precipitation kinetics, which then establish
galvanic couples, leading to localized attack at a susceptible microstructural zone.
The use of seamless linepipe is, of course, one way to avoid preferential weld
corrosion in CO2 environments. It should be noted that not all types of localized CO2
corrosion are avoided by using seamless linepipe. The seamless X42-S linepipe had uniform
ferritic pearlitic microstructure throughout, however, it was still susceptible to mesa
corrosion. SEM analysis showed mesa corrosion resulted from a localized break in the
corrosion product layer on one of the X42-S electrodes, which suddenly established a strong
galvanic couple where the siderite covered electrodes were cathodic and the freshly
exposed steel was anodic.
106
4.4 Conclusions
The susceptibility of three X42 commercially produced ERW linepipes to localized

corrosion were compared to seamless in various 3% NaCl CO2 environments. Seam heat
treatment of the longitudinal weld formed a narrow region in the HAZ where cementite
morphology was significantly modified for X42-A and X42-B. This was found to vary siderite
precipitation kinetics resulting in the establishment of strong galvanic couples. Multi-channel
zero resistance ammetry showed galvanic coupling currents between the various
microstructural zones increased with temperature and CO2 partial pressure. Scanning
electron microscopy revealed corrosion product layer morphology was depended upon the
microstructure from which it grew, and this was directly related to microstructural zone
nobility. ERW linepipe with lower carbon and manganese content made via TMCP (X42-C)
had a more uniform microstructure across the ERW weld region. This produced
morphologically similar corrosion product layers, and susceptibility to localized attack was
considerably reduced.
Localized corrosion rates for the seamless linepipe were consistently 1 to 2 orders of
magnitude smaller than the X42-A and X42-B ERW linepipes. Therefore while seam heat
treated ERW linepipes have mechanical properties comparable to seamless, if the seam
heat treatment process results in localized cementite morphology variations, they have a
significant susceptibility to CO2 preferential weld corrosion.
107
Chapter 5 Effect of normalization heat treatments and
flow velocity on CO2 preferential weld
corrosion
5.1 Introduction
The experiments presented in Chapter 4 showed that resistance to preferential weld

corrosion in CO2 environments was increased as carbon and manganese content were
decreased. The X42 ERW linepipe with the highest resistance to PWC (X42-C) had the
lowest carbon and manganese content, and was also the only linepipe made via TMCP.
X42-C also had the most uniform ERW microstructure.
In this chapter, four new TMCP API grade X52 ERW linepipes were prepared by a
commercial manufacturer with low carbon and manganese content. All four linepipes were
made from the same strip material in the same production run, and therefore had identical
chemical composition. Each linepipe, however, was given a different heat treatment after
welding. This allowed the ‘pure’ effect of microstructure and heat treatment to be
investigated.
Four X52 ERW linepipes from a commercial manufacturer were investigated. The
linepipes were made via TMCP from the same low carbon/manganese strip material;
chemical composition is given in Table 3.2. Each linepipe received a different heat treatment
after welding by the manufacturer, as follows:
► X52-AW was left in the as-welded condition, and did not receive any heat
treatment.
► X52-SH had the weld seam locally normalized at 930 ºC.
► X52-450 had the weld seam locally normalized at 930 ºC, followed by full body
stress relief at 450 ºC.
stress relief at 650 ºC.
The full body stress relief was via induction, and lasted for approximately 5 seconds.
108
Descriptions of the different microstructural zones present in the X52 ERW linepipes
are given in Table 3.4, and corresponding optical and SEM micrographs in Section 3.4.3.2.
The primary difference between the X52 ERW linepipes investigated here, and the X42-C
ERW linepipe from Chapter 4, is that the X52 ERW linepipes contained granular bainite in
their base metal microstructures. Granular bainite is essentially ferrite with very small,
granular-like, martensite/austenite (MA) constituent. This gives granular bainite a rough
surface when etched compared to ferrite, which remains smooth (Figure 5.1). X42-C had
similar chemical composition, however, its base metal was ferritic pearlitic.
Figure 5.1: SEM SE image of X52-AW base metal (BM 2), 180º from the weld centreline. Rough grains are
granular bainite (GB), smooth grains are polygonal ferrite (PF), grain boundaries mostly MA constituent.
Etched 3% Nital.

described in Table 3.4 becoming an electrode on the ZRA (example hockey puck electrode
shown by Figure 3.3). All electrodes had approximately the same surface area of
approximately 0.10 cm2.
109
The multi-channel ZRA experiments were performed inside a stirring autoclave

modified for in-situ electrochemical measurements. Section 3.3.2 explains the experimental
procedure in detail, however, for convenience is summarised here. The five-segment ZRA
electrodes were freshly ground to 2400 grit, rinsed with ethanol, dried, and placed inside the
autoclave, which held 3.3 litres of electrolyte. The electrolyte was 3% NaCl purged with CO2
for 2 hours. A back pressure valve was used to slowly purge the autoclave with CO2 during
the experiment. The stirrer was operating at 150 RPM, which gave an approx. flow velocity
of 0.5 m/s at the electrode surfaces, in the direction indicative of Figure 4.1.
The stirring autoclave was then configured to one of the test conditions shown in Table
5.1 and ran for approximately 168 hours. The pH and Fe2+ concentrations were measured
throughout each experiment; the results are also shown in Table 5.1.
(ppm)
1-60-D2 60 1 3.72 5.25 28.7
150
1-90-B 90 1 3.89 5.73 75.2
3% NaCl
1-90-C 0 90 1 3.84 5.15 11.1
10-60-B 150 60 10 3.29 5.98 1 312
2
2… rotation stopped after 128 hours
Average galvanic current density (AGCD168hrs) values for the X52 ERW linepipes are
shown by Figure 5.2 for 1 bar CO2 and Figure 5.3 for 10 bar CO2. The AGCD168hrs values
measured for X42-C and X42-S from Chapter 4 are also included for comparison.
Overall, there was very good agreement between the four X52 ERW linepipes.
At 1 bar CO2, the WM, HAZ 1, and HAZ 2 were cathodic, and BM 1 and BM 2 were
anodic for all four linepipes. There was a tendency for BM 2 (base metal taken at 180º from
weld seam) to have a larger anodic current density than BM 1 (base metal taken near weld).
X52-AW had the largest galvanic interactions, which was expected as its microstructural
zones varied significantly.
110
At 10 bar CO2 there was no change for X52-AW; the WM, HAZ 1, and HAZ 2 remained
dominant cathodes, and BM 1 and BM 2 remained dominant anodes. However, there was a
clear change in WM nobility for the heat treat samples (X52-SH, X52-450, and X52-650).
The WM made a complete switch from being a strong cathode at 1 bar CO2 to a weak anode
and 10 bar CO2.
5.3.1.1 As-welded linepipe
X52-AW was in the as-welded condition, and while the magnitude of its galvanic
interactions changed with each test condition, the nobility of the different microstructural
zones did not. The weld centreline (microstructural zone designated WM) was unique as it
was the only microstructural zones to contain acicular ferrite. The WM also contained quasi-
polygonal ferrite and granular bainite. Adjacent the WM, HAZ 1 had a fine quasi-polygonal
microstructure with granular bainite. Both the WM and HAZ 1 were consistently strong
cathodes in all test conditions (Figure 5.2 and Figure 5.3). The two base metal electrodes,
one taken near the weld region (BM 1) and the other taken at 180º (BM 2), were consistently
strong anodes. Galvanic interactions were considerably stronger at 10 bar CO2, 60 ºC.
Compared to the WM and HAZ 1, the BM 1 and BM 2 microstructural zones had coarser
grains and contained significantly more granular bainite (Figure 3.15). HAZ 2, which was the
transition microstructure between the weld region and the base metal, had heavily
subgrained granular bainite with elongated polygonal ferrite, and was moderately cathodic in
all test conditions.
SEM cross sections of the X52-AW corrosion product layers are shown in Figure 5.4.
The cathodic microstructures (WM, HAZ 1, and HAZ 2) precipitated siderite at the
steel/cementite interface, whereas the anodic microstructural zones (BM 1 and BM 2) did
not, in agreement with observations in Chapter 4.
5.3.1.2 Heat treated linepipe
X52-SH received localized seam heat treatment after welding, which resulted in the
WM and HAZ 1 being a mixture of fine polygonal ferrite and granular bainite. Seam heat
treatment also removed the heavily subgrained structure in HAZ 2, leaving behind a mixture
of coarse and fine polygonal ferrite and granular bainite. Figure 5.2 shows how seam heat
treatment reduced the WM cathodic current density, especially for the 1 bar CO2, 90 ºC
condition. At 10 bar CO2, 60 ºC, seam heat treatment further reduced the WM cathodic
current density, and forced it into the anodic region (Figure 5.3).
111
Following the seam heat treatment with a full body stress relief at 450 ºC (X52-450)
and 650 ºC (X52-650) did not have any significant effect, except for a slight lowering of
galvanic interactions at 10 bar CO2, 60 ºC. This was probably because the hold time for the
full body stress relief was only for approx. 5 seconds, and could not cause any significant
microstructural changes. A longer hold time would homogenise the microstructural zones,
assisting with uniform corrosion product layer formation, and therefore smaller galvanic
couples. Nevertheless, the BM was the dominate anode which is a desirable characteristic of
the material.
SEM cross sections for X52-650 for the 1 bar CO2, 90 ºC test condition are shown by
Figure 5.5. Again, the WM, HAZ 1, and HAZ 2 were the dominant cathodes and precipitated
siderite at the steel/cementite interface, while the anodic BM 1 and BM 2 did not, further
agreeing with the findings of Chapter 4.
It should be noted that the heat treated samples were approaching the performance of
X42-C and the seamless X42-S for the 10 bar CO2, 60 ºC test condition.
112
1 bar CO2
300 3.5
X52-AW X52-SH X52-450 X52-650 X42-C X42-S
2.9
200 2.3

1.7
100 1.2
0.6
0 0
-100
WM WM WM WM WM E1
HAZ 1 HAZ 1 HAZ 1 HAZ 1 HAZ 1 E2
-200 HAZ 2 HAZ 2 HAZ 2 HAZ 2 E3
HAZ 2
BM 1 BM 1 BM 1 BM 1 BM 1 E4
-300
-400
Temperature
Figure 5.2: Average galvanic current densities (AGCD168hrs) for X52 ERW linepipe with different heat treatments, and a comparison to X42-C and seamless X42-S.
Conditions: 1 bar CO2, 3% NaCl, 150 RPM, area ratios 1:1. Positive values are anodic. Note: AGCD128hrs values shown for 1 bar CO2, 60 ºC.
113
10 bar CO2, 60 ºC
600 7.0
X52-AW X52-SH X52-450 X52-650 X42-C X42-S
500 5.8
400 4.6

300 3.5
200 2.3
100 1.2
0 0
-100
-200
-300
WM WM WM WM WM E1
-400 HAZ 1 HAZ 1 HAZ 1 HAZ 1 HAZ 1 E2
HAZ 2 HAZ 2 HAZ 2 HAZ 2 HAZ 2 E3
-500 BM 1 BM 1 BM 1 BM 1 E4
BM 1
-600
Figure 5.3: Average galvanic current densities over 168 hours (AGCD168hr) for X52 ERW linepipe with different heat treatments, and a comparison to X42-C and
seamless X42-S. Conditions: 10 bar CO2, 60 ºC, 3% NaCl, 150 RPM, area ratios 1:1. Positive values are anodic.
114
Sample ID: X52-AW
Test Condition: 1 bar CO2, 90 C, 150 RPM (0.5 m/s)
WM HAZ 1
HAZ 2 BM 1
BM 2
Figure 5.4: SEM BSD cross sections of X52-AW, for 1 bar CO2, 90 ºC, 150 RPM showing different
corrosion product layers forming on each microstructural zone. Base electrolyte 3% NaCl.
115
Sample ID: X52-650
Test Condition: 1 bar CO2, 90 C, 150 RPM (0.5 m/s)
WM HAZ 1
HAZ 2 BM 1
BM 2
Figure 5.5: SEM BSD cross sections of X52-650, for 1 bar CO2, 90 ºC, 150 RPM showing different
corrosion product layers forming on each microstructural zone. Base electrolyte 3% NaCl.
116
5.3.1.3 Effect of flow velocity
The previous section showed that the X52 linepipe in the as-welded condition (X52-
AW), which had significant microstructural variations, was able to form the strongest galvanic
couples. The samples that received subsequent heat treatment had overall smaller galvanic
couples. For all X52 linepipes however, at 1 bar CO2, 90 ºC, siderite only precipitated on the
cathodic electrodes. Table 5.1 shows the final pH of the electrolyte was 5.73 and had an
Fe2+ concentration of 75.2 ppm. According to the siderite solubility curves derived in Section
2.1.2 (Figure 2.3), an Fe2+ concentration of 3 ppm should be sufficient to reach saturation at
this pH, therefore it can be assumed flow turbulences were preventing siderite formation.
Furthermore, for the heavily banded samples investigated in Chapter 4 (X42-A, X42-B, and
X42-S) siderite precipitated readily at all microstructural zones for this test condition.
The 1 bar CO2, 90 ºC experiment was repeated (experiment ID: 1-90-C, Table 5.1)
with the as-welded (X52-AW) and maximum heat treated (X52-650) linepipes, however, the
fluid was stationary (i.e. stirring autoclave was set to 0 RPM). The ZRA curves for the 150
RPM (approx. 0.5 m/s) and 0 RPM test conditions are compared in Figure 5.6, and clearly
show the influence of microstructure and flow rate on galvanic couples for materials with
identical chemical compositions.
For the 150 RPM case, both X52-AW and X52-650 developed strong galvanic couples,
with the two base metal electrodes (BM 1 and BM 2) being dominant anodes, and the WM
and HAZ 1 electrodes being dominant cathodes. Notably, the X52-AW WM electrode has a
higher cathodic current density than the X52-650 WM electrode, due to its significantly
different acicular microstructure. Nevertheless, the nobility of the different microstructural
zones were the same, and both linepipes were able to develop strong galvanic couples.
When the experiment was repeated at 0 RPM, the X52-AW linepipe was still able to
develop the same strong galvanic couples. However, the X52-650 linepipe did not develop
any significant galvanic couples. This shows the microstructural zones present in the
X52-AW linepipe were sufficiently different enough to develop galvanic couples regardless of
flow, whereas X52-650 specifically required a flow velocity. From this information, one would
assume that the flow velocity helped X52-650 form different corrosion product layers, which
then led to the development of galvanic couples.
SEM cross sections for the 0 RPM case are shown by Figure 5.7 and Figure 5.8 for
X52-AW and X52-650, respectively, and show this was indeed the case. Comparing these
cross sections to those developed at 150 RPM (Figure 5.4 and Figure 5.5) clearly shows the
influence of microstructure and flow rate on corrosion product layer morphology, and further
validates the findings of Chapter 4.
117
At 0 RPM, X52-AW precipitated dense siderite at the steel/cementite interface for the
cathodic microstructures (WM, HAZ 1, HAZ 2), and at the centre of the cementite layer for
the anodic microstructures (BM 1 and BM 2). This was sufficient to form strong galvanic
couples. X52-650, however, formed morphologically similar corrosion product layers on all
microstructural zones, precipitating siderite at the centre of the cementite layer. As the
corrosion product layers were similar, no significant galvanic couples developed, similar to
the seamless X42-S linepipe in Chapter 4 (Figure 4.2 and Figure 4.11).
At 150 RPM, however, both X52-AW and X52-650 precipitated morphologically

different corrosion product layers, and both linepipes formed strong galvanic couples (Figure
5.4 and Figure 5.5). This is a demonstration on how localized differences in siderite
precipitation kinetics can establish galvanic cells.
5.3.1.3.1 Relationship to grain size
The ability of X52-650 to form strong galvanic couples at 150 RPM, but inability at
0 RPM, can be related to the grain size of the different microstructural zones and the ability
of the cementite layer to act as a diffusion barrier.
While the microstructural zones of X52-650 are similar, the WM and HAZ 1 regions
have a significantly smaller grain size than the BM 1 and BM 2 microstructural zones (Figure
3.20 and Figure 3.21). The grain boundaries are retained martensite/austenite (MA)
constituent, and form an interconnected network similar to pearlite banding (discussed in
Section 4.3.4). Therefore, as the ferrite corrodes the initial corrosion product layer is the
remnants of the MA constituent network, and this porous mesh acts as a diffusion barrier. As
the WM and HAZ 1 have the smallest grain size, their MA constituent corrosion product layer
is more interconnected and has smaller pores. This denser, more interconnected mesh
makes it difficult for ferrous ions to be washed away from flow turbulences, therefore siderite
saturation is reached more easily and precipitation occurs.
The X52-650 BM 1 and BM 2 microstructures have a larger grain size, therefore, their
MA constituent mesh has larger pores and fewer interconnections. This of course makes it
easier for flow turbulences to carry away ferrous ions, preventing local siderite saturation.
Consequently, when there is a flow velocity, it is more difficult for the X52-650 BM 1
and BM 2 microstructural zones to precipitate siderite compared to the WM and HAZ 1. This
difference in siderite precipitation kinetics, as described in Section 4.3.4, starts to form
different corrosion product layers, and galvanic couples result. At 0 RPM, the subtle
difference in MA constituent mesh density is less important, as the flow is stagnant.
The microstructural variations for X52-AW are far more dramatic than X52-650. The
X52-AW WM and HAZ 1 are low temperature transformation microstructures, and are
118
considerably finer than the base metal. Therefore when the ferrite corrodes, the differences
in MA constituent meshes are far more significant, which causes easier siderite saturation at
the WM and HAZ 1 microstructural zones, developing strong galvanic couples, regardless of
flow rate.
5.4 Conclusions
Four X52 ERW linepipes were produced by a commercial manufacturer from the same
low carbon (0.058 wt%) and low manganese (0.82 wt%) strip material. Each linepipe then
received a different heat treatment so the effect of microstructure on CO2 preferential weld
corrosion could be investigated using multi-channel zero resistance ammetry.
The results showed that the linepipe in the as-welded condition, strong galvanic
couples could be established where the acicular ferritic weld seam was cathodic relative to
the granular bainitic base metal. Local seam normalization reduced the magnitude of
galvanic interactions, however, did not significantly affect microstructural nobility. Performing
a 5 second full body stress relief, at 450 or 650 ºC, was able to further reduce galvanic
interactions at 10 bar CO2, but not at 1 bar CO2.
Flow velocity was found to assist with the development of galvanic couples, which was
attributed to differences in diffusion characteristics of the MA constituent corrosion product
layer. The as-welded linepipe was able to develop strong galvanic couples at both 0 and
150 RPM, however, the maximum heat treated sample could only form galvanic couples
at150 RPM.
119
400
X52-AS X52-650 X52-AS X52-650
4.6

150 RPM 150 RPM 0 RPM 0 RPM
200 2.3
0 0
-200
WM WM WM WM
HAZ 1 HAZ 1 HAZ 1 HAZ 1
-400 HAZ 2
HAZ 2 HAZ 2 HAZ 2
BM 1 BM 1 BM 1 BM 1
BM 2 1-90-B BM 2 1-90-B BM 2 1-90-C BM 2 1-90-C
-600
0 48 96 144 0 48 96 144 0 48 96 144 0 48 96 144
Figure 5.6: ZRA curves showing the effect of flow velocity on galvanic interactions for X52 ERW linepipe in the as-welded (X52-AW) and seam heat treated with 650 ºC full body
stress relief (X52-650) condition. Experimental conditions: 1 bar CO2, 90 ºC, 3% NaCl, area ratios 1:1. Positive values are anodic.
120
Sample ID: X52-AW
Test Condition: 1 bar CO2, 90 C, 0 RPM (0 m/s)
WM HAZ 1
HAZ 2 BM 1
BM 2
Figure 5.7: SEM BSD cross sections of X52-AW, for 1 bar CO2, 90 ºC, 0 RPM showing different corrosion
product layers forming on each microstructural zone.
121
Sample ID: X52-650
Test Condition: 1 bar CO2, 90 C, 0 RPM (0 m/s)
WM HAZ 1
HAZ 2 BM 1
BM 2
Figure 5.8: SEM BSD cross sections of X52-650, for 1 bar CO2, 90 ºC, 0 RPM showing different corrosion
product layers forming on each microstructural zone.
122
Chapter 6 Effect of quenched and tempered heat
treatment on CO2 preferential weld
corrosion
6.1 Introduction
Ferritic pearlitic ERW linepipe is typically made from normalized strip material, hot
rolled into a tube, and longitudinally welded to form a linepipe. The longitudinal ERW weld
seam is then locally normalized to remove the as-cast weld microstructure, and the entire
linepipe is typically ferritic pearlitic. Preferential weld corrosion can occur if the seam heat
treatment procedure causes localized microstructural variations, especially with regard to
cementite morphology (see Chapter 4). The temperature gradient between the weld seam
undergoing a highly localized normalization heat treatment, and the much cooler base metal,
acts as the driving force for localized microstructural variations. As the carbon concentration
of the steel increases, the microstructural transformations become easier for a given cooling
gradient, and up to five different microstructural zones may be present around the weld
region (e.g. Figure 3.7). This then causes different corrosion product layers to form, which
can establish strong galvanic couples, leading to localized corrosion.
ERW tubing can also be ordered with quenched and tempered heat treatments, such
as OCTG (Oil Country Tubular Goods) API grade L80. The high cooling rate of a quenched
and tempered heat treatment significantly hinders carbon diffusion, and therefore variations
in cementite morphology around the ERW weld region become negligible. Based on the
results of Chapter 4 and Chapter 5, this means that quenched and tempered ERW linepipes
should have superior resistance to preferential weld corrosion than normalized ERW
linepipes. To verify this, multi-channel zero resistance ammetry experiments were performed
with two ERW OCTG materials, one with a quenched and tempered microstructure (grade
L80), and one with a normalized ferritic pearlitic microstructure (grade J55).
Two ERW OCTG materials of API grade L80 and J55 were investigated, with sample
IDs L80-A and J55-A. Chemical compositions are given in Table 3.2. Micrographs of the
123
different microstructural zones present in the ERW material are given in Section 3.4.3.3, and
a summary is provided by Table 3.5.

interactions between the different microstructural zones present in each ERW OCTG. As
each OCTG. This recreated the original weld with each different microstructural zone
present in the OCTG (Section 3.4.3.3) becoming an electrode on the ZRA (example hockey
puck electrode shown by Figure 3.3). All electrodes had approximately the same surface
area of approximately 0.10 cm2.

6.1 and ran for approximately 168 hours. The pH and Fe2+ concentrations were measured
throughout each experiment; the results are also shown in Table 6.1.
124
(ppm)
1-60-I 60 1 3.82 5.51 112
10-60-C 60 10 3.30 5.532 198
3% NaCl 150
10-90-C 90 10 3.40 5.192 141
10-90-D 90 10 3.48 4.601,2 351
1… value taken at 43 hours

2
The average galvanic current densities measured over the 168 hour experimental
period (AGCD168hrs) for both the normalized (J55-A) and quenched and tempered (L80-A)
OCTGs are shown by Figure 6.1. The results clearly show that a quenched and tempered
heat treatment, which gives a very uniform microstructure around the ERW weld region,
significantly reduces the susceptibility to preferential weld corrosion compared to a
normalized heat treatment.
6.3.1 Normalized heat treatment (J55-A)
The local normalization seam heat treatment of J55-A introduced significant

microstructural variations around the ERW weld region (Figure 3.24 and Figure 3.25). As the
multi-channel ZRA measurements show (Figure 6.1), J55-A HAZ 3 consistently behaved as
the dominant anode, indicating this microstructural zone was highly susceptible to localized
attack. The localized corrosion rate for HAZ 3 was 295 µA/cm2 (3.4 mm/y) at 1 bar CO2,
60 ºC. Increasing the CO2 partial pressure to 10 bar CO2 significantly increased the localized
corrosion rate, averaging 738 µA/cm2 (8.6 mm/y) at 60 ºC, and 1723 µA/cm2 (20.0 mm/y) at
90 ºC.
Chapter 4 showed galvanic passivation was achievable at 10 bar CO2, 90 ºC, after an
initial period with very high localized corrosion rates (Figure 4.7). The mechanism of this was
discussed in detail in Section 4.3.1.2.4. The same was observed with the OCTG samples.
The multi-channel ZRA curves for 10 bar CO2, 90 ºC are given in Figure 6.2, and show
J55-A HAZ 3 experienced a peak instantaneous corrosion rate of 46 mm/y, which then
started to decay, as galvanic passivation started to occur.
125
6.3.2 Quenched and tempered heat treatment (L80-A)
The L80-A OCTG received a quenched and tempered heat treatment, which resulted
in almost negligible microstructural variations throughout the entire ERW weld region (Figure
3.22 and Figure 3.23). The multi-channel ZRA measurements (Figure 6.1) showed the
susceptibility of L80-A to preferential weld corrosion was almost negligible compared to the
J55-A OCTG, with anodic AGCD168hrs values an order of magnitude smaller.
There was no dominant anode at 60 ºC (at both 1 and 10 bar CO2), however, the WM
became dominant at 10 bar CO2, 90 ºC. While this may lead to the initial assumption that the
WM is susceptible to localized attack, it is actually related to randomized siderite
precipitation kinetics at this severe test condition. As observed in Chapter 4, even a
seamless linepipe (X42-S) with nominally uniform microstructure will have a certain number
of its ZRA electrodes randomly acting as dominant anodes at 10 bar CO2, 90 ºC (Figure 4.7).
The reason is associated with the intense siderite precipitation regime at the higher
temperature. Repeating the 10 bar CO2, 90 ºC experiment confirmed that the anodic L80-A
microstructural zones were randomly selected, similar to a seamless linepipe. The ZRA
curves for the repeated experiment, which was only ran for approximately 48 hours as part
of a repeatability check, are shown by Figure 6.3. Clearly, the quenched and tempered
OCTG (L80-A), with uniform microstructure throughout the entire ERW weld region, behaved
similar to a seamless linepipe. The magnitude of localized attack was comparatively small,
and the locations were randomized. By contrast, the normalized OCTG (J55-A), which had
significant microstructural variations around its ERW weld, had high levels of localized
attack, consistently at the same microstructural zone (J55-A HAZ 3).
126
Normalized vs Quenched & Tempered ERW OCTGs
2000 23.2
J55-A L80-A
1750 20.3
WM WM
1500 17.4

HAZ 1 HAZ 1
HAZ 2 HAZ 2
1250 14.5
HAZ 3 HAZ 3
BM BM
1000 11.6
750 8.7
500 5.8
250 2.9
0 0
-250
-500
-750 1 bar CO2 10 bar CO2 10 bar CO2 1 bar CO2 10 bar CO2 10 bar CO2
-1000 60 ºC 60 ºC 90 ºC 60 ºC 60 ºC 90 ºC
Figure 6.1: Average galvanic current densities over 168 hours (AGCD168hrs) for normalized (J55-A) and quenched and tempered (L80-A) ERW OCTGs.
Conditions: 3% NaCl, 150 RPM (approx. 0.5 m/s), surface area ratios 1:1. Positive values are anodic.
127
Galvanic Current Density (µA/cm2) J55-A L80-A

WM WM
4000 46.4
HAZ 1 HAZ 1
HAZ 2 HAZ 2
3000 HAZ 3 HAZ 3 34.8
BM BM
2000 23.2
1000 11.6
0 0
-1000
-2000
0 48 96 144 0 48 96 144
Figure 6.2: Current density curves for 10 bar CO2, 90 ºC, showing galvanic passivation of ERW OCTG
microstructural zones as corrosion product layers form. Experimental ID 10-90-C. Electrolyte 3% NaCl,
150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive values are anodic.
J55-A L80-A

WM WM
4000 46.4
HAZ 1 HAZ 1
HAZ 2 HAZ 2
3000 HAZ 3 HAZ 3 34.8
BM BM
2000 23.2
1000 11.6
0 0
-1000
-2000
0 48 96 144 0 48 96 144
Figure 6.3: Current density curves for the repeated 10 bar CO2, 90 ºC experiment, showing that the anodic
microstructural zones for the quenched and tempered OCTG (L80-A) are selected at random, similar to a
seamless linepipe. Experimental ID 10-90-D. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area
ratio 1:1. Positive values are anodic.
128
6.4 Conclusions
Multi-channel zero resistance ammetry performed inside a stirring autoclave at various

CO2 partial pressures and temperatures was performed on two commercially produced,
ERW OCTGs of grade J55 and L80. The J55 OCTG received a localized seam heat
treatment normalization that resulted in several different microstructural zones being present
in the ERW weld region. The L80 OCTG received a quenched and tempered heat treatment,
which resulted in a uniform microstructure around the ERW weld region, approaching the
quality of a seamless linepipe.
In full agreement with Chapter 4 and Chapter 5, having different microstructural zones
around the ERW weld region increases susceptibility to preferential weld corrosion in CO2
environments. By opting for the quenched and tempered heat treatment, susceptibility to
preferential weld corrosion was significantly reduced. Furthermore, the location of any
localized attack on the quenched and tempered ERW OCTG was randomized, and an order
of magnitude smaller than the normalized ERW OCTG. Localized attack on the normalized
ERW OCTG consistently occurred at the same microstructural zone, which is highly
undesirable, as this increases the likelihood of premature material failure and a loss of
hydrocarbon containment.
129
Chapter 7 Effect of acetic acid on CO2 preferential
weld corrosion
7.1 Introduction
Oil and gas environments often contain short chain carboxylic acids in addition to CO2.
Of these carboxylic acids, acetic acid (CH3COOH, abbreviated to HAc) is the most common.
The precise effect of acetic acid on CO2 corrosion is unclear, however, there is a general
agreement in the literature that the presence of HAc can cause localized corrosion9, 40, 45, 62-
65. Generally, if HAc is present in large quantities the general corrosion rate of the steel will
increase due to an increase in the hydrogen evolution rate (Equation (2.9)). Gulbrandsen
and Bilkova63 showed that HAc was the dominating cathodic reactant for concentrations
greater than 60 ppm (1 mM) at 1 bar CO2. At higher CO2 partial pressures the corrosion rate
of steel is already high, and the relative effect of HAc concentration becomes less significant.
In the previous chapters, it was shown that different microstructural zones present
around the ERW weld region can form morphologically different corrosion product layers,
which slowly establish galvanic couples, leading to localized attack. HAc can form
complexes with Fe2+ ions, which of course affects the local siderite saturation factor in the
corrosion product layer, hindering siderite precipitation. This chapter repeats some of the
experiments presented in previous chapters with the addition of HAc, and investigates if its
presence can cause a change in galvanic behaviour, such as increasing the rate of localized
attack.
The effect of HAc on the X42 (Chapter 4), X52 (Chapter 5), and J55 and L80 (Chapter
6) ERW materials were investigated. Details are summarised by Table 7.1, and
metallographic analysis of the different microstructural zones present in each material was
given in Section 3.4.
130
Table 7.1: Investigated materials with corresponding experimental ID and HAc concentration information.
Experimental Investigated Materials HAc Concentration
ID
Without HAc
1-60-A X42-A, X42-B, X42-C, X42-S
1-60-D X52-AW, X52-SH, X52-450, X52-650 0 ppm
1-60-E J55-A, L80-A, X42-B
With HAc
1-60-F
X42-A, X42-B, X42-C, X42-S 60 ppm injected at 0 hrs
10-60-D
60 ppm injected at 0 hrs
1-60-G X52-AW, X52-SH, X52-450, X52-650
1-60-H J55-A, L80-A, X42-B, X52-AW 80 ppm injected at 71 hrs

each linepipe and OCTG shown in Table 7.1. This recreated the original weld with each
different microstructural becoming an electrode on the ZRA (example hockey puck electrode
shown by Figure 3.3). All electrodes had approximately the same surface area of
approximately 0.10 cm2.

7.2 and ran for a minimum of 168 hours. In some experiments the rotation was stopped part
131
way though the experiment to see the effect of flow velocity. As shown in Table 7.1, various
amounts of HAc was injected into the electrolyte. The pH and Fe2+ concentrations were
measured throughout each experiment; the results are shown in Table 7.2. A Ag/Agcl
electrode was used to measure the corrosion potential of each sample (Figure 7.5).
Table 7.2: Experimental test conditions.

(ppm)
1-60-A 150 60 1 3.81 5.53 75
1-60-D 3% NaCl 150 2 60 1 3.72 5.25 28
1-60-E 150 60 1 3.80 5.51 112
1-60-F 150 60 1 3.55 5.47 90
1-60-G 3% NaCl 150 3 60 1 3.51 4.21 111
1-60-H with HAc 150 60 1 3.50 4.21 125
10-60-D 150 60 10 3.49 4.151 227
2
7.3.1 X42 linepipes
The 1 bar CO2, 60 ºC and 10 bar CO2, 60 ºC experiments presented in Chapter 4 for
the X42 linepipes (experiment ID: 1-60-A and 10-60-A, Table 4.1) were repeated and the
electrolyte was given an initial HAc concentration of 60 ppm (experiment ID: 1-60-F and
10-60-D). HAc was found to generally increase the rate of localized attack, however, it
depended on steel type, in agreement with field observations and literature summarised by
Gulbrandsen and Bilkova63. AGCD168hrs values summarising the results are shown by Figure
7.8 and Figure 7.9, for 1 bar and 10 bar CO2, respectively. As expected, the addition of
60 ppm HAc to the electrolyte was most notable at 1 bar CO2, as the localized corrosion
rates at 10 bar CO2 were already high.
As X42-B was the most sensitive to HAc additions, it was included in an additional 1
bar CO2, 60 ºC experiment (experiment ID: 1-60-H). As shown in Table 7.1, the electrolyte
had an initial HAc concentration of 60 ppm, with an additional 60 ppm injected at 71 hours,
and 600 ppm at 144 hours.
The following section presents the relevant multi-channel ZRA curves for the four X42
linepipes.
132
7.3.1.1 X42-A
The ZRA curves showing the effect of adding 60 ppm HAc to the initial electrolyte are
given in Figure 7.1. The two graphs are very similar, with the grain refined region free of
pearlite banding (HAZ 2) and the weld seam (WM) being anodic and therefore galvanically
attacked. While the addition of HAc did not increase the magnitude of galvanic attack, it did
make the current density curve for HAZ 2 unstable, suggesting some instability with the
corrosion film on the surface. SEM cross sections and EDX element mapping of HAZ 2’s
corrosion product layer is shown by Figure 7.2 showing the effect of HAc. For the HAc free
test condition (experiment ID: 1-60-A) internal acidification had occurred, indicated by the
hollow region at the steel/cementite interface rich with chlorides. The chlorides are attracted
to the steel/cementite interface by electro-migration due to the high Fe2+ concentration
(discussed in Section 4.3.2.5). For the case with 60 ppm HAc added to the solution, this
internal acidification did not occur, and siderite had precipitated directly at the
steel/cementite interface. Furthermore, chlorides could not be detected. This was most likely
due to the buffering effect of HAc.
HAc ↔ H+ + Ac- (7.1)
Fe2+ + 2Ac- ↔FeAc2 (7.2)
100
X42-A X42-A
1.2
Galvanic Current Density (µA/cm 2)

Without HAc 1 mM HAc
75 0.9
50 0.6
25 0.3
0 0
-25
WM WM
-50 HAZ 1 HAZ 1
HAZ 2 HAZ 2
-75 HAZ 3 HAZ 3
BM 1-60-A BM 1-60-F
-100
0 48 96 144 0 48 96 144
Figure 7.1: X42-A ZRA current density curves showing the effect of 60 ppm HAc on galvanic interactions
for 1 bar CO2, 60 ºC. Electrolyte 3% NaCl, 150 RPM, area ratios 1:1. Positive values are anodic.
133
Sample ID: X42-A HAZ 2
Test Condition: 1 bar CO2, 60 ºC, 150 RPM (approx. 0.5 m/s) with and
without 60 ppm HAc
Without HAc 60 ppm HAc

Experiment ID: 1-60-A Experiment ID: 1-60-F
SEM BSD
EDX Element Mapping
Figure 7.2: EDX element mapping showing chlorides (bright colour) for X42-A HAZ 2 corrosion product
layer, for 1 bar CO2, 60 ºC, with and without 60 ppm HAc.
7.3.1.2 X42-B
X42-B HAZ 3 had a quenched and tempered morphology and was constantly locally
attacked in the experiments presented in Chapter 4. The ZRA curves showing the effect of
various HAc additions on galvanic interactions between each microstructural zone are
shown in Figure 7.3. Clearly the HAc increased the severity of localized galvanic attack at
HAZ 3. A 60 ppm addition nearly doubled the attack rate of HAZ 3 compared to the HAc free
test condition, increasing from 2.26 to 3.94 mm/y. SEM cross sections of HAZ 3 showed the
60 ppm addition of HAc made the corrosion product layer more broken (Figure 7.4). This
may be related back to the local siderite saturation factor. As discussed in Section 7.3.1.1,
HAc removes Fe2+ ions form the electrolyte, lowering the local siderite saturation factor. As
discussed in Section 4.3.2.1, siderite can act as a ‘glue’ holding the HAZ 3 corrosion product
layer together, as its footprint is the remnants of the poorly interconnected cementite
network, which has limited mechanical strength. This hindrance to siderite precipitation
134
brought about by the presence of HAc, may be why the corrosion product layer appears
more broken.
As X42-B HAZ 3 was the most responsive to the 60 ppm HAc experiments
(experiment ID: 1-60-F), it was included in an additional experiment (experiment ID: 1-60-H)
with addition HAc injections (Table 7.1). Figure 7.3 (right) shows that every time HAc is
injected into the electrolyte, HAZ 3’s galvanic current density spikes in the anodic direction,
indicating an increase in localized attack. Its current density then slowly decays as the acetic
acid is consumed. A water sample was taken at 71 hours just before the second 80 ppm
HAc injection, and the electrolyte was found to contain 5 ppm HAc, indicating most of the
initial 80 ppm HAc had been consumed. The Ag/AgCl electrode used to measure the
corrosion potential of each sample showed, in agreement with the literature, that the
injection of HAc caused the corrosion potential to shift into the anodic (positive) direction
(Figure 7.5).
7.3.1.3 X42-C
X42-C had the most uniform microstructure out of the X42 ERW linepipes, and while
the addition of 60 ppm HAc to the initial electrolyte increased galvanic coupling currents
initially, they ultimately decayed to similar values (Figure 7.6). This was not surprising as the
relatively similar microstructural zones of X42-C where shown in Chapter 4 to produce
morphologically similar corrosion product layers, and therefore the potential for HAc to cause
localized siderite precipitation differences is lessened. Nevertheless, the WM and HAZ 2
were attacked in both cases. As described in Section 3.4.3.1, HAZ 1 and HAZ 2 were the
heat affected zones taken from the left and right side of the weld centreline (WM). They had
identical microstructure, except HAZ 2 contained a noticeable segregation band at the centre
(Figure 3.9).
135
X42-B X42-B X42-B
Galvanic Current Density (mA/cm 2) 800 9.3

Without HAc With HAc With HAc
600 7.0
400 4.6
200 2.3
0 0
-200
-400 80 ppm HAc 600 ppm HAc

60 ppm HAc added
added
added
1-60-A 1-60-F 1-60-H
-600
0 48 96 144 0 48 96 144 0 48 96 144 192
Time (Hrs)
WM HAZ 1
HAZ 2 HAZ 3
BM
Figure 7.3: X42-B current density curves showing the effect of various acetic acid (HAc) additions on galvanic interactions for 1 bar CO2, 60 ºC. Electrolyte 3% NaCl, 150 RPM, area
ratios 1:1. Positive values are anodic.
136
Sample ID: X42-B HAZ 3
Test Condition: 1 bar CO2, 60 ºC, 150 RPM (approx. 0.5 m/s) with and without 60 ppm
HAc
Test Duration 168 hours
Without HAc 60 ppm HAc
Experiment ID: 1-60-A Experiment ID: 1-60-F
Figure 7.4: SEM BSD images of X42-B HAZ 3 corrosion product layer at 1 bar CO2, 60 ºC. The addition of
60 ppm (60 ppm) HAc to the initial electrolyte caused the corrosion product layer to become more
broken.
1 bar CO2, 60 ºC
-0.60
With HAc
Corrosion Potential (V, Ag/AgCl)
-0.62
-0.64
600 ppm HAc
added
80 ppm HAc
added
-0.66
J55-A
L80-A
X42-B
-0.68 X52-AW
80 ppm HAc
added 1-60-H
0 48 96 144 192
Time (Hrs)
Figure 7.5: Corrosion potential of samples for 1 bar CO2, 60 ºC with HAc injections at 0, 71, and 143
hours. Experiment ID: 1-60-H. Electrolyte 3% NaCl, 150 RPM, area ratios 1:1.
137
X42-C X42-C
100 1.2

75 0.9
50 0.6
25 0.3
0 0
-25
WM WM
-50 HAZ 1 HAZ 1
HAZ 2 HAZ 2
-75 BM 1 BM 1
BM 2 1-60-A 1-60-F BM 2
-100
0 48 96 144 0 48 96 144
Figure 7.6: X42-C current density curves showing the effect of 60 ppm HAc on galvanic interactions for 1
bar CO2, 60 ºC. Electrolyte 3% NaCl, 150 RPM, area ratios 1:1. Positive values are anodic.
7.3.1.4 X42-S
Literature on the effect of HAc in CO2 environments was recently summarised by

Gulbrandsen and Bilkova63 and showed several authors related the presence of HAc to an
increase in mesa corrosion. Mesa corrosion can occur in seamless linepipe with nominally
uniform microstructure, where the corrosion product layer is degraded, for some reason, at a
particular location. As presented in Section 4.3.1.2.3 and Section 4.3.2.2, this was only
observed for the seamless X42-S linepipe at the severe test condition of 10 bar CO2, 60 ºC.
The ZRA curves showing the effect of 60 ppm HAc on the seamless X42-S linepipe
are shown by Figure 7.7. For the case without HAc, the galvanic interactions between the
nominally uniform seamless X42-S electrodes are small (approx. 0.1 mm/y), and there was
no clearly dominant anode or cathode. This was expected as all five ZRA electrodes had
nominally identical microstructure, and this behaviour for the X42-S was frequently observed
in Chapter 4. The addition of 60 ppm HAc to the initial electrolyte, however, clearly resulted
in one of the seamless X42-S electrodes being preferentially attacked (E5). This supports
observations in the literature63 that HAc encourages mesa type corrosion.
138
X42-S X42-S
60 0.69

40 0.46
20 0.23
0 0
-20 E1
E1
E2 E2
-40 E3 E3
E4 E4
1-60-A E5 1-60-F E5
-60
0 48 96 144 0 48 96 144
Figure 7.7: Seamless X42-S current density curves showing the effect of 60 ppm HAc on galvanic
interactions for 1 bar CO2, 60 ºC. Electrolyte 3% NaCl, 150 RPM, area ratios 1:1. Positive values are
anodic.
139
1 bar CO2, 60 ºC
250 2.9
X42-A X42-B X42-C X42-S

200 2.6
WM WM E1

WM
150 1.7
HAZ 3 HAZ 3 BM 1 E4
BM BM BM 2 E5
100 1.2
50 0.6
0 0
-50
-100
Without 60 ppm Without 60 ppm Without 60 ppm Without 60 ppm
HAc HAc HAc HAc HAc HAc HAc HAc
-150
Figure 7.8: Average galvanic current densities over 168 hours (AGCD168hrs) for X42 ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe, showing effect of 60 ppm HAc.
Conditions: 1 bar CO2, 60 ºC, 3% NaCl, 150 RPM, area ratios 1:1. Positive values are anodic.
140
10 bar CO2, 60 ºC
1400 16.2
1200 X42-A X42-B X42-C X42-S 14.0

WM WM E1 11.6
1000 WM

800 9.3
HAZ 3 HAZ 3 BM 1 E4
BM BM BM 2 E5
600 7.0
400 4.6
200 2.3
0 0
-200
-400
-600
HAc HAc HAc HAc HAc HAc HAc HAc
-800
Figure 7.9: Average galvanic current densities over 168 hours (AGCD168hrs) for X42 ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe, showing effect of 60 ppm HAc.
Conditions: 10 bar CO2, 60 ºC, 3% NaCl, 150 RPM, area ratios 1:1. Positive values are anodic.
141
7.3.2 X-52 linepipe
The 1 bar CO2, 60 ºC experiments presented in Chapter 5 (experiment ID: 1-60-D,

Table 5.1) for the X52 ERW linepipe were repeated with the addition of HAc. As described in
Section 3.4.1.2, all X52 samples had the same chemical composition, however, received
different heat treatments. The repeated experimental IDs are 1-60-G and 1-60-H, exact
experimental conditions are detailed in Table 7.1 and Table 7.2.
In experiment 1-60-G, all four X52 linepipe samples were studied. 60 ppm HAc was
injected into the electrolyte at the start of the experiment, followed by 600 ppm at 96 hours.
Rotation was stopped at 168 hours to study the effect of flow velocity.
Experiment 1-60-H only investigated the as-welded (X52-AW) sample. 80 ppm HAc
was injected into the electrolyte at the start of the experiment, followed by another 80 ppm at
71 hours, and 600 ppm at 144 hours.
The notable finding was that the presence of HAc forced the WM microstructural zone
into the anodic region. This was especially noticeable for the X52-AW, where the WM went
from being a dominant cathode to a dominant anode.
7.3.2.1 X52-AW
The X52-AW weld centreline (WM) had a notably different microstructure from the
other microstructural zones, filled with low temperature transformation phases (Table 3.4
and Figure 3.14). As shown in Figure 5.2 and Figure 5.3, the WM was consistently a strong
cathode, and the base metal was a strong anode. This is somewhat of an ideal situation to
be in, as the large surface area of the base metal can afford to cathodically protect the small
surface area of the WM.
ZRA curves showing the effect of HAc on galvanic interactions between the different
microstructural zones present in the as-welded X52-AW linepipe are shown by Figure 7.10.
All ZRA curves are for 1 bar CO2, 60 ºC. For the case without HAc, the WM acted as a
strong cathode, even when the rotation was stopped. Repeating the experiment with an
initial HAc concentration of 60 ppm (1-60-G) caused the WM to move into the anodic region.
As the HAc was consumed, the WM started to drift back towards the cathodic region
(approximately between 36 and 96 hours). At 96 hours the WM crossed the horizontal axis
and became cathodic, at which point, an addition 600 ppm HAc was injected. The WM
suddenly spiked in the anodic direction, experienced some transience for approx. 12 hours,
and then drifted back into the anodic region. At 168 hours the rotation was stopped, and the
WM instantly became cathodic. This is an excellent example of how the presence of acetic
142
acid in a flowline can cause localized corrosion in CO2 environments. It has the ability to
cause complete current reversal of a very strong cathodic microstructural zone, forcing it to
become anodic, leading to localized attack. It is also another example of how flow rate can
affect galvanic coupling currents. The combination of acetic acid and a flowrate of 0.5 m/s
(150 RPM) led to localized attack of the weld centreline (WM), however, acetic acid in a
stationary electrolyte did not.
Repeating the experiment once more (1-60-H) with an initial HAc concentration of
80 ppm, again caused the WM to become anodic. In agreement with the 60 ppm experiment,
once the HAc was consumed the WM started to drift back to the cathodic region. At 71 hours
the HAc concentration in the electrolyte was measured at 5 ppm, indicating most of the
original 80 ppm addition had been consumed. An additional 80 ppm was injected at 71
hours, which caused the WM current density to increases slightly upon injection, but then it
resumed its downward trend into the cathodic region. At 71 hours the Fe2+ concentration of
the bulk electrolyte was 40 ppm, therefore, the injected HAc was probably quickly consumed
by Equation (7.2) and had little effect. At 144 hours the WM had clearly become a strong
cathode again, at which point an additional 600 ppm HAc was injected. This caused the WM
to immediately change trend, moving back into the anodic region.
Therefore while Chapter 5 showed that the X52-AW weld centreline microstructural
zone (WM) was a strong cathode, and was essentially cathodically protected at the expense
of the base metal microstructure, HAc clearly has the ability to shift the location of localized
attack. This highlights the sensitivity of preferential weld corrosion to water chemistry and
flow conditions.
143
X52-AW X52-AW X52-AW
Galvanic Current Density (mA/cm2) 400 4.6
Without HAc With HAc

With HAc
300 3.5
150 RPM 0 RPM 150 RPM
200 2.3
150 RPM 0 RPM
100 1.2
0 0
-100
-200
80 ppm HAc 600 ppm HAc
-300 60 ppm HAc 600 ppm HAc added
added
added added
1-60-D 1-60-G 1-60-H
-400
0 48 96 144 0 48 96 144 192 0 48 96 144 192
Time (Hrs)
WM HAZ 1
HAZ 2 BM 1
BM 2
Figure 7.10: ZRA curves for X52-AW showing the effect of acetic acid (HAc) and flow rate on the susceptibility of the WM to localized attack. Test condition 1 bar
CO2, 60 ºC, 3% NaCl. Positive values are anodic.
144
7.3.2.2 X52-SH
X52-SH was produced by locally seam heat treating the as-welded X52-AW linepipe at
930 ºC, removing the as-welded microstructure (Figure 3.16). The ZRA curves showing the
effect of HAc on galvanic interactions for X52-SH are shown by Figure 7.11. For the case
without HAc (1-60-D), the seam heat treatment made the WM essentially galvanically
neutral. Repeating the experiment with 80 ppm HAc forced the weld slightly into the anodic
region, and the addition of 600 ppm HAc at 96 hours forced the WM further into the anodic
region. Therefore, while seam heat treatment made the WM more resistant to becoming
anodic in the presence of HAc, the susceptibility was not completely removed.
X52-SH X52-SH
400 4.6
Galvanic Current Density (mA/cm2)

300 3.5
0 RPM
150 RPM
200 2.3
150 RPM 0 RPM
100 1.2
0 0
-100
-200
-300 added added
1-60-D 1-60-G
-400
0 48 96 144 0 48 96 144 192
WM HAZ 1
HAZ 2 BM 1
BM 2
Figure 7.11: ZRA curves for X52-SH showing the effect of acetic acid (HAc) and flow rate on galvanic
interactions. Test condition 1 bar CO2, 60 ºC, 3% NaCl. Positive values are anodic.
7.3.2.3 X52-450
X52-450 was produced by performing a five second full body stress relief on the
X52-SH linepipe at 450 ºC. Microstructural zones are shown by Figure 3.18, and ZRA curves
showing the effect of HAc on galvanic interactions are shown by Figure 7.12. Similar to X52-
SH, the WM was essentially galvanically neutral in the absence of HAc, and the addition of
145
80 ppm and the 600 ppm HAc forced the WM into the anodic region, although to a slightly
lesser extent.
X52-450 X52-450
400 4.6

300 0 RPM
3.5
150 RPM
200 2.3
150 RPM 0 RPM
100 1.2
0 0
-100
-200
-300 added added
1-60-D 1-60-G
-400
0 48 96 144 0 48 96 144 192
WM HAZ 1
HAZ 2 BM 1
BM 2
Figure 7.12: ZRA curves for X52-450 showing the effect of acetic acid (HAc) and flow rate on galvanic
7.3.2.4 X52-650
X52-650 was produced by performing a five second full body stress relief on the
X52-SH linepipe at 650 ºC. Microstructural zones are shown by Figure 3.20, and ZRA curves
showing the effect of HAc on galvanic interactions are shown by Figure 7.13. The higher full
body stress relief temperature did not cause any visible microstructural changes, however,
did prevent the WM from behaving anodically. Unlike X52-SH and X52-450, the WM was
cathodic for both cases, with and with HAc. In fact, the addition of 80 ppm and then 600 ppm
HAc forced the WM further into the cathodic region.
146
X52-650 X52-650
400 4.6

300 3.5
0 RPM
150 RPM
200 2.3
150 RPM 0 RPM
100 1.2
0 0
-100
-200
-300 added added
1-60-D 1-60-G
-400
0 48 96 144 0 48 96 144 192
WM HAZ 1
HAZ 2 BM 1
BM 2
Figure 7.13: ZRA curves for X52-650 showing the effect of acetic acid (HAc) and flow rate on galvanic
7.3.3 OCTGs
The effect of HAc on the galvanic interactions of the two ERW OCTG materials (J55-A
and L80-A) was also investigated. The 1 bar CO2, 60 ºC experiment presented in Chapter 6
(experimental ID: 1-60-E) was repeated with various HAc additions. The repeated
experiment (experimental ID: 1-60-H, Table 7.1) had an initial HAc concentration of 80 ppm,
with an additional injection of 80 ppm at 71 hours and 600 ppm at 144 hours.
J55-A was a 0.159 wt% C seam heat treated OCTG with significant microstructural
variations around the ERW weld seam; microstructural zone descriptions are given in Table
3.5 and micrographs in Figure 3.24.
L80-A was a 0.280 wt% C OCTG with a full body quenched and tempered heat
treatment, which resulted in a very uniform microstructure around the ERW weld region;
microstructural zone descriptions are given in Table 3.5 and micrographs in Figure 3.22.
147
7.3.3.1 J55-A
J55-A HAZ 3 acted as a dominate anode in all Chapter 6 experiments and was
strongly attacked. ZRA curves showing the effect of HAc are shown by Figure 7.14. The
addition of 80 ppm HAc at the beginning of the experiment did not significantly affect the
magnitude of attack at HAZ 3, but rather made the first 12 hours of the curve steeper.
Further additions of HAc during the experiment concentrated the localized attack at HAZ 3.
J55-A J55-A
1500 17.4

1250 14.5
1000 11.6
750 8.7
500 5.8
250 2.9
0 0
-250
-500
-750 80 ppm HAc 600 ppm HAc
-1000 added added
1-60-E 1-60-H
-1250
0 48 96 144 0 48 96 144 192
WM HAZ 3
HAZ 1 BM
HAZ 2
Figure 7.14: ZRA curves for J55-A showing the effect of acetic acid (HAc) and flow rate on galvanic
interactions. Test condition 1 bar CO2, 60 ºC, 3% NaCl, 150 RPM (approx. 0.5 m/s). Positive values are
anodic.
7.3.3.2 L80-A
As L80-A had a full body quenched and tempered heat treatment, its microstructure
was quite uniform around the ERW weld region, especially with respect to carbide
morphology. This resulted in L80-A performing similar to a seamless linepipe in all Chapter 6
experiments, where the galvanic interactions between the different microstructural zones
were almost negligible compared to J55-A. ZRA curves showing the effect of HAc are shown
by Figure 7.15. Unsurprisingly, the addition of 80 ppm HAc at the start of the experiment had
a negligible effect. The 80 ppm addition at 71 hours and was also negligible, however, there
was somewhat of a noticeable response to the 600 ppm addition at 144 hours. The larger
148
addition of 600 ppm HAc caused the current density curves to become more unstable with a
slight increase in magnitude. However, the current densities measured for L80-A were still
an order of magnitude lower than J55-A.
L80-A L80-A
400 4.6
Without HAc

With HAc
300 3.5
200 2.3
100 1.2
0 0
-100
600 ppm HAc
-200 added
80 ppm HAc
-300 added
1-60-E 1-60-H
-400
0 48 96 144 0 48 96 144 192
WM HAZ 3
HAZ 1 BM
HAZ 2
Figure 7.15: ZRA curves for L80-A showing the effect of acetic acid (HAc) and flow rate on galvanic
interactions. Test condition 1 bar CO2, 60 ºC, 3% NaCl, 150 RPM (approx. 0.5 m/s). Positive values are
anodic.
7.4 Conclusions
Multi-channel zero resistance ammetry showed the presence of HAc could significantly
increase the localized corrosion rate of certain ERW linepipes and OCTGs. In agreement
with literature and field observations, the susceptibility and magnitude of localized attack
depended on the steel type. In the absence of HAc, X42-B and J55-A were the most
susceptible ERW linepipes and OCTGs to localized attack. These two materials were also
the most sensitive to HAc additions, where the presence of HAc intensified localized attack.
The Multi-channel ZRA results also showed HAc can cause a current reversal for some
ERW linepipe microstructural zones. Concentrations as low as 60 ppm HAc were able to
cause the X52-AW weld seam to change from a dominant cathode to a dominate anode.
The nobility of the microstructural zone was also found to depend on flow rate.
149
Generally, the more uniform the microstructure across the ERW weld region, the
smaller the response to HAc additions. However, as the X52 linepipe experiments showed,
the response to HAc cannot always be predicted based on microstructure. This further
shows how the multi-channel ZRA approach proposed by this thesis, for investigating the
localized corrosion susceptibility of ERW linepipes and OCTGs, is a powerful tool.
150
Chapter 8 Corrosion inhibitors and CO2 preferential
weld corrosion
8.1 Introduction
The previous chapters have shown that ERW linepipe and OCTGs, depending on their
chemical composition and heat treatment, can be susceptible to preferential weld corrosion
in CO2 environments. Multi-channel zero resistance ammetry experiments performed inside
a stirring autoclave showed that when different microstructural zones were present around
the ERW weld region, different corrosion product layers would form, and strong galvanic
couples were established. As the microstructure around the ERW weld region became more
uniform, the corrosion product layers became more similar, the galvanic coupling effect was
reduced, and resistance to preferential weld corrosion was increased.
The above information is certainly valuable during the material selection phase of a
pipeline, however, in existing pipelines localized corrosion must be mitigated by the use of
corrosion inhibitors. This section investigates the effectiveness of a commercially available
corrosion inhibitor at preventing preferential weld corrosion.
The effect of 500 ppm CRW85579 (Baker Hughes) corrosion inhibitor was investigated
on the X42 linepipe presented in Chapter 4, and the OCTG materials presented in Chapter 6
(see Table 8.1). Chemical composition and metallographic analysis was given in Section 3.4.

becoming an electrode on the ZRA (Figure 3.3). A five-segment ZRA electrode was also
made by taking five random cross sections from the seamless linepipe (X42-S), defined as
E1 to E5. All electrodes had approximately the same surface area of 0.10 cm2.
151

the experiment, and 500 ppm of corrosion inhibitor CRW85579 was injected for select
experiments (experiment ID CRW-A and CRW-B). The stirrer was operating at 150 RPM,
which gave an approx. flow velocity of 0.5 m/s at the electrode surfaces, in the direction
indicative of Figure 4.1.
The stirring autoclave was then configured to 10 bar CO2, 60 ºC, and ran for
approximately 168 hours. The pH and Fe2+ concentrations were measured throughout each
experiment; the results are also shown in Table 8.2.
Table 8.1: Investigated materials for inhibitor experiments.

Experimental ID Investigated Materials
CRW-A X42-A, X42-B, X42-C, X42-S
CRW-B J55-A, L80-A
10-60-A X42-A, X42-B, X42-C, X42-S
10-60-C J55-A, L80-A
Table 8.2: Experimental test matrix. All experiments performed at 10 bar CO2, 60 ºC. Electrolyte 3% NaCl,
purged with CO2 for 2 hours, 150 RPM (approx. 0.5 m/s). Corrosion inhibitor injected at start of
experiment after CO2 purging.
Experiment Electrolyte pHinitial pH168hrs Bulk Fe2+168hrs
ID (ppm)
CRW-A 3% NaCl, 500 ppm Corrosion Inhibitor 4.121 5.011 34
CRW-B CRW85579 4.101 4.991 16
10-60-A 3.36 5.751 275
3% NaCl
10-60-C 3.30 5.531 199
1… measurements made at 1 bar CO
2
152
The multi-channel zero resistance ammetry experiments showed the addition of

500 ppm of corrosion inhibitor CRW85579 significantly reduced preferential weld corrosion.
The level of galvanic interactions between the different microstructural zones present in the
ERW material typically reduced by one to two orders of magnitude, as shown by Figure 8.1
for the X42 linepipe, and Figure 8.2 for the OCTGs.
8.3.1 Effect of inhibitor on ERW X42 linepipe PWC
8.3.1.1 Multi-channel zero resistance ammetry
As shown in Chapter 4, 10 bar CO2, 60 ºC was a very severe test condition, and X42-A
and X42-B had a high susceptibility to preferential weld corrosion. As shown by Figure 8.1,
the addition of 500 ppm CRW85579 corrosion inhibitor significantly reduced the galvanic
interactions between the different ERW microstructural zones. The ZRA curves for each
linepipe are shown by Figure 8.3 for the inhibited condition, and Figure 8.4 for the
uninhibited, showing in more detail the effectiveness of the corrosion inhibitor.
For the uninhibited condition (Figure 8.4), X42-B HAZ 3 was the dominant anode for
the entire experiment, with an anodic AGCD168hrs value of 1013 µA/cm2 (11.8 mm/y). When
repeating the experiment with 500 ppm corrosion inhibitor (Figure 8.3), there was no clear
dominant anode, and the highest anodic AGCD168hrs value was a mere 6.0 µA/cm2
(0.07 mm/y), a reduction of three orders of magnitude.
The other two ERW linepipes, X42-A and X42-C, along with the seamless linepipe
X42-S, also had significant reductions in their galvanic interactions (Figure 8.1).
8.3.1.2 Scanning electron microscopy (SEM)
It was shown in Chapter 4 that galvanic interactions resulted from different

microstructural zones around the ERW weld region forming morphologically different
corrosion product layers (see Section 4.3.2). As the differences in these layers becomes
more dramatic, the galvanic couples become stronger.
X42-B corrosion product layers for the uninhibited 10 bar CO2, 60 ºC condition are
shown by Figure 8.5, where there are clear morphological differences between the various
ERW microstructural zones (see Section 4.3.2.1 for more detail). SEM cross sections for the
10 bar CO2, 60 ºC condition with 500 ppm corrosion inhibitor are given in Figure 8.6, and
show the absence of any significant corrosion product layers. This is further evidence that
153
CO2 preferential weld corrosion of ERW linepipe is caused by the formation of different
corrosion product layers at different microstructural zones. The suppression of corrosion
product layer formation by the addition of corrosion inhibitor, even at the severe test
condition of 10 bar CO2, 60 ºC, completely prevented the formation of any significant
galvanic couples.
8.3.2 Effect of corrosion inhibitor on ERW OCTGs
Similar to the X42 linepipe, the addition of 500 ppm corrosion inhibitor significantly
reduced galvanic interactions between the different microstructural zones present in the
ERW OCTG material. Average galvanic current densities for each microstructural zone are
summarised by Figure 8.2. ZRA curves for the inhibited condition are shown by Figure 8.7,
and for the uninhibited by Figure 8.8.
J55-A received a local normalization heat treatment after welding, which in

combination with its high carbon and manganese content, cause significant microstructural
variations around its ERW weld (Figure 3.24). For the uninhibited condition, J55-A HAZ 3
was severely attacked, with an AGCD168hrs value of 738 µA/cm2 (8.6 mm/y). With the addition
of corrosion inhibitor, the highest anodic AGCD168hrs value was 10.4 µA/cm2 (0.12 mm/y).
L80-A had a quenched and tempered heat treatment, which resulted in a very uniform
microstructure around its ERW weld (Figure 3.22). As a result, its galvanic interactions for
the uninhibited condition were already comparatively low, with a maximum anodic AGCD-
168hrs value of 50.9 µA/cm2 (0.59 mm/y). The addition of corrosion inhibitor was able to
reduce the maximum anodic AGCD168hrs value to 14.9 µA/cm2 (0.17 mm/y).
It therefore appears that once corrosion inhibitor is added, the performance differences
between normalized (J55-A) and quenched and tempered (L80-A) become less significant.
154
10 bar CO2, 60 ºC
1200 13.9
1000 X42-A X42-B X42-C X42-S 11.6


800 WM WM WM E1
9.3
600 HAZ 2 HAZ 2 HAZ 2 E3 6.7
HAZ 3 HAZ 3 BM 1 E4
400 BM BM BM 2 E5
4.6
200 2.3
0 0
-200
-400
-600
Inhibitor Inhibitor Inhibitor Inhibitor Inhibitor Inhibitor Inhibitor Inhibitor
-800
Figure 8.1: Average galvanic current densities over 168 hours (AGCD168hrs) for X42 ERW (X42-A, X42-B, X42-C) and seamless (X42-S) linepipe, showing effect of 500 ppm CRW85579
corrosion inhibitor. Conditions: 10 bar CO2, 60 ºC, 3% NaCl, 150 RPM (approx. 0.5 m/s), surface area ratios 1:1. Positive values are anodic.
155
10 bar CO2, 60 ºC
800 9.3
J55-A L80-A
Average Galvanic Current Density (µA/cm2) 600 7.0
WM WM

HAZ 1 HAZ 1
HAZ 2 HAZ 2
400 4.6
HAZ 3 BM 1
BM BM 2
200 2.3
0 0
-200
-400
Without 500 ppm Without 500 ppm

Inhibitor Inhibitor Inhibitor Inhibitor
-600
Figure 8.2: Average galvanic current densities over 168 hours (AGCD168hrs) for ERW OCTGs, showing effect of 500 ppm CRW85579 corrosion inhibitor. Conditions: 10 bar CO2, 60 ºC,
3% NaCl, 150 RPM (approx. 0.5 m/s), surface area ratios 1:1. Positive values are anodic.
156
X42-A X42-B X42-C X42-S
100 1.2

500 ppm Inhibitor 500 ppm Inhibitor 500 ppm Inhibitor 500 ppm Inhibitor
75 0.9
50 0.6
25 0.3
0 0
-25
WM E1
WM WM
-50 HAZ 1 E2
HAZ 1 HAZ 1
HAZ 2 E3
HAZ 2 HAZ 2
HAZ 3 E4
-75 HAZ 3 BM 1
BM E5
BM BM 2
-100
0 48 96 144 0 48 96 144 0 48 96 144 0 48 96 144
Figure 8.3: Current density curves for 10 bar CO2, 60 ºC, with 500 ppm CRW85579 corrosion inhibitor, showing galvanic interactions between different microstructural zones present
in ERW linepipe (X42-A, X42-B, X42-C) compared to a seamless linepipe (X42-S) linepipe. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive values are
anodic. Experiment ID CRW-A.
157
4000
X42-A X42-B X42-C X42-S
46

WM Without WM Without WM Without E1 Without
HAZ 1 Inhibitor HAZ 1 Inhibitor HAZ 1 Inhibitor E2 Inhibitor
3000 HAZ 2 HAZ 2 HAZ 2 E3 35
HAZ 3 HAZ 3 BM 1 E4
BM BM BM 2 E5
2000 23
1000 12
0 0
-1000
0 48 96 144 0 48 96 144 0 48 96 144 0 48 96 144

Figure 8.4: Current density curves for 10 bar CO2, 60 ºC, showing galvanic interactions between different microstructural zones present in ERW linepipe (X42-A, X42-B, X42-C)
compared to a seamless linepipe (X42-S) linepipe. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive values are anodic. Experiment ID 10-60-A.
158
Sample ID: X42-B
Test Condition: 10 bar CO2, 60 ºC, 3% NaCl, 150 RPM, uninhibited
WM HAZ 1
HAZ 2 HAZ 3
BM
Figure 8.5: SEM BSD cross sections of X42-B for uninhibited 10 bar CO2, 60 ºC, showing different
corrosion product layers formed on each microstructural zone. HAZ 3 was the dominant anode.
159
Sample ID: X42-B
Test Condition: 10 bar CO2, 60 ºC, 3% NaCl, 150 RPM, 500 ppm CRW85579
WM HAZ 1
HAZ 2 HAZ 3
BM
Figure 8.6: SEM BSD cross sections of X42-B, for 10 bar CO2, 60 ºC, with the addition of 500 ppm
CRW85579 corrosion inhibitor, showing the absence of any significant corrosion product layers.
160
J55-A L80-A
100 1.2

500 ppm Inhibitor 500 ppm Inhibitor
75 0.9
50 0.6
25 0.3
0 0
-25
WM WM
-50 HAZ 1 HAZ 1
HAZ 2 HAZ 2
HAZ 3 HAZ 3
-75
BM BM
-100
0 48 96 144 0 48 96 144
Figure 8.7: Current density curves for 10 bar CO2, 60 ºC, with 500 ppm CRW85579 corrosion inhibitor,
showing galvanic interactions between different microstructural zones present in ERW OCTGs.
Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface area ratio 1:1. Positive values are anodic.
Experiment ID CRW-B.
2000
J55-A L80-A
23

Without Inhibitor Without Inhibitor
1500 17
1000 12
500 5.8
0 0
-500
WM WM
-1000 HAZ 1 HAZ 1
HAZ 2 HAZ 2
HAZ 3 HAZ 3
-1500
BM BM
-2000
0 48 96 144 0 48 96 144
Figure 8.8: Current density curves for 10 bar CO2, 60 ºC, showing galvanic interactions between different
microstructural zones present in ERW OCTGs. Electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s). Surface
area ratio 1:1. Positive values are anodic. Experiment ID 10-60-C.
161
8.4 Conclusions
The multi-channel zero resistance ammetry method was used to investigate the effect
of a commercially available corrosion inhibitor on the preferential weld corrosion
susceptibility of various ERW X42 linepipes, and grade J55 and L80 OCTGs. Experiments
were performed at 10 bar CO2, 60 ºC, which was severe and caused localized attack rates
as high as 11.8 mm/y for the uninhibited condition. The addition of corrosion inhibitor was
able to reduce galvanic coupling currents by up to three orders of magnitude in some cases.
Furthermore, without inhibitor, quenched and tempered ERW OCTGs and seamless linepipe
were superior compared to locally normalized seam heat treated ERW linepipe. However, in
the presence of inhibitor, there was a negligible performance difference, and galvanic
coupling currents were low for all materials.
Therefore for existing installations, where material changes are impractical, corrosion
inhibitors are an effective way to reduce galvanic coupling currents between different
microstructural zones present in ERW linepipe and OCTGs, significantly mitigating the threat
of preferential weld corrosion.
162
Chapter 9 Conclusions and recommendations for
avoiding CO2 preferential weld corrosion in
ERW linepipes and OCTGs
9.1 A new methodology for assessing CO2 preferential weld corrosion

susceptibility
This thesis introduced a new methodology for assessing the susceptibility of

longitudinally welded carbon steel linepipe (and OCTGs) to CO2 preferential weld corrosion
(PWC). It used a method termed multi-channel zero resistance ammetry to investigate the
galvanic interactions between the various microstructural zones present in several electric
resistance welded (ERW) linepipes.
The method used a careful metallographic examination to identify the different

microstructural zones present in each ERW linepipe. Typically, an ERW weld consisted of a
weld seam microstructure, a large heat affected zone with three different microstructures
present, before transitioning to the base metal microstructure. This was attributed to the local
seam heat treatment normalization process, where a cooling gradient exists between the
weld seam and the much cooler base material. The different microstructural zones present in
each ERW linepipe were then physically segmented and used to make a five-segment multi-
channel ZRA electrode, which virtually recreated the original linepipe with the ERW weld.
The multi-channel ZRA electrodes were then placed inside a stirring autoclave for
approximately one week. This allowed the ERW linepipe to corrode naturally, however,
galvanic interactions between the different microstructural zones present in the ERW
linepipe could be measured in real time. Initially, galvanic interactions between the different
microstructural zones were negligible, implying the intrinsic corrosion potentials of each
microstructural zone were similar. However, as the linepipe corroded, strong galvanic
couples developed. SEM analysis at the end of the experiment showed the establishment of
these strong galvanic couples was directly related to the growth of different corrosion
product layers on different microstructural zones.
This new approach, which uses multi-channel ZRA based off of a microstructural
analysis, can directly assess the susceptibility of a particular longitudinally welded linepipe to
CO2 preferential weld corrosion. This method may be of significant use to materials and
corrosion engineers during the material selection phase of a particular project, where the
performance of several ERW linepipes can be assessed and compared before procurement.
163
9.2 Mechanism of CO2 preferential weld corrosion in ERW linepipe
Multi-channel zero resistance ammetry showed that after exposure to saline CO2
environments for several days inside a stirring autoclave, certain microstructural zones
slowly formed strong galvanic couples. Scanning electron microscopy revealed that each
different microstructural zone acted as a footprint for corrosion product layer morphology. In
other words, the different microstructural zones around the weld seam each formed
morphologically different corrosion product layers. When one microstructural zone started to
form significantly different corrosion product layers than the others, strong galvanic couples
developed, and highly localized attack resulted. Furthermore, for ERW materials that
showed this susceptibility, localized attack was always at the same type of microstructural
zone; pCO2 and temperature only affected the severity of attack, not the location.
The formation of different corrosion product layers was related to cementite

morphology. Ferrite is anodic relative to cementite, therefore as the steel corrodes the ferrite
dissolves and leaves behind an un-corroded cementite layer. If the steel has pearlite
banding, which is essentially a strong, interconnected network of cementite, then the
corrosion product layer will be a porous sponge-like network of cementite. In this case, the
cementite film can be considerably thick and well adhered to the surface. In contrast, if the
cementite phase is present as poorly interconnected carbides, then the corrosion product
layer can be quite weak and may break away from flow turbulences. Ultimately this affects
local siderite precipitation conditions, leading to dense siderite layers at some locations
around the weld but not others.
When ERW linepipes corrode, the variations in cementite morphology around the weld
seam create morphologically different cementite layers. These local variations then affect the
local siderite saturation factor, which further influences corrosion product layer morphology.
Once different corrosion product layers start to form at each microstructural zone, the
intrinsic corrosion potential of each zone changes. This then establishes galvanic couples,
and localized attack at the anodic microstructural zones results. This behaviour is captured
in real time by multi-channel zero resistance ammetry, and the attack rate at the anodic
microstructural zone can be measured and compared.
164
9.3 Correlation with base metal (strip material) microstructure and
chemical composition
In terms of linepipe base metal microstructure (i.e. the strip material microstructure
used for manufacturing the ERW linepipe), the investigated materials can be broadly
grouped into the following categories:
► Ferritic pearlitic
► X42-A, X42-B, X42-C, X42-S, J55-A
► Ferritic bainitic
► X52-AW, X52-SH, X52-450, X52-650
► Quenched and tempered
► L80-A
Metallographic analysis of the different microstructural zones present in each linepipe

and OCTG were given in Section 3.4. For the multi-channel ZRA method introduced in this
thesis, if the weld seam or one of the HAZ microstructures has an anodic galvanic current
density, then that microstructural zone is being locally attacked. Therefore the larger the
anodic average galvanic current density (AGCD, described in Section 3.3.3.1) for one of
these microstructural zones, the more susceptible the linepipe is to preferential weld
corrosion. Susceptibility to CO2 preferential weld corrosion for each material is summarised
in Figure 9.1, where the largest weld/HAZ anodic AGCD168hrs values have been plotted for
each linepipe/OCTG for various test conditions. Note the logarithmic scale of the axis.
There was a clear correlation with the base metal microstructure used for
manufacturing the ERW linepipe/OCTG, and its susceptibility to PWC.
9.3.1 Ferritic pearlitic ERW linepipes
For ERW linepipes and OCTGs made from ferritic pearlitic normalized strip material,
some had a significant susceptibility to CO2 preferential weld corrosion, especially at 60 and
90 ºC.
As Figure 9.1 shows, for the ferritic pearlitic ERW materials there was a clear
correlation between carbon content and galvanic attack rate. J55-A and X42-B had the
highest carbon concentration, and consistently developed the highest galvanic attack rates.
X42-C had the lowest carbon content of the ERW ferritic pearlitic linepipe, and had the
smallest galvanic attack rates. X42-C also had the desirable characteristic that its BM
microstructure acted as the dominant anode for the severe test condition of 10 bar CO2,
165
60 ⁰C, therefore the WM and HAZ microstructures were cathodically protected and very low
galvanic current densities resulted.
The carbon concentration correlation is explainable as galvanic couples result from the
growth of morphologically different corrosion product layers, which in turn results from
localized microstructural variations around the ERW weld. Microstructural transformations
are easier (i.e. require less dramatic cooling gradients) as carbon content increases.
The maximum galvanic couples formed between the nominally identical X42-S
seamless electrodes are also included in Figure 9.1, and serve as a reference point for what
can be expected when the microstructure is uniform and not affected by welding. Figure 9.1
also shows the effect of adding 500 ppm inhibitor, which was able to reduce galvanic
interactions for all linepipes and OCTGs by up to two orders of magnitude.
9.3.2 Ferritic bainitic ERW linepipes
Investigations were also made on four ERW X52 linepipes made from the same ferritic
bainitic strip material (0.058% C), however, each received a different heat treatment:
► X52-AW was left in the as-welded condition, and did not receive any heat
treatment.
► X52-SH had the weld seam locally normalized at 930 ºC.
stress relief at 450 ºC for approx. 5 seconds.
stress relief at 650 ºC for approx. 5 seconds.
As Figure 5.2 and Figure 5.3 show, the ferritic pearlitic base material was constantly
the dominant anode, regardless of heat treatment or test condition. Therefore while galvanic
interactions were significant between the various microstructural zones, as the base metal
was the dominant anode, the WM and HAZs where always cathodically protected. This is a
favourable situation, as the base metal has a significantly larger surface area than the weld
and HAZs, and can afford to act as a sacrificial anode. Figure 9.1 (X52-450) highlights how
this microstructural configuration significantly improves CO2 PWC resistance compared to
the other ERW materials. This finding also fits with the literature, where bainitic steels have
shown good resistance to HAZ corrosion37, 38 in CO2 environments.
9.3.3 Quenched and tempered ERW OCTGs
Multi-channel ZRA measurements showed quenched and tempered ERW materials

had excellent resistance to CO2 preferential weld corrosion. This was attributed to the very
166
fast cooling rates preventing carbon diffusion, and hindering the formation of different
microstructural zones. Essentially, the quenched and tempered heat treatment resulted in a
very uniform microstructure across the entire ERW weld region. The strongest anodic
galvanic attack rates for the ERW quenched and tempered OCTG (L80-A) are also shown in
Figure 9.1, where it performed at a level comparable to a ferritic pearlitic seamless linepipe
(X42-S).
9.4 Avoiding CO2 preferential weld corrosion in ERW linepipe
CO2 preferential weld corrosion occurs when the ERW welding process and the
subsequent seam heat treatment process causes localized microstructural variations. When
selecting carbon steel ERW linepipe, specific attention should be paid to cementite
morphology and grain size around the ERW weld and HAZ region. The following
microstructural characteristics should be avoided as they lead to the formation of different
corrosion product layers, which then induces galvanic attack:
► Regions where pearlite banding is significantly modified, such as becoming

finer, coarser, or almost disappearing (e.g. Figure 3.5 X42-B HAZ 2, and Figure
3.24 J55-A HAZ 2 and HAZ 3).
► Regions where low temperature transformation phases have formed (e.g.
Figure 3.7 X42-B HAZ 2 and HAZ 3).
► Welding a ferritic pearlitic linepipe to a quenched and tempered linepipe will
result in attack on the quenched and tempered side of the weld (Section
4.3.1.2.5).
Quite simply, the ERW weld region must have a uniform microstructure, similar to
X42-C (Figure 3.9) and L80-A (Figure 3.22). This results in morphologically similar corrosion
product layers and small galvanic interactions between the weld seam, heat affected zones,
and base metal. In this way the performance of ERW linepipe can approach the performance
of seamless linepipe (Figure 9.1). An alternative is to use low carbon (0.058% C) ERW
linepipe with a bainitic ferritic base metal microstructure, as the base metal has a tendency
to be the dominant anode, which protects the weld seam and heat affected zones.
9.5 Conclusion
A new electrochemical method, using multi-channel zero resistance ammetry, was

shown to be a powerful tool for determining the susceptibility of a longitudinally welded
linepipe or OCTG to CO2 preferential weld corrosion. This thesis focused on ERW linepipes
167
and OCTGs, however, the technology can be applied to any weld type. The method
conclusively showed why ERW linepipes and OCTGs of the same material grade can have
significantly different susceptibilities to CO2 preferential weld corrosion. SEM examination of
the corrosion product layers conclusively showed that differences in siderite precipitation
kinetics, by virtue of the local microstructure around the weld, induces localized galvanic
attack.
The results showed ferritic pearlitic ERW linepipes with a carbon concentration below
0.710 wt% C had comparable performance to a seamless linepipe. As carbon content was
increased, CO2 preferential weld corrosion susceptibility also increased. For low carbon
(<0.058% C) ferritic bainitic ERW linepipes, the base metal was found to be the dominant
anode, which offered the weld seam and HAZs a form of cathodic protection, agreeing with
literature observations that bainitic steels rarely experience corrosion in the HAZ. Quenched
and tempered ERW OCTGs were found to be superior to ferritic pearlitic ones.
Not only can this method give insight into troublesome microstructural combinations
that should be avoided in the weld region, it can also be a useful tool for examining the
complex interdependencies of inhibitor type and water chemistry on CO2 PWC susceptibility.
For example, the presence of acetic acid was found to increase PWC susceptibility
significantly for some linepipes, but not so much for others.
The above microstructural relationships (Section 9.4) can be used directly by oil and
gas companies to avoid CO2 preferential weld corrosion. The multi-channel ZRA approach
with this microstructure based methodology can also be used to directly assess and
compare various ERW linepipes (Figure 9.1), further assisting with material selection
reliability and increasing asset integrity.
168
Maximum Anodic WM/HAZ Values (mm/y)
1 bar
60 °C
100
10
10 bar 0.1 1 bar

90 °C 90 °C
0.01
ERW (ferritic pearlitic)
X42-A (0.115C, 0.950Mn)
0.001
X42-B (0.130C, 0.960Mn)
X42-C (0.071C, 0.750Mn)
J55-A (0.159C, 1.104Mn)
ERW (ferritic bainitic)

X52-450 (0.058C, 0.820Mn)
ERW (quench and tempered)

L80-A (0.280C, 1.492Mn)
10 bar 10 bar
60 °C Seamless (ferritic pearlitic)
60 °C X42-S (0.090C, 1.220Mn)
500 ppm Inhibitor
Figure 9.1: Susceptibility of various linepipes/OCTGs to CO2 preferential weld corrosion. Plot shows the effect of pCO2 and temperature on the galvanic corrosion rates
measured for weld seam and heat affected zone microstructures (AGCD168hrs values). Base electrolyte 3% NaCl, 150 RPM (approx. 0.5 m/s).
169
References
1. S. Papavinasam, Corrosion Control in the Oil and Gas Industry, (Elsevier, 2013).
2. R. Javaherdashti, C. Nwaoha, H. Tan, Corrosion and Materials in the Oil and Gas
Industries, (CRC Press, 2016).
3. M. Kermani, D. Harrop, SPE Production & Facilities 11, 03 (1996): p. 186-190.
4. C.-M. Lee, P. Woollin, "Preferential Weld Corrosion: Effects of Weldment
Microstructure and Composition," Paper No. 05277, CORROSION 2005 (Houston,
Tx: NACE International 2005).
5. P.J. Carvalho, L.M. Pereira, N.P. Gonçalves, A.J. Queimada, J.A. Coutinho, Fluid
Phase Equilibria 388, (2015): p. 100-106.
6. J.J. Carroll, A.E. Mather, Journal of Solution Chemistry 21, 7 (1992): p. 607-621.
7. E. Dayalan, F. De Moraes, J.R. Shadley, E.F. Rybicki, S.A. Shirazi, "CO2 Corrosion
Prediction in Pipe Flow under FeCO3 Scale-Forming Conditions," Paper No. 51,
CORROSION 98 (Houston, Tx: NACE International 1998).
8. F. Millero, F. Huang, T. Graham, D. Pierrot, Geochimica et Cosmochimica Acta 71, 1
(2007): p. 46-55.
9. A. Dugstad, "Fundamental Aspects of CO2 Metal Loss Corrosion-Part 1:
Mechanism," Paper No. 06111, CORROSION 2006 (Houston, Tx: NACE
International 2006).
10. Y.A. Çengel, M.A. Boles, Thermodynamics: An Engineering Approach, (McGraw-Hill,
2008).
11. S. Nesic, M. Nordsveen, A. Stangel, "A Mechanistic Model for CO2 Corrosion with
Protective Iron Carbonate Films," Paper No. 01040, CORROSION 2001 (Houston,
Tx: NACE International 2001).
12. A. Dugstad, "Mechanism of Protective Film Formation During CO2 Corrosion of
Carbon Steel," Paper 31, CORROSION 98 (Houston, Tx: NACE International 1998).
13. Y. Garsany, D. Pletcher, D. Sidorin, W. Hedges, Corrosion 60, 12 (2004): p. 1155-
1167.
14. S. Nesic, J. Postlethwaite, S. Olsen, Corrosion 52, 4 (1996): p. 280-294.
15. L. Gray, B. Anderson, M. Danysh, P. Tremaine, "Mechanisms of Carbon Steel
Corrosion in Brines Containing Dissolved Carbon Dioxide," Paper 464, CORROSION
89 (Houston, Tx: NACE International 1989).
16. C. De Waard, D. Milliams, Corrosion 31, 5 (1975): p. 177-181.
17. W. Sun, S. Nešić, R.C. Woollam, Corrosion Science 51, 6 (2009): p. 1273-1276.
18. P. Bénézeth, J. Dandurand, J. Harrichoury, Chemical Geology 265, 1 (2009): p. 3-
12.
19. C.A. Silva, X. Liu, F. Millero, Journal of Solution Chemistry 31, 2 (2002): p. 97-108.
20. Dugstad, Arne. "The importance of FeCO3 supersaturation on the CO2 corrosion of
carbon steels," Paper No. 14, CORROSION 92 (Houston, Tx: NACE International
1992).
21. R. Barker, X. Hu, A. Neville, Tribology International 68, (2013): p. 17-25.
22. S. Bordbar, M. Alizadeh, S.H. Hashemi, Materials & Design 45, (2013): p. 597-604.
23. Y. Lu, H. Jing, Y. Han, L. Xu, Journal of Materials Engineering and Performance 25,
3 (2016): p. 960-965.
170
24. S. Turgoose, J.W. Palmer, "Preferential Weld Corrosion of 1% Ni Welds: Effects of
Solution Conductivity and Corrosion Inhibitors," Paper No. 05275, CORROSION
25. Y. Lu, H. Jing, Y. Han, Z. Feng, L. Xu, Applied Surface Science 389, (2016): p.
609-622.
26. M.W. Joosten, J. Kolts, P.G. Humble, J. Kiefer, J. Marlow, "Aspects of Selective
Weld and Haz Attack in CO2 Containing Production Environments," Paper No. 79,
27. R. Barker, X. Hu, A. Neville, S. Cushnaghan, Corrosion 69, 11 (2013): p. 1132-
1143.
28. S.P. Mahajanam, M.W. Joosten, "Selection of Filler Materials to Minimize Preferential
Weld Corrosion in Pipeline Steels," SPE International Conference on Oilfield
Corrosion (2010).
29. S.P. Mahajanam, M.W. Joosten, SPE Projects, Facilities & Construction 6, 01
(2011): p. 5-12.
30. D. McNaughtan, I. Winning, "Comparison of Segmented Weld Corrosion Tests with
Short and Long Pre-Corrosion and the Influence of Synergist in Corrosion Inhibitors,"
SPE International Symposium on Oilfield Corrosion (2004).
31. M. Martinez, K. Alawadhi, M. Robinson, G. Nelson, A. MacDonald, "Control of
Preferential Weld Corrosion of X65 Pipeline Steel in Flowing Brines Containing
Carbon Dioxide," Paper No. 11268, CORROSION 2011 (Houston, Tx: NACE
International 2011).
32. D.R. McIntyre, R.P. Case, "Environmental Effects on Fitness-for Service Parameters
for 1% Nickel Steel Pipe Welds with Preferential Weld Corrosion Damage," Paper
No. 5820, CORROSION 2015 (Houston, Tx: NACE International 2015).
33. R. Case, M. Achour, J. Daniels, "Evaluation of Preferential Weld Corrosion
Susceptibility and Its Mitigation in Slightly Sour Conditions," Paper No. 5640,
34. S. Olsen, B. Sundfaer, J. Enerhaug, "Weld Corrosion in C-Steel Pipelines in CO2
Environments - Comparison between Field and Laboratory Data," Paper No. 43,
35. D. Queen, C.-M. Lee, J. Palmer, E. Gulbrandsen, "Guidelines for the Prevention,
Control and Monitoring of Preferential Weld Corrosion of Ferritic Steels in Wet
Hydrocarbon Production Systems Containing CO2," SPE International Symposium on
Oilfield Corrosion (2004).
36. K. Denpo, H. Ogawa, Corrosion Science 35, 1-4 (1993): p. 285-288.
37. S. Endo, M. Nagae, S. Fujita, O. Hirano, "Preferential Corrosion of Weldment of
Carbon Steel in CO2 Containing Environment," Proceedings of the International
Coference on Offshore mechanics and arctic engineering (1992).
38. S. Endo, M. Nagae, T. Wada, "Preferential Corrosion Properties in CO2 Containing
Environment and Mechanical Properties of Welded Joints of Line Pipes," The Third
International Offshore and Polar Engineering Conference (1993).
39. K. Alawadhi, M. Robinson, Corrosion Engineering, Science and Technology 46, 4
(2011): p. 318-329.
40. N. Bretherton, S. Robb, K. Richterova, D. Donaldson, R. Smith, "Impact of Acetic
Acid on Weld Corrosion and Its Mitigation," Paper No. 09562, CORROSION 2009
(Houston, Tx: NACE International 2009).
41. D.A. Jones, Principles and Prevention of Corrosion, (Macmillan, 1992).
42. C. Palacios, J. Shadley, Corrosion 47, 2 (1991): p. 122-127.
43. E.S. Akeer, “Effect of Carbon Steel Composition and Microstructure on CO2
Corrosion,”, Master’s thesis, Ohio University, 2014.
44. M. Ueda, H. Takabe, "Effect of Environmental Factor and Microstructure on
Morphology of Corrosion Products in CO2 Environments," Paper 13, CORROSION
45. M. Kermani, A. Morshed, Corrosion 59, 8 (2003): p. 659-683.
171
46. M.A. Islam, Z.N. Farhat, Journal of Materials Engineering and Performance 24, 8
(2015): p. 3142-3158.
47. F. Farelas, B. Brown, S. Nesic, "Iron Carbide and Its Influence on the Formation of
Protective Iron Carbonate in CO2 Corrosion of Mild Steel," Paper No. 2291,
48. J. Han, "Galvanic Mechanism of Localized Corrosion for Mild Steel in Carbon Dioxide
Environments," Ph.D diss., Ohio University, 2009.
49. R. Singh, Pipeline Integrity: Management and Risk Evaluation, (Gulf Professional
Publishing, 2017).
50. Welding Handbook - Volume 3 Welding Processes, (American Welding Society,
2007).
51. E. Gulbrandsen, A. Dugstad, "Corrosion Loop Studies of Preferential Weld Corrosion
and Its Inhibition in CO2 Environments," Paper No. 05276, CORROSION 2005
52. I.G. Winning, D. Mcnaughtan, N. Bretherton, "Evaluation of Weld Corrosion Behavior
and the Application of Corrosion Inhibitors and Combined Scale/Corrosion Inhibitors,"
Paper No. 04538, CORROSION 2004 (Houston, Tx: NACE International 2004).
53. A.N. Rothwell, J.L. Dawson, D.A. Eden, J.W. Palmer, "Interpreting Electrochemical
Impedance Spectra from Segmented Electrode Arrangements," Electrochemical
Impedance: Analysis and Interpretation, ASTM STP 1188, J.R. Scully, D.C.
Silverman, M.W. Kendig, Eds., American Socienty for Testing and Materials,
Philadephia, 1993, p. 237-251.
54. A. Ikeda, "Prevention of CO2 Corrosion of Line Pipe and Oil Country Tubular Goods,"
Central Research Laboratories, Sumitomo Metal Industries, Ltd., 1-3, Nishinagasu-
Hondori, Amagasaki, Japan (1985).
55. J. Crolet, G. Beranger, H. Mazille, "Corrosion in Oil and Gas Production," Corrosion
and Anticorrosion, (Paris, France: Hermes Science, 2002).
56. K. Videm, A. Dugstad, "Effect of flow velocity, pH, Fe2+ concentration and steel
quality on the CO2 corrosion of carbon steels", Paper No. 42, CORROSION 87
57. K. Videm, A. Dugstad, "Corrosion of Carbon Steel in an Aqueous Carbon Dioxide
Environment Part 1," Mater. Performance (United States), 28.3 (1989).
58. K. Videm, A. Dugstad, L. Lunde, "Influence of Alloying Elements Upon the CO2
Corrosion Rate of Low-Alloyed Carbon Steels," Paper No. 473, CORROSION 91
59. A. Dugstad, H. Hemmer, M. Seiersten, Corrosion 57, 4 (2001): p. 369-378.
60. G. Schmitt, T. Gudde, E. Strobel-Effertz, "Fracture Mechanical Properties of CO2
Corrosion Product Scales and Their Relation to Localized Corrosion," Paper No. 9,
61. J. Crolet, N. Thevenot, S. Nesic, Corrosion 54, 3 (1998): p. 194-203.
62. M.R. Bonis, J.L. Crolet, "Why So Low Free Acetic Acid Thresholds, in Sweet
Corrosion at Low pCO2?," Paper No. 05272, CORROSION 2005 (Houston, Tx:
NACE International 2005).
63. E. Gulbrandsen, K. Bilkova, "Solution Chemistry Effects on Corrosion of Carbon
Steels in Presence of CO2 and Acetic Acid," Paper No. 06364, CORROSION 2006
64. A. Dugstad, H. Hemmer, H. Kooyman, W. Wilhelmsen, "Kjeller Sweet Corrosion III–
Final Report," report no. IFE/KR/F-93/091, Institute for Energy Technology, 1993.
65. E. Gulbrandsen, "Acetic Acid and Carbon Dioxide Corrosion of Carbon Steel
Covered with Iron Carbonate," Paper No. 07322, CORROSION 2007 (Houston, Tx:
NACE International 2007).
172
Rob Muggleton
M: +43 664 6120935 | robmuggleton@outlook.com
Summary
Rob is a materials & corrosion engineer with OMV Upstream, an international oil & gas company
headquartered in Vienna, Austria. He joined OMV Upstream while working on his PhD, investigating the
preferential weld corrosion of ERW linepipe in production environments. Originally from Australia, he also
holds a Masters' degree in mechanical engineering. He now works with OMV Upstream's TECH Center &
Lab, and has performed many failure analyses on metallic materials. Rob is also heavily involved with
inhibitor selection, materials selection, the development of internal standards, and risk based inspection.
Highlights
 Failure analysis  Corrosion science, research

 Fractography, SEM/XRD examination  Academic writing
 Metallography  Developing technical standards
 Electrochemistry, inhibitor selection  Fitness for service
Experience
Materials & Corrosion Engineer Sept 2017 – Current

Materials & Corrosion Department Vienna, Austria
OMV Upstream
 Detailed failure analysis of metallic materials, corrosion product layers, recommendations, report
writing, technical presentations to clients, managed corrosion R&D projects
 Fitness for service assessments of corroded pipelines, developed technical specifications, corrosion
databases, risk based inspection, incident investigations
 Electrochemistry (EIS, LPR, ZRA, PPR), corrosion inhibitor selection
 Material selection for sour service (NACE MR0175/ISO 15156)
Doctoral Scholar Jan 2015 – Sept 2017

Materials & Corrosion Department Vienna, Austria
OMV Upstream
 Developed new technology that evaluates the susceptibility of longitudinally welded linepipe to
preferential weld corrosion in CO2 environments, presented at NACE conference
 Various failure analyses utilising SEM/EDX/XRD, optical microscopy, metallography, fractography,
and mechanical testing (turbine blades, welds, sucker rods, heat exchangers, drill pipes, water
treatment plants…)
 Developed internal technical standard for stainless steel linepipe, specifically with regard to pitting
resistance, pitting potentials etc…
Education
Master of Engineering (Mechanical) 2014

The University of Queensland Brisbane, Australia
Bachelor of Engineering (Mechanical) 2012

The University of Queensland Brisbane, Australia
Publications
R. Muggleton, P. Linhardt, G. Zehethofer, "Role of Microstructure in the Susceptibility of X42 ERW Linepipe
to CO2 Preferential Weld Corrosion", CORROSION 2018, Paper No. 10522, (Houston, TX: NACE
International, 2018).
R. Muggleton, M. Haghshenasfard, K. Hooman, "Numerical simulation of mixture homogenization through

jet impingement on cylindrical obstacles", Fluid Dynamics Research (2018).
Referees
Referees are available upon request.

CO2 Preferential Weld Corrosion of Longitudinally Welded Linepipe - Effect of Microstructure, Corrosion Product Layers, and The Environment

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

CO2 Preferential Weld Corrosion of Longitudinally Welded Linepipe - Effect of Microstructure, Corrosion Product Layers, and The Environment

Uploaded by

Copyright:

Available Formats

Dissertation

CO2 Preferential Weld Corrosion of

Robert Muggleton, MEngSc, BE

under the supervision of

Univ. Prof. Dipl.-Ing. Dr. Ernst Kozeschnik

Vienna, August, 2018

R. Muggleton, P. Linhardt, G. Zehethofer, “Role of Microstructure in the Susceptibility of X42

The oil and gas industry therefore requires:

2. An experimental test method that can quantitatively identify a particular linepipe’s

Wissenschaftliche Veröffentlichungen zu CO2-Korrosion von Kohlenstoffstahl-

Längsnahtgeschweißtes ERW-(elektrisch widerstandsgeschweißtes) Rohrmaterial

Die Öl- und Gasindustrie benötigt daher:

1. Eine Erklärung für stark unterschiedliche Empfindlichkeit von relativ ähnlichem

Chapter 2 Literature review 3

Chapter 3 Experimental methodology for investigating CO2

Chapter 4 Effect of ERW X42 linepipe microstructure on CO2

Chapter 5 Effect of normalization heat treatments and flow velocity on

Chapter 6 Effect of quenched and tempered heat treatment on CO2

Chapter 7 Effect of acetic acid on CO2 preferential weld corrosion 130

Chapter 8 Corrosion inhibitors and CO2 preferential weld corrosion 151

Chapter 9 Conclusions and recommendations for avoiding CO2

Curriculum Vitae 173

Figure 2.3: Effect of temperature, pCO2, and pH on siderite precipitation in 3% NaCl

Figure 2.4: Effect of solution conductivity (NaCl concentration) on preferential weld

Figure 3.4: Experimental setup, showing stirring autoclave, multi-channel ZRA

Figure 3.5: Optical micrographs of X42-A microstructural zones. Etched 3% Nital,

Figure 3.10: SEM SE micrographs of X42-C microstructural zones. Etched 3% Nital,

Figure 3.14: Optical micrographs of X52-AW microstructural zones. Etched 3% Nital,

Figure 3.15: SEM SE micrographs of X52-AW microstructural zones. Etched 3% Nital.

Figure 3.16: Optical micrographs of X52-SH microstructural zones. Etched 3% Nital,

Figure 3.17: SEM SE micrographs of X52-SH microstructural zones. Etched 3% Nital.

Figure 3.18: Optical micrographs of X52-450 microstructural zones. Etched 3% Nital,

Figure 3.19: SEM SE micrographs of X52-450 microstructural zones. Etched 3% Nital.

Figure 3.20: Optical micrographs of X52-650 microstructural zones. Etched 3% Nital,

Figure 3.21: SEM SE micrographs of X52-650 microstructural zones. Etched 3% Nital.

Figure 3.22: Optical micrographs of L80-A microstructural zones. Etched 3% Nital,

Figure 3.24: Optical micrographs of J55-A microstructural zones. Etched 3% Nital,

Figure 4.33: Acidification at the steel/cementite interface from the production of

Figure 9.1: Susceptibility of various linepipes/OCTGs to CO2 preferential weld

Table 2.1: Relevant equation values for (2.5)5, 10. .......................................................... 4

Table 3.2: Chemical composition (wt%) of investigated steel linepipes/OCTGs,

Table 7.1: Investigated materials with corresponding experimental ID and HAc

Table 7.2: Experimental test conditions. .................................................................... 132

Table 8.1: Investigated materials for inhibitor experiments. ...................................... 152

AGCD Average Galvanic Current Density

Furthermore, the construction of a pipeline often uses longitudinally welded linepipe

Traditionally, longitudinally welded linepipes are known to be more susceptible to

Modern longitudinally welded linepipes are fabricated by electric resistance welding

2.1 Fundamentals of CO2 corrosion

2.1.1 The carbon dioxide system

CO2(g) ⟷ CO2(l) (2.1)

2.1.2 Siderite (FeCO3) precipitation

2H+ + 2e- → H2 (2.9)

Figure 2.1: Effect of pCO2 and temperature on pH for 3% NaCl solution.

Siderite Solubility, Ksp (mol2/L2)

2.2 Preferential weld corrosion in CO2 environments

Preferential weld corrosion of carbon steel linepipes in CO2 environments is a serious

2.2.1 Effect of nickel and copper

Cu+Ni WM - Cu+Ni BM >0.5% (2.15)

∆ = 3.8 CuBM - CuWM + 1.1 NiBM - NiWM + 0.3 (2.16)

SMAW of an unalloyed C-Mn X65 steel (Steel 1) welded with a 1% Ni electrode

Bretherton, et al.40 investigated preferential weld corrosion experienced in an inhibited

2.2.2 Autogenous and matched filler welds